Heterogeneous

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Heterogeneous Catalysis for Todays Challenges
Synthesis, Characterization and Applications
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RSC Green Chemistry

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Professor Peter Siedl, Federal University of Rio de Janeiro, Brazil
Professor Yuan Kou, Peking University, China
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The Future of Glycerol: New Uses of a Versatile Raw Material

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Heterogeneous Catalysis for

Todays Challenges
Synthesis, Characterization and
Applications
Edited by
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Colorado School of Mines, USA
Email: btrewyn@mines.edu
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Dedication
This book is dedicated to Dr Victor S.-Y.

Lin, who was a professor of chemistry at
Iowa State University from 1999 until he
unexpectedly passed away in 2010. Victor
received a bachelors degree in chemistry
from National Chung Hsing University
in Taichung, Taiwan and earned a PhD
in chemistry from the University of
Pennsylvania in 1996, working under the
direction of Professor Michael Therein.
Following graduate studies, he was awarded a Skaggs postdoctoral fellow at the
Scripps Research Institute in La Jolla, CA
with Professor Reza Ghidari. Victor became a member of the chemistry faculty at
ISU in 1999. He joined the Department of
EnergyAmes Laboratory in 2001 and became program director for its
Chemical and Biological Sciences Program in 2007. Victor was also director
of the Center for Catalysis at the ISU Institute for Physical Research and
Technology.
His colleagues and students remember Victor as a highly creative chemist
with a seemingly endless supply of energy; I often see him in my minds eye
under the poster of Einstein stating how imagination is more important than
knowledge. Victor is best known for his seminal contributions to the syntheses
and applications of mesoporous silica nanoparticles (MSNs), a term he coined
to describe nanometre-sized mesoporous silica materials with a well-defined
and controllable morphology. He not only developed reliable synthetic
Heterogeneous Catalysis for Todays Challenges: Synthesis, Characterization and Applications
Edited by Brian Trewyn
Published by the Royal Society of Chemistry, www.rsc.org
vii
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viii
Dedication
protocols for MSNs but also demonstrated the applications of this interesting
class of nanomaterials in including heterogeneous catalysis, renewable energy,
biosensing, and nanomedicine. He is still frequently cited and the techniques
we developed together are still visible in the current literature today.
Victor was profoundly interested in focusing research time and eort on
exploring heterogeneous catalysis, specifically those supported on MSNs.
He developed novel methods to eectively control the pore environment to
tune catalytic properties. He also developed a bifunctional mesoporous
calcium-silicate mixed-oxide heterogeneous catalyst for the cooperative
and economic conversion of bio-based high-free-fatty-acid feedstocks into
biodiesel, and founded a startup company, Catilin, to bring this technology
to the market. Shortly after his death, Catilin merged with a multinational
catalyst company, Albemarle.
One characteristic that comes to mind when I think about Victor was his
generosity with his time and knowledge. He always answered the door to his
oce with a smile on his face and was sincerely happy to see you. He played the
role of an important father figure for those of us working in his research group.
Along with his astounding intelligence, Victor had a very clever sense of humor
and knew exactly when a mood needed lightening with a joke. He allowed and
often encouraged us to pursue our own ideas in the research laboratory,
oering both financial and intellectual support to them. This exemplary
attitude extended outside our laboratory, frequently inviting other students to
group meetings and into the lab, openly discussing research ideas and goals.
His positive attitude rubbed o on the people around him, often turning a gray
day sunny; even when every reaction failed, Victor would find the silver lining
and you would leave his oce feeling much better than when you arrived. If
you ever had the opportunity to meet Victor and spend even a little bit of time
with him, I am sure you understand what I mean his smile was contagious.
Victor made a number of significant accomplishments in his brief
scientific career, holding an impressive number of professional honors. In
addition to his appointment as the John D. Corbett Professor in Chemistry
that he received shortly prior to his passing, Victor was recognized for his
outstanding research contributions with a National Science Foundation
CAREER Award, the LAS Award for Early Achievements in Research, an
Outstanding Technology Development Award from the Federal Laboratory
Consortium, and the ISU Award for Mid-Career Achievement in Research. He
was also very proud to serve on the Editorial Advisory Board of Advanced
Functional Materials.
I will never forget the time I spent with Victor, first as a graduate student
in his research group (one of his first) and later as a research scientist
assisting him in running his group. Today I have my own research group in
the chemistry department at the Colorado School of Mines and hope to be a
fraction as successful as he was in the short time he spent on earth.
I frequently find myself thinking What would Victor do in this situation?,
thankful to have known such a great man.
Brian Trewyn
08:23:52.
Contents
Chapter 1 Synthesis of Multi-functionalized Mesoporous
Silica Nanoparticles for Cellulosic Biomass
Conversion
Kevin C.-W. Wu
1.1
1.2
Introduction
1.1.1 Background of Cellulosic Biomass
Conversion
1.1.2 Cellulosic Conversion in Ionic Liquid
Systems
1.1.3 Enzyme-assisted Cellulose Conversion
1.1.4 Production of 5-Hydroxymethylfurfural from
Cellulosic Conversion
1.1.5 Mesoporous Catalysts from Cellulosic
Conversion
Cellulase-immobilized Mesoporous Silica
Nanocatalysts for Ecient Cellulose-to-glucose
Conversion
1.2.1 Optimization of Reaction Conditions
1.2.2 Characterization of Mesoporous Silica
Nanomaterials
1.2.3 Cellulase Immobilization
1.2.4 Cellulose Hydrolysis by using
Cellulase-immobilized MSN
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1.3
Conversion and Kinetics Study of Fructose-to-5Hydroxymethylfurfural (HMF) using Sulfonic and

Ionic Liquid Groups Bi-functionalized MSNs as
Recyclable Solid Catalysts in DMSO Systems
1.3.1 Synthetic Process for Bi-functionalized MSN
1.3.2 Characterization of Mesoporous Silica
Nanomaterials
1.3.3 Fructose-to-HMF Conversion using
Bi-functionalized MSN Catalysts
1.3.4 Kinetic Study
1.4 AcidBase Bi-functionalized, Large-pored MSNs for
Cooperative Catalysis of One-pot Cellulose-to-HMF
Conversion
1.4.1 Functionalization of MSNs with Acid and
Base Groups
1.4.2 Conversion of Cellulose, Cellobiose, Glucose,
and Fructose using Bi-functionalized MSNs
1.4.3 Characterization of the Bi-functionalized
MSNs
1.4.4 Cellulosic Conversion by using
LPMSN-based Catalysts
1.5 Conclusions
References
Chapter 2 Mesoporous Silica Supported Single-site Catalysis
Pranaw Kunal and Brian G. Trewyn
2.1
2.2
Introduction
Synthesis and Structural Aspects of Mesoporous
Silica
2.2.1 Functionalization Techniques for
Mesoporous Silica
2.3 Single-site Heterogeneous Catalysts
2.3.1 Examples of Single-site Catalysts
2.3.2 Surface Distribution of Immobilized Species
2.4 Conclusion
References
Chapter 3 Supported Metal Catalysts for Green Reactions
K. Hara, H. Kobayashi, T. Komanoya, S.-J. Huang, M. Pruski
and A. Fukuoka
3.1
Introduction
13
13
15
15
16
19
19
19
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24
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3.2
Recent Developments in Supported Metal Catalysts

for Bioindustry
3.2.1 Conversion of Biomass to Chemicals and
Fuels
3.2.2 Catalytic Conversion of Cellulose
3.2.3 Hydrolytic Hydrogenation of Cellulose by
Supported Metal Catalysts
3.2.4 Hydrolytic Hydrogenation of Hemicellulose
by Supported Metal Catalysts
3.2.5 Catalytic Conversion of Cellulose to Ethylene
Glycol and Propylene Glycol
3.2.6 Hydrolysis of Cellulose to Glucose
3.2.7 Valorization of Lignin by Supported
Metal Catalysts
3.2.8 Direct Formation of Syngas or Pure
Hydrogen from Biomass
3.3 Mechanistic Aspects in Preferential Oxidation of
Carbon Monoxide under Excess Hydrogen
(PROX Reaction)
3.3.1 Preferential Oxidation of Carbon Monoxide
in Excess Hydrogen (PROX Reaction)
3.3.2 PROX Reaction by Pt Catalysts Supported on
Mesoporous Silica
3.4 Surface-selective Functionalization of Mesoporous
Silica
3.4.1 Novel Types of Functionalized Support
Materials
3.4.2 Surface-selective Modification of
Mesoporous Silica
3.5 Conclusions
References
Chapter 4 Zeolites in the 21st Century

ejka
Wieslaw J. Roth, David Kubicka and Jir C
4.1
4.2
4.3
Introduction
History of Zeolites
Conventional Zeolites
4.3.1 Structures
4.3.2 Synthesis
4.3.3 Role of Organic Structure-directing Agents
4.3.4 Role of Inorganic Species
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67
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Contents
4.4 From 2D to 3D Zeolites and Vice Versa

4.5 Adsorption
4.6 Catalysis
4.7 Summary
Acknowledgments
References
86
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89
94
95
95
Chapter 5 Enzyme Immobilization on Mesoporous Silica Supports

Cheng-Yu Lai and Daniela R. Radu
100
5.1
Introduction Biocatalysis and Porous Silica

Materials
5.2 Types of Porous Silica Support Utilized in Enzyme
Immobilization
5.2.1 Introduction
5.2.2 Enzyme Immobilization/Encapsulation in
Hexagonally Ordered Porous Silica Materials
5.2.3 Enzyme Immobilization/Encapsulation in
Hierarchically Ordered Mesoporous Silica
Materials
5.3 Enzyme Immobilization Strategies in Porous Silica
5.3.1 Introduction
5.3.2 Non-covalent Binding of Enzymes on Porous
Silica Supports Adsorption
5.3.3 Covalent Immobilization of Enzyme onto
Porous Silica Supports
5.4 Characterization of Catalytic Activity for Enzyme
Immobilized in Porous Silica
5.4.1 Introduction
5.4.2 Determination of Enzyme Concentration in
Porous Silica
5.4.3 Enzymatic Activity
5.5 Conclusions
References
Chapter 6 Heterogeneous Catalysts for Biodiesel Production
Daniela R. Radu and George A. Kraus
6.1
6.2
Introduction
Previous Work using Mesoporous Materials
6.2.1 StructureActivity Studies of Mesoporous
Sulfonic Acids
6.2.2 Catalysis of Organic Reactions
6.2.3 Lin Group Contributions
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6.3 Industrial Partnership

6.4 Conclusions
References
Subject Index
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Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00001
CHAPTER 1
Synthesis of Multi-functionalized
Mesoporous Silica
Nanoparticles for Cellulosic
Biomass Conversion
KEVIN C.-W. WU
Department of Chemical Engineering, National Taiwan University, No. 1,
Sec. 4, Roosevelt Road, Taipei 10617, Taiwan
Email: kevinwu@ntu.edu.tw
1.1 Introduction
1.1.1
Background of Cellulosic Biomass Conversion
The usage of fossil fuels causes serious problems like the energy crisis and
global warming. In order to solve these problems, so far much attention has
been paid to the development of renewable energies such as solar or wind
energy. Biofuel produced from biomass is one of the potential alternatives.
First-generation biofuels (i.e. biodiesel) produced from corn and soybean oil
have proved that biomass-to-biofuel conversion is possible; however, the use
of edible agriculture as a source will cause other problems such as food
deficiency.1 Therefore, second-generation biofuels generated from nonedible lignocellulosic biomass have attracted more attention recently.
Lignocellulosic (or so-called wood-based) biomass consists of three
major components: cellulose (41%), hemicellulose (28%), and lignin (27%).2
Generally, cellulose and hemicellulose can be used to produce bioethanol,
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Chapter 1
and lignin oers a broad spectrum of conversion (thermal cracking, fast

pyrolysis, and complete gasification) to achieve valuable chemicals and
transportation fuels.3 So far, a great deal of eort has been put toward the
degradation of cellulose with enzymes,4 mineral acids,5 bases,6 and supercritical water.7 The enzymatic hydrolysis of cellulose is eective, but the
system is sensitive to contaminants originating from other biomass components. Furthermore, pre-treatment of cellulose (e.g., ammonia or steam
treatments in a high-pressure process or mechanical milling) is typically
required to increase the accessible area of cellulose for a reasonable rate of
enzymatic hydrolysis.8 Mineral acids have been extensively investigated to
catalyze hydrolysis at a variety of acid concentrations and temperatures.
A rather high temperature (180230 1C) has been used in order to obtain an
acceptable rate of cellulose hydrolysis. Furthermore, degradation of the
resulting glucose becomes an issue at such high temperatures.9
1.1.2
Cellulosic Conversion in Ionic Liquid Systems
Recently, ionic liquids (ILs) have attracted a lot of attention and have been
utilized as solvents for the degradation of the lignocellulosic biomass.1014
The importance of ionic liquids in cellulose dissolution has been emphasized in several reviews.1517 ILs are a kind of novel green solvent. They
are organic salts with relatively low melting points. In other words, ILs
usually appear as crystals under normal conditions; however, they can be
melted and dissociated into two ionic parts at relatively high temperatures
(usually less than 100 1C). In contrast to other crystalline salts (e.g. NaCl),
the attractive characteristic of ILs is that they can transform into a
liquid phase.
The utilization of ILs for the dissolution of lignocellulose started in early
2000. Numerous papers have been published on controlling the viscosity and
polarity of ionic liquids by varying their ionic structures.16,17 The main focus
of these papers was the solubility of the synthesized ILs toward dierent
carbohydrates such as glucose, sucrose, amylose, cellulose, and so on. In
2002, Rogers et al. reported that cellulose could be dissolved in ILs at
100 1C.10 The solubility of cellulose in ionic liquids results from its anions.
It can disrupt the hydrogen bonds between polysaccharide chains of
cellulose and then dissolve it.18 This discovery started a new pathway to deal
with cellulose at low temperatures and ambient pressure.
In 2007, Zhang and his co-workers discovered that CrCl2 in [EMIM]Cl
(1-ethyl-3-methylimidazolium chloride, an imidazolium-type ionic liquid)
can eciently catalyze the glucose-to-HMF conversion.19 HMF is a
promising platform chemical because it can further transform to a widely
used biofuel called 2,5-dimethylfuran (DMF)20 and other useful materials.21
Since then, many have worked on the production of HMF from cellulose or
glucose in ionic liquid systems. Binder and Raines combined HCl, CrCl2 or
CrCl3, DMA/LiCl and [EMIM]Cl to convert cellulose to HMF;13 Zhang and
his co-workers used CrCl2/CuCl2 as catalysts in [EMIM]Cl;14 Han and his
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Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles
co-workers also discovered SnCl4 in [EMIM]BF4 can convert glucose to HMF

with a high yield;22 Riisager and his co-workers discussed HMF produced
from lanthanide-containing ionic liquid systems;23 Bell and Chidambaram
discovered that 12-molybdophosphoric acid in [EMIM]Cl/acetonitrile or
[BMIM]Cl/acetonitrile can selectively convert glucose to HMF.24 Although
there has been much research focused on the addition of various kinds of
catalysts in ionic liquid systems, very few papers discussed the eects of
reaction conditions (such as dissolution temperatures and times of ILs, reaction temperatures and times, and the amounts of water) on the conversion
eciency in ionic liquids without additional catalysts.25 In fact, in the abovementioned papers, HMF could still be produced when using ILs only (no
other additives), although the yields were very low. This indicates that ILs in
these systems serve not only as solvents but also as catalysts. We suggest that
the low HMF yield was because the reaction conditions for HMF production
in these cases were not optimized. For example, Zhao et al. has shown that
the yield of HMF converted from fructose was greatly aected by the reaction
temperature in an [EMIM]Cl only system.14 Very recently, Binder and Raines
discussed the sequence and timing of the addition of water into the cellulosic conversion and showed that an optimal sequence and timing strongly
aected the conversion eciency.26
1.1.3
Enzyme-assisted Cellulose Conversion
In recent decades, cellulase was broadly studied for the hydrolysis of cellulose.2731 Cellulase is a mixture of enzymes containing three main components: (1) endo-1,4-beta-D-glucanase (EG) which randomly cleaves the
cellulose chain to lower the crystallinity; (2) cellobiohydrolase (CBH) which
degrades cellulose by releasing cellobiose units; (3) beta-glucosidase which
hydrolyzes cellobiose and other oligomers to get glucose units. To date, the
reaction conditions and the hydrolytic processes of hydrolyzing cellulose by
using free cellulase have been optimized with a glucose yield as high as
70%.29 However, one critical problem when using cellulase as a catalyst is
the easy deactivation of cellulase by environmental factors (e.g., temperature), which greatly hinder its practical use in industry.32,33 In order to
overcome such diculties, the immobilization of cellulase onto solid
materials is a feasible way to enhance its stability.
Many research papers have demonstrated that immobilizing cellulase
onto organic and inorganic materials could improve the stability and
reusability of cellulase without reducing its catalytic ability.3441 Among the
host materials, mesoporous silica materials have gained much attention
because of their large specific surface area, high mechanical strength, and
tunable surface functionality.34,35 Recently, Sakaguchi et al. studied the encapsulation of cellulase by using mesoporous silica SBA-15 with various pore
sizes as hosts.36 They found that the enzymatic activity of cellulase strongly
depended on the pore size of SBA-15. The best performance of cellulase
could be obtained when using SBA-15 with pore diameter around 8.9 nm.
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Chapter 1
However, the structure of SBA-15 is 2D hexagonal with length of several mm,

which would inhibit the adsorption of cellulase into the inner surface of the
SBA-15 and result in a low adsorption amount. Lu et al. studied the eect of
surface functionalities of a mesoporous silica FDU-12 (pore size is around
25.4 nm) on the immobilization of cellulase.35 They functionalized FDU-12
with phenyl, thiol, amino and vinyl groups. The results showed that the
electrostatic and hydrophobic interactions between cellulase and functionalized FDU-12 play significant roles on the activity and stability of immobilized cellulase. Amine-functionalized FDU-12 adsorbed the largest amount
of cellulase but exhibited the lowest activity. They explained this was due to
the interaction between amine groups of FDU-12 and the carboxyl groups of
catalytic site of cellulase which thereby inhibited the activity of cellulase. In
contrast, vinyl-functionalized FDU-12 not only maintained the activity of
cellulase up to 80% but also temporal enzyme stability owing to the existence
of hydrophobic groups. Despite these pioneering studies, none of them has
studied dierent immobilization methods (i.e., physical adsorption and
chemical binding) on the eciency of cellulase, and cellulosic hydrolysis by
immobilized cellulase has never been reported yet.
1.1.4
Production of 5-Hydroxymethylfurfural from Cellulosic

Conversion
5-Hydroxymethylfurfural (HMF), converted from lignocellulosic biomass, is

considered one of the top value-added chemicals; this results from its
utilization as a building-block platform between biomass and promising
chemical intermediates, such as 2,5-furandicarboxylic acid (FDCA),42 2,5dimethylfuran (DMF),43 5-ethoxymethylfurfural (EMF),44 and ethyl levulinate
(EL),45 which have been studied extensively in recent years and demonstrate
the significance of HMF.
HMF has been successfully generated from fructose, glucose, and cellulose using various kinds of reaction systems with homogeneous or heterogeneous catalysts.4648 The mechanism of cellulose-to-HMF conversion is
still unclear, but the conversion can be divided into several reactions. First,
cellulose is usually pre-treated by alkaline, acid, or certain ionic solutions to
destroy its rigid framework. The pre-treated cellulose then goes through the
depolymerization process in an acidic system in order to break the 1,4-bglycosidic bonds of cellulose and produce glucose. Subsequently, glucose
converts to fructose via isomerization, which is a so-called Lobry de Bruyn
Alberda van Ekenstein transformation.49 Finally, the dehydration of fructose
generates HMF. The mechanism of fructose-to-HMF conversion has been
discussed in numerous studies.5052 The micro-kinetic model for this threestage water-removed process53 has been constructed to determine an apparent activation energy.54 In addition, according to computational results,
both the estimated equilibrium constant and activation energy can be
greatly influenced by reaction conditions, including temperature, solvent,
and catalysts.55
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Dierent solvents have been used in the fructose-to-HMF conversion because of the contrast between water-soluble reactants (e.g., fructose and
glucose) and organic-solvent-soluble products (e.g., HMF). The careful selection of solvents can promote the preferential reaction and enhance
product yield. The Dumesic group studied the eects of solvents on the
dehydration of fructose in biphasic systems, and demonstrated the catalytic
ability of dimethylsulfoxide (DMSO), which is able to suppress the undesired
side reactions eectively.55 Recently, ILs have been widely used as both
catalysts and solvents for producing HMF from lignocelluloses because of
their comparatively higher catalytic activity and adjustable composition.56
However, despite the excellent activity and recyclability of ILs, their potential
is restricted to laboratory-scale experiments due to high costs. Therefore, a
low-price solvent with the desired properties (e.g., high boiling point and low
viscosity) such as DMSO can have more potential in industrial applications.
In recent years, several groups have reported the production of HMF from
fructose in DMSO-based reaction systems via homogeneous and heterogeneous catalysts, including acids, salts, and metal ions.57 The Dumesic
group has investigated the catalytic capabilities of various homogeneous
mineral acids.58 Recently, Wang et al. used carbon-based p-toluenesulfonic
acid (TsOH) at 130 1C for 1.5 h resulting in a 91.2% yield of HMF.59 Although
these pioneering studies showed high yields of HMF, harsher reaction
conditions are always needed in such homogeneous catalytic systems. From
economic and sustainable viewpoints, scientists have turned to heterogeneous solid catalysts and mild reaction conditions. For example, the
Sidhpuria group immobilized ILs onto silica particles as an ecient heterogeneous catalyst for fructose-to-HMF conversion with a yield of 63% in a
DMSO system.60
1.1.5
Mesoporous Catalysts from Cellulosic Conversion
Mesoporous silica nanoparticles (MSNs) have attracted a great deal of attention in the field of catalysis because of their high surface area and controllable pore size. In addition, abundant SiOH groups on the surface of
MSNs provide the possibility of further functionalization with other organic
groups.61 For example, the Lin group has used a co-condensation method to
functionalize MSNs with a general acid (i.e., a ureidopropyl (UDP) group) and
a base (i.e., a 3-[2-(2-aminoethylamino)ethylamino]-propyl (AEP) group) as a
cooperative acidbase catalyst for aldol, Henry, and cyanosilylation reactions.62 We also have used a grafting method to functionalize MSNs with
several metalhistidine complexes for H2O2-assisted tooth bleaching. However,
the conventional MSNs synthesized from the cationic surfactant cetyltrimethylammonium bromide (CTAB) exhibit a pore size of around 2 nm. For
several catalytic reactions involving large molecules (e.g., proteins or cellulose),
this pore size is too small to allow the reactants to diuse into the mesopores,
thus losing the advantage of high surface area inside the MSNs. Therefore, the
synthesis of MSNs with pore sizes large than 10 nm is highly desirable.
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Chapter 1
The MSNs with large pore sizes can be synthesized through two approaches: (1) using high-molecular-weight surfactants as templates; and (2)
adding hydrophobic additives as swelling agents. For example, the Zhao
group succeeded in synthesising mesoporous silica with an ultra-large pore
size of approximately 37.0 nm by using a high-molecular-weight surfactant
(poly(ethylene oxide)-b-poly(methyl methacrylate); PEO-b-PMMA).63 The
same group has also reported the addition of 1,3,5-trimethylbenzene (TMB)
as a swelling agent to synthesize mesoporous silica with a large pore of 25.4
nm (as denoted as FDU-12).63,64 The Lu group has functionalized FDU-12
materials with phenyl, thiol, amino, and vinyl groups and studied the eect
of these functional groups on the immobilization ecacy of an enzyme (i.e.,
cellulase).65 Despite these pioneering studies, researchers have not yet
utilized large-pored MSNs with various functional groups for cellulosic
conversion in ionic liquid systems. In general, cellulosic conversion involves
three main reactions: (1) cellobiose-to-glucose depolymerization, (2) glucoseto-fructose isomerization, (3) fructose-to-HMF dehydration. These reactions
need acid, base, and acid catalysts, respectively, as illustrated in Scheme 1.1.
Consequently, to synthesize large-pored MSNs with both acid and base
functionalities as a new cooperative solid catalyst would be helpful for
one-pot cellulose-to-HMF conversion.
1.2 Cellulase-immobilized Mesoporous Silica

Nanocatalysts for Ecient Cellulose-to-glucose
Conversion
1.2.1
Optimization of Reaction Conditions
Optimal reaction conditions with respect to temperature, the amount of

catalyst and the reaction time are crucial to maximising the final yield of
Scheme 1.1
An illustration showing the production of 5-HMF converted from

cellulose through a series of reactions.
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(a)
(b)
(c)
Figure 1.1
Optimization of reaction conditions for cellulase-assisted celluloseto-glucose conversion: (a) reaction temperature; (b) cellulase amount;
(c) reaction time.
cellulosic hydrolysis when using cellulase as a catalyst. Therefore, we first

optimized the reaction temperatures, the amount of free cellulase and the
reaction time. As shown in Figure 1.1a, 15 mg of cellulose was hydrolyzed
using free cellulase (50 Unit, 1 Unit indicates the amount of enzyme that can
catalyze 1106 mole substrate in one minute) as the catalyst at dierent
temperatures for 24 h; the maximum yield of glucose was obtained at 50 1C.
By repeating the experiment, we found that 50 1C is also the most stable
operating condition for cellulose. Thus, we chose 50 1C as the suitable
temperature for cellulase-assisted cellulose hydrolysis. From the economic
point of view, an optimal amount of cellulase means the minimum amount
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Chapter 1
of cellulase while keeping the maximum yield of glucose. Various amounts

of cellulase, ranging from 1 mg to 23 mg, were used for the hydrolysis of
cellulose (15 mg) at 50 1C for 24 h. Based on the results in Figure 1.1b, we
found that the optimal amount of celluase was 25 Unit (i.e., 4.5 mg). More
cellulase than 25 Unit did not increase the yield of glucose at the current
operation coniditions. After obtaining the optimal reaction temperature and
the amount of cellulase, the optimal reaction time was also examined. 15 mg
of cellulose was hydrolyzed using free cellulase (25 Unit) at 50 1C for various
reaction times (i.e., ranging from 3 to 48 hours). According to the results
shown in Figure 1.1c, in order to reach 90% glucose yield, cellulose has to be
hydrolyzed for at least 24 h although 80% glucose yield could be obtained in
12 h. For consistency, here we chose 24 hours as the optimal reaction time.
1.2.2
Characterization of Mesoporous Silica Nanomaterials
The morphology and porous properties of the synthesized MSNs with two
dierent pore sizes (NB these are referred to as large-pore MSNs (LPMSNs)
and small-pore MSNs (SPMSNs) hereafter) are characterized with scanning
electron microscopy (SEM) and nitrogen adsorptiondesorption isotherms.
The SEM images in Figure 1.2a and b show the uniform and spherical
morphology for both LPMSNs and SPMSNs with diameters around 600 and
150 nm, respectively. In Figure 1.2c and d, LPMSNs and SPMSNs exhibit type
III and type IV nitrogen adsorptiondesorption isotherms, respectively. The
type III isotherm of LPMSNs exhibits prominent adsorption at high relative
pressures (P/P0), which is indicative of adsorption in macropores. In contrast, the type IV isotherm of SPMSNs has been widely shown to occur in a
typical mesoporous material with a two-dimensional hexagonal structure.
The BrunauerEmmettTeller (BET) specific surface areas for LPMSNs and
SPMSNs are 262.6 and 820.1 m2 g1, respectively. In addition, the pore-size
distribution calculated from the BarrettJoynerHalenda (BJH) method
clearly shows that LPMSNs exhibit a broad pore size around 2040 nm while
SPMSNs exhibit a narrow pore size around 25 nm, as depicted in Figure 1.2e
and f, respectively. The structural properties of LPMSNs and SPMSNs are
summarized in Table 1.1.
In addition to pore size and surface area, the surface functionality of the
MSN also aects the immobilization of cellulase. We qualitatively and
quantitatively study the functional groups on the SPMSNs and LPMSNs by
29
Si and 13C solid-state nuclear magnetic resonance (NMR). Because the
synthetic methods for SPMSNs and LPMSNs are dierent, the organic
functional groups and their amounts on the surface of the prepared materials are dierent. As shown in the 29Si NMR spectra (Figure 1.3a), LPMSNs
exhibited Q3, Q4, T3 and T2 bonds, indicating that there are SiOH and
SiOC bonds in the material. Because we added 3-aminopropyltrimethoxysilane (APTMS) during the synthesis of LPMSN, the SiOC bonds should be
due to the presence of APTMS. On the other hand, SPMSN exhibited only Q3
and Q4 peaks that represent the presence of SiOSi and SiOH bonds, as
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(a)
(b)
(c)
(d)
(e)
(f)
Figure 1.2
Characterization of LPMSNs and SPMSNs. SEM, nitrogen adsorption

desorption isotherms and pore-size distribution, respectively, for (a, c
and e) LPMSNs and (b, d and f) SPMSNs.
Table 1.1
Summary of structural properties and functionalities of SPMSNs, LPMSNs

and TESP-SA-functionalized LPMSNs.a
Sample
SPMSN
LPMSN
TESP-SA
LPMSN
a
Particle
size/nm
Specific
surface
area/m2 g1
Pore
size/nm
R grafted/
mmol g1
OH residues/
mmol g1
ca. 150
ca. 600
ca. 600
820.1
262.6
N.D.
25
2040
N.D.
N.D.
1.06
1.49
9.89
6.12
4.37
N.D. not done.
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10
Chapter 1
(a)
(b)
(c)
(d)
Figure 1.3
29
Si solid-state NMR spectra of (a) LPMSN and (b) SPMSN. 13C solid-state
NMR spectra of (c) LPMSN and (d) TESP-SA-functionalized LPMSN.
shown in Figure 1.3b. These two materials were used as hosts for physical
adsorption of cellulase. For chemically binding cellulase, we further functionalize LPMSN with carboxyl groups by reacting LPMSN with an organosilane 3-triethoxysilylpropyl succinic acid anhydride (TESP-SA). Based on
the 13C NMR spectra of LPMSN and TESP-SA-functionalized LPMSN in
Figure 1.3c and d, respectively, we could conclude that the TESP-SA was
successfully grafted onto the surface of LPMSN. The TESP-SA-functionalized
LPMSN should exhibit two functional groups, i.e., the amino group from
APTMS and the carboxyl group from TESP-SA, on its surfaces. The amounts
of the functional groups on the SPMSN, LPMSN, and TESP-SA-functionalized
LPMSN were calculated and summarized in Table 1.1.
1.2.3
Cellulase Immobilization
Cellulase was immobilized into SPMSN and LPMSN by physical adsorption

and into TESP-SA-functionalized LPMSN by chemical binding. The amounts
of cellulase immobilized into these materials were quantitatively measured
by UV-Vis spectroscopy. As shown in Table 1.2, on the basis of the same
amount of host materials (i.e., 50 mg), the amounts of the immobilized
cellulase are 14.6 mg, 23.4 mg, and 19.2 mg for SPMSN, LPMSN, and
TESP-SA-functionalized LPMSN, respectively. The highest amount of
immobilized cellulase was found in the case of cellulase-adsorbed LPMSN,
which was 1.6 times the amount in cellulase-adsorbed SPMSN. Although the
SPMSN exhibits a higher surface area than LPMSN, the small pore size of
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Table 1.2
Summary of cellulase loading amount and yields of glucose for free

cellulase, cellulase-adsorbed SPMSN, cellulase-adsorbed LPMSN and
cellulase-linked TESP-SA-functionalized LPMSN.
Sample
Cellulase/mg
Free cellulase
Cellulase-adsorbed
SPMSN
Cellulase-adsorbed
LPMSN
Cellulase-linked
TESP-SA LPMSN
a
11
4.5
14.6
Glucose
yield (%)
before
Glucose
yield (%)
after
85.86
53.39
(24.89)a
4.59
(24.89)a
10.64
(42.71)a
82.15
23.4
33.3
(46.14)a
77.89
19.2
83.79
Percentage
lost (%)
37.78
83.30
86.56
4.61
Yield of cellobiose.
SPMSN (i.e., 25 nm) made the diusion of cellulase into the pore dicult
due to the large size of cellulase (around 8 nm). Therefore, a pore size larger
than 8 nm in MSNs is essential for the immobilization of cellulase. In
addition, although the amount of cellulase chemically bonded with TESP-SAfunctionalized LPMSN was less than that of cellulase-adsorbed LPMSN, the
amount was still larger than 4.5 mg which had been considered to be the
minimum amount for maximum glucose production under optimal reaction
conditions.
Another factor aecting the immobilization of cellulase is surface charge.
The surface charges of cellulase and SPMSN at pH 4.8 are both negative
(6.7 and 14.8 mV, respectively). Therefore, the electrostatic interaction
between SPMSN and cellulase was negligible. The surface charge of LPMSN
is around zero (1.0 mV) because of the existence of both SiOH and SiNH2
groups. Therefore, in addition to the larger pore size of LPMSN, the increased adsorption amount in the case of cellulase-adsorbed LPMSN also
resulted from the electrostatic interaction between cellulase and SiNH2
groups of LPMSN. It is worth noting that the surface charge of TESP-SAfunctionalized LPMSN was negative (40.5 mV) owing to the existence of
carboxylic acid groups in TESP-SA. Therefore the immobilized cellulase
amount in this case was less than that of cellulase-adsorbed LPMSN. However, we have confirmed that the immobilized cellulases here were covalently
linked with TESP-SA-functionalized LPMSN by 13C NMR, and such chemically linked cellulases could avoid the problem of cellulase detachment,
resulting in excellent stability (see discussion below).
1.2.4
Cellulose Hydrolysis by using Cellulase-immobilized

MSN
As we have previously examined, 4.5 mg of free cellulase was enough to

convert 15 mg of cellulose to glucose with a high yield of around 85% at
50 1C for 24 hours. However, although the amounts of cellulase immobilized
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12
Figure 1.4
Chapter 1
Yields of glucose for free cellulase, cellulase-adsorbed SPMSN, cellulaseadsorbed LPMSN, and cellulase-linked TESP-SA-functionalized LPMSN
of LPMSN and TESP-SA-functionalized LPMSN. Glucose_before indicates that the catalysts were used immediately after preparation.
Glucose_after indicates that the catalysts were used after aging at
room temperature for 23 days.
in the MSN materials are all larger than 4.5 mg, their glucose yields were all
less than 85% at the same optimal reaction conditions. As shown in
Figure 1.4 and Table 1.2, the glucose yields for cellulase-adsorbed SPMSN,
cellulase-adsorbed LPMSN, and cellulase-linked TESP-SA LPMSN were
33.30%, 77.89%, and 83.79%, respectively. It is clearly seen that the cellulase
chemically bonded with TESP-SA functionalized LPMSN exhibited almost
the same activity with free cellulase. For the case of cellulase-adsorbed
SPMSN, the glucose yield was the smallest, which might be due to the formation of a byproduct (i.e., cellobiose with yield of 46.14%). Because the
cellulase-adsorbed LPMSN catalyst still exhibited a respectable glucose yield
of 77.89%, we suggest that the low glucose yield for cellulase-adsorbed
SPMSN was due to the small pore size. When the pore size of MSN was small,
not only could cellulase not be adsorbed in the pores but also the pre-treated
cellulose could not diuse into the pores. This result again proved the significance of suitable pore size when using MSN materials as hosts.
One may be concerned that the chemically linked cellulase will lose its
activity due to the change of its conformation via covalent binding. The Lu
group has utilized amino-group-functionalized mesoporous silica materials
to immobilize cellulase and found that the activity of the immobilized cellulase decreased although the amount of immobilized material was large, as
compared to free cellulase.35 They suggested that the amino group of the
materials would bind to the catalytic domains of the cellulase, thereby
reducing its catalytic ability. In contrast to their result, our data indicated
that the activity of chemically linked cellulase was similar with that of free
cellulase. We conclude that the carboxylic-group-functionalized LPMSN used
in this study would bind with the cellulose binding domains (not catalytic
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13
domains) of the cellulase, thereby retaining the activity of cellulase. In fact,

several papers have also reported the preservation/enhancement of cellulolytic activity by connecting the cellulose binding domains (CBD) of cellulase
with scaolds.66
One of the advantages of immobilizing cellulase within porous materials
is to increase the stability of cellulase. To examine the stability of the
immobilized cellulase, this study tests dierent cellulase-immobilized materials, including free cellulase, cellulase-adsorbed SPMSN, cellulaseadsorbed LPMSN and cellulase-linked TESP-SA-functionalized LPMSN by
storing these catalysts at room temperature (usually cellulase should be
stored at 4 1C). After 23 days, these materials were used to hydrolyze
cellulose, and the results are refered as After_storage in contrast to
Before_storage, which involved catalysts before stability experiments.
Figure 1.4 and Table 1.2 show that after 23 days the glucose yields for free
cellulase, cellulase-adsorbed SPMSN, cellulase-adsorbed LPMSN, and cellulase-linked TESP-SA-functionalized LPMSN all decreased, yielding 53.39%,
4.59%, 10.64%, and 82.15%, respectively. The corresponding percentage loss
of glucose yields for free cellulase and cellulase-immobilized catalysts were
37.78%, 83.30%, 86.56% and 4.61%, respectively.
The stability experiments in this study reveal three important findings. (i)
The SPMSN and LPMSN could not protect cellulase when the cellulase was
merely immobilized by physical adsorption. The large percentage loss (over
80%) of glucose yield in these two cases indicated that cellulase easily detached from MSN at room temperature, resulting in deactivation. (ii) In
addition to glucose, cellobiose was formed in the cases of free cellulase and
cellulase-adsorbed SPMSN and LPMSN. This result indicates that the activity
of cellobiohydrolase, an enzyme in cellulase that hydrolyzes disaccharides
into individual monosaccharides, decreased after storage at room temperature for 23 days. (iii) The cellulase chemically linked to TESP-SA-functionalized LPMSN exhibited the best stability. This indicates that the
chemical bonding between cellulase and TESP-SA-functionalized LPMSN
decreased its hydrolytic activity while preserving the catalytic specificity
toward cellulose-to-glucose conversion, which is the best way to immobilize
cellulase with a stable eciency.
1.3 Conversion and Kinetics Study of Fructose-to-5Hydroxymethylfurfural (HMF) using Sulfonic and
Ionic Liquid Groups Bi-functionalized MSNs as
Recyclable Solid Catalysts in DMSO Systems
1.3.1
Synthetic Process for Bi-functionalized MSN
The synthetic process of the bi-functionalized MSN is shown in Scheme 1.2

and is described as follows: Brij-97 was used as the template and was first
dissolved in 180 g of deionized water. Then, APTMS and DOP were added to
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14
Scheme 1.2
Chapter 1
Synthetic process for preparing the bi-functionalized MSN.
the Brij-97 solution with stirring at room temperature. After stirring for
30 min, organosilanes (i.e., MPTMS and CPTES) were added to the reaction
system along with TEOS, and the whole system, with a composition (in
molar ratios) of water: Brij-97 : TEOS : MPTMS : CPTES 433 : 0.293 : 1 : 0.009 :
0.009, was prepared and kept stirred for 24 h at room temperature. The
mixture was subsequently heated at 100 1C overnight. Finally, the precipitated solid was collected by filtration and washed sequentially with water
and methanol. It is worth noting that the template can be extracted by this
washing step. To further convert the thiol group of (MP CP)-MSN to a
sulfonic group, the (MP CP)-MSN was oxidized in an H2O2 solution with a
composition of (MP CP)-MSN : H2O : MeOH : H2O2 0.5 g : 10 ml : 10 ml :
10 ml. After reaction at room temperature overnight, the obtained sample
(i.e., (HSO3 CP)-MSN) was washed and dried in vacuum. To further functionalize the (HSO3 CP)-MSN with ionic liquid, the (HSO3 CP)-MSN
sample and solid imidazole were degassed for 3 h before the addition of
anhydrous benzene and chlorobutane with the molar ratio of imidazole :
chlorobutane 1 : 2. After one day of reflux, the product (i.e., (HSO3 ILs)MSN) was collected through filtration and washed with anhydrous benzene.
Finally, the (HSO3 ILs)-MSN sample was immersed in CrCl2 solution, and
the whole mixture was kept stirred overnight. CrCl2 can be physically
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15
absorbed on the surface of (HSO3 IL)-MSN. The final product

([HSO3 (ILs/CrCl2)]-MSN) was collected by centrifugation.
08:23:53.
1.3.2
Characterization of Mesoporous Silica Nanomaterials
The morphology and porous properties of the series of synthesized bifunctionalized MSN were characterized with SEM and nitrogen adsorption
desorption isotherms. The SEM image shows an uniform and spherical
morphology for bi-functionalized MSN with particle size of sub-microns. In
addition, the bi-functionalized MSNs exhibit a type IV nitrogen adsorption
desorption isotherm, indicating multilayer adsorption by capillary condensation. Moreover, the results of BET specific surface area and pore-size
distribution calculated from the BJH method are listed in Table 1.3 together
with other structural properties of bi-functionalized MSNs.
Next, we qualitatively and quantitatively investigated the functional
groups on the bi-functionalized MSN using 29Si and 13C solid-state NMR.
The 13C NMR spectrum contains ten identified signals, and these results
evidenced the successful grafting of the organosilane MPTMS and ILs on the
MSN. Additionally, we further quantified the amounts of each functional
group on the MSN by 29Si NMR. There were Qn and Tn peaks, which represents the relative amount of silica framework and their covalent bonding
with organosilanes. The amounts of functional groups are summarized in
Table 1.3. In addition, results of element analysis indicated the presence of
the sulfonic acid (S, around 2.3%) and ionic liquid (N, around 1.7%).
1.3.3
Fructose-to-HMF Conversion using Bi-functionalized

MSN Catalysts
In order to demonstrate the eect of bi-functionalized MSN on the fructoseto-HMF conversion, the reaction was executed without catalysts (blank
sample), with MSN and bi-functionalized MSN. The result including the
ecacy of fructose conversion, HMF yield, and selectivity is depicted in
Figure 1.5a. The cases labeled blank (no catalyst) and MSN (with nonfunctionalized MSN as the catalyst) showed low conversion (around 25%)
and almost no HMF yield, indicating that the dehydration of fructose to
generate HMF was dicult to achieve in such reaction conditions (i.e.,
DMSO solvent, 90 1C, 3 h). In contrast, with the same reaction conditions,
Table 1.3
Summary of characterization of bi-functionalized MSNs.
Physical properties
Functionalization
Specific
surface
Pore
area/m2 g1 size/nm
Particle
size/nm
Number
of SiOH/
mmol g1
Functional
group/mmol
g1
Elemental
analysis
N% C% H%
98.0
400
6.12
1.06
1.7
4.4
S%
16.0 27.6 2.3
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16
Chapter 1
the reaction with the presence of the bi-functionalized MSN surprisingly

exhibited enhanced fructose conversion (almost 100%) and HMF yields as
high as 72.5%, as shown in Figure 1.5a. These results clearly demonstrate
the eectiveness of the bi-functionalized MSN on the catalytic production of
HMF, which was due to the contributions of the functional groups of
RHSO3 acid and [EMIM]Cl/CrCl2 ionic liquid. It has been reported that the
dehydration of fructose can be promoted with the assistance of dierent
homogeneous acids and metal chlorides.61 Here we report a successful
functionalization of both sulfonic acid and ionic liquid/metal chloride onto
the surface of MSN materials as a new method to provide ecient heterogeneous catalysts. In addition to the sulfonic acid groups, chloride ions can
act as an eective catalyst due to their nucleophilicity, and the acidic C-2
proton of the imidazolium part of the ionic liquid also promotes the dehydration of fructose.52 Furthermore, in contrast to other solid nanoparticles,
MSN exhibits a high surface area and large mesopores, which should enhance
the eciency greatly, owing to the increased number of reaction sites.
Reusability of the [HSO3 (ILs/CrCl2)]-MSN was further studied over five
cycles. As shown in Figure 1.5b, it is seen that the conversions of fructose
were maintained at almost 98% until the fifth run. Additionally, no significant loss of HMF yield was observed. It means that the grafted functional
groups (i.e. sulfonic acid (HSO3) and ILs) did not leach during the complicated reiterating process and further hold their original activity without
obvious decay. Therefore, the recyclability of the synthesized bi-functionalized material has been exactly confirmed.
1.3.4
Kinetic Study
We further study the kinetics of the fructose-to-HMF conversion and compare the rate constants, reaction orders, and activation energies for the
systems with and without bi-functionalized MSN catalysts. First, we
(a)
Figure 1.5
(b)
(a) Results of fructose-to-HMF conversion in dierent systems.

Blank: without any catalyst. MSN: with non-functionalized MSN.
[HSO3 (ILs/CrCl2)]-MSN: with bi-functionalized MSN. (b) Recyclability
of [HSO3 (ILs/CrCl2)]-MSN in fructose-to-HMF conversion.
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(a)
Figure 1.6
17
(b)
(a) Eect of reaction time and catalyst on the yield of HMF. (b) The
kinetics profiles of HMF decomposition in DMSO at dierent temperatures. Diamonds: 120 1C; squares: 140 1C.
conducted two reaction systems (i.e., with and without catalyst) at the same
reaction temperature (i.e., 90 1C) but for dierent reaction time periods.
We observed the variation of HMF yields with reaction time and the data is
shown as Figure 1.6a. The reaction rates of both cases are initially higher but
tend to be almost constant after a time-span, indicating that the reactants
have already run out, resulting in no more HMF being produced. However,
adding our synthesized catalysts, [HSO3 (ILs/CrCl2)]-MSN, obviously accelerates the generation of HMF to some extent. Three hours later, there is
about 73.4% of HMF, which is nearly three times larger than the percentage
in blank (25.3%). That is to say, our material has an eect on the catalytic
fructose conversion.
For the purpose of identifying the relationships between kinetic parameters (such as rate constants, reaction orders, and activation energies)
and the addition of the bi-functionalized catalyst, we further comprehensively constructed the kinetics profiles at dierent temperatures for systems
with and without [HSO3 (ILs/CrCl2)]-MSN (Figure 1.6a). We supposed that
the ultimate product of fructose dehydration is HMF only, i.e. we did not
take other by-products into account. Besides, we assumed the degradation of
HMF would not occur under our designed condition (90 1C, 06 h). This
hypothesis can be supported by the test results of HMF decomposition, as
shown in Figure 1.6b. In this experiment, HMF is considered as the reactant,
placed in an identical environment as before. From the data shown, we can
see that the apparent decay of HMF (15.18%) could be noticed only under
sucient reaction temperature and time (140 1C, 6 h), which is very far from
our practical operating conditions. That is to say, in our milder conditions
(90 1C, 3 h), the decomposition of HMF is negligible and this outcome
bolsters the previous model we have set up.
In Figure 1.7, we analyzed the kinetics profiles in order to systematically
understand the shifts of each kinetics parameter caused by the catalysts.
Referring to the previous published research,54 we assumed that the
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Chapter 1
08:23:53.
transformation of fructose is a 1st order process and that the reaction rate
could be expressed as follows:
dHMF
dfructose
kfructose
dt
dt
dHMF
dfructose
kfructose
dt
dt
where [ ] means the molar concentration of each chemical and k is the rate
constant for fructose conversion at a certain temperature. Next, we transformed this equation into a numerical form and made the [fructose] in terms
of conversion X, i.e. [fructose]t [fructose]t0 (1 X). After the subsequent
integral calculation, the original equation will become:
ln(1 X) kt C
where t is the reaction time and C is an arbitrary constant. Therefore, we
plotted a figure with ln(1 X) as the y-axis and t as the x-axis, fitting the
data linearly, and evaluated reaction constants from the slopes. As shown in
Figure 1.7, there is an obvious increase of k in the presence of bi-functionalized MSNs, confirming their ability to promote this reaction. Next, we
calculated the activation energy (Ea) of each system from rate constants we
obtained by the Arrhenius equation. The Ea values of systems with and
without catalysts are 67.5 and 80.05 kJ mol1, respectively. This fact indicated that our addition of [HSO3 (ILs/CrCl2)]-MSN has altered the reaction
route to a certain degree, consequently lowering the activation energy and
leading to a higher reaction rate.
(a)
Figure 1.7
(b)
The kinetics profiles of fructose-to-HMF conversion (fitted by 1st

order assumption) (a) without catalysts and (b) with [HSO3 (ILs/
CrCl2)]-MSN.
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1.4 AcidBase Bi-functionalized, Large-pored MSNs

for Cooperative Catalysis of One-pot Cellulose-toHMF Conversion
1.4.1
Functionalization of MSNs with Acid and Base Groups
To functionalize LPMSN with acid and base groups, the organosilane, i.e.,
MPTMS and APTMS, was grafted onto the surface of LPMSN. Typically, 1 g of
LPMSN in a two-necked round-bottom flask was degassed in vacuum at
110 1C for 3 h. After that, dried toluene (40 mL) was injected into the flask
under nitrogen atmosphere, followed by injecting organosilanes. The
amount of organosilane used was 1.3 times the amount of silanol group
on the LPMSN that was previously calculated by solid-state NMR (i.e.,
6 mmol g1). Then, the mixture was heated and refluxed at 110 1C for 24 h.
Finally, the acid- and/or base-functionalized LPMSN was collected by
filtration, washed with toluene several times in order to remove the
residual reactant, and dried in vacuum. The resulting samples were called
LPMSN-NH2 and LPMSN-SH. Then, the LPMSN-SH was oxided to become
LPMSN-SO3H by modifying a published procedure.67 Typically, 0.5 g
of LPMSN-SH was added to the mixture of hydrogen peroxide (10 mL),
deionized water (10 mL), and methanol (10 mL). The mixture was stirred
at room temperature for 12 h. After that, the resulting precipitate was collected by filtration, washed with deionized water several times and dried in
vacuum. The resulting sample was named LPMSN-SO3H. LPMSN-SO3H
and LPMSN-NH2 are used as acid and base solid catalysts, respectively,
in this study. For preparation of bi-functionalized LPMSN exhibiting
both acid and base groups (denoted as LPMSN-Both), APTMS was grafted
onto the pre-synthesized LPMSN-SO3H using the same grafting process
described above.
1.4.2
Conversion of Cellulose, Cellobiose, Glucose, and

Fructose using Bi-functionalized MSNs
The cellulosic conversion includes pre-treatment and reaction. For pretreatment, cellulose (15 mg) was added into [EMIM]Cl (150 mL), and the
whole mixture was heated at 120 1C for 0.5 h with stirring for dissolution of
cellulose. For reaction, LPMSN-based catalysts (4 mg) and water (16.67 mL)
were added to the cellulose/[EMIM]Cl solution while keeping heating
at 120 1C for another 3 h. All reactions were repeated three times and
the average yields of products were obtained. After the optimization of the
reaction conditions beforehand, the amount of catalyst was determined as
4 mg. The conversion process for cellobiose, glucose and fructose was the
same as that for cellulose except for exclusion of the pre-treatment step.
When using glucose and fructose as reactants, water did not be added into
the reaction systems.
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Chapter 1
08:23:53.
1.4.3
Characterization of the Bi-functionalized MSNs
Before functionalizing LPMSN with other functional groups, we qualitatively

and quantitatively investigated the amounts of hydroxyl group in the LPMSN
using 29Si and 13C solid-state NMR. As shown in the 29Si NMR spectra,
LPMSN exhibited Q3, Q4, T3 and T2 bonds, indicating that there are SiOH
and SiOC bonds in the material. Since 3-aminopropyltrimethoxysilane
(APTMS) was added during the synthesis of LPMSN, the SiOC bonds
should be due to the presence of APTMS. For functionalization of LPMSN
with acid (SO3H) or base (NH2) groups, the as-synthesized LPMSN was further reacted with an organosilane 3-(mercaptopropyl)trimethoxysilane
(MPTMS) or APTMS, respectively. As shown in the 13C NMR spectra of
LPMSN-SO3H (Figure 1.8a), three peaks at 11, 18 and 54 ppm correspond to
the carbons of the SiCH2CH2CH2SO3H from left to right, respectively,
indicating the appearance of the acid functionality. On the other hand, there
are three distinct peaks at approximately 11, 22 and 42 ppm representing the
carbons of the SiCH2CH2CH2NH2 from left to right, respectively,68 as
depicted in the 13C NMR spectra of LPMSN-NH2, proving the existence of the
base functionality (Figure 1.8b). The peak of around 71 ppm indicates the
existence of Brij97 residue.
Since the as-synthesized LPMSNs also exhibit base functionality, we
quantified the amounts of functional groups for all four samples (i.e.,
LPMSN, LPMSN-SO3H, LPMSN-NH2 and LPMSN-Both) by 29Si NMR in order
to distinguish the degree of dierent functionality. After deconvolution of
29
Si NMR peaks, we calculated the amounts of hydroxyl group and functional
group on the surface of each sample. As summarized in Table 1.4, on the
basis of the functionality of LPMSN (i.e., 1.06 mmol g1), LPMSN-Both exhibited the highest amount of functional groups (i.e., 2.32 mmol g1), indicating the successful addition of both acid and base groups. Although
LPMSN contains base groups (from APTMS during synthesis), the amount of
its functional group is less than LPMSN-NH2 that was further grafted with
APTMS. In addition, the surface areas and pore sizes of LPMSN-SO3H,
(a)
Figure 1.8
(b)
13
C solid-state NMR spectra of (a) LPMSN-NH2 and (b) LPMSN-SO3H.
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Table 1.4
08:23:53.
Samples
LPMSN
LPMSNNH2
LPMSNSO3H
LPMSNBoth
21
Summary of porous properties, acidity, and surface functionality of

LPMSN-based catalysts.
Specific
surface
area/m2 g1
Pore
size/nm
Acidity/pKa
Functional
group/mmol g1
Hydroxy
group/mmol g1
233.2
166.3
31.4
32.2
2.04.8
9.315
1.06
1.67
6.12
5.28
170.0
28.1
0.82.0
1.35
5.14
63.0
26.7
7.79.3
2.32
2.51
LPMSN-NH2 and LPMSN-Both decreased as compared to those of LPMSN,

indicating a pore filling eect upon functionalization (Table 1.4).69
The acidity of each LPMSN catalyst was estimated using following process.
Samples were added into properly chosen indicator solution, and the color
change of the solution was observed. As summarized in Table 1.4, the sequence of acidity (i.e., lower pKa value) is LPMSN-SO3H4LPMSN4LPMSNBoth4LPMSN-NH2, indicating that LPMSN-SO3H is the strongest acid
catalyst and LPMSN-NH2 is the strongest base catalyst. Although LPMSN also
contains NH2 groups, the silanol groups on the surface of LPMSN would
provide acidity, giving a weak acid property in total.
1.4.4
Cellulosic Conversion by using LPMSN-based Catalysts
Fructose (15 mg) and LPMSN-based catalysts (4 mg) were added into
[EMIM]Cl (150 mL), and the whole mixture was heated at 120 1C for 3 h. As
shown in Figure 1.9a, the yields of HMF converted from fructose with the
presence of four LPMSN-based catalysts were similar with each other (in
the range around 6670%). It has been considered that an acid catalyst is
necessary for the dehydration of fructose to produce HMF. However, we
suggested that fructose could be easily converted into 5-HMF in the ILs
system with a high temperature (120 1C) because such conditions (ILs and
high temperature) favor dehydration. Therefore, there is no dierence
between all LPMSN-based catalysts. Other groups have also reported similar
findings.
The yields of HMF converted from glucose with the presence of four
LPMSN-based catalysts are shown in Figure 1.9b. It can be clearly seen that
the cases with LPMSN-Both and LPMSN-NH2 catalysts exhibited the highest
yield around 13%, in contrast to that of LPMSN-SO3H (ca. 10%) and LPMSN
(ca. 7%). The conversion of glucose to HMF involves two steps: isomerization
of glucose to fructose and dehydration of fructose to HMF. In general, base
catalysts are helpful for isomerization of glucose to fructose.51 From the
result of fructose-to-HMF conversion, we have confirmed that four dierent
LPMSN catalysts had a similar eect on the dehydration of fructose to HMF;
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08:23:53.
(a)
(c)
Figure 1.9
Chapter 1
(b)
(d)
Yields of products converted from dierent reactants with the presence

of four LPMSN-based catalysts. (a) Fructose-to-HMF, (b) glucose-to-HMF,
(c) cellobiose-to-HMF, and (d) cellulose-to-HMF conversions.
in other words, HMF can be easily converted from fructose in our reaction
system. Therefore, the high HMF yields for the cases using LPMSN-Both and
LPMSN-NH2 indicate that base catalysts indeed promote the production of
fructose converted from glucose, and the glucose-to-fructose conversion can
be regarded as the rate-determining step in the glucose-to-HMF conversion.
To stimulate the structure of pre-hydrolyzed cellulose, we used cellobiose
as the reactant and studied its conversion with the presence of LPMSN-based
catalysts. The yields of glucose and HMF converted from cellobiose are
shown in Figure 1.9c. It can be seen that the LPMSN-SO3H exhibited the
highest yields of both glucose and HMF (25.6 and 18.9%, respectively). The
cellobiose-to-HMF conversion contains three steps: hydrolysis of cellobioseto-glucose, isomerization of glucose-to-fructose and dehydration of fructose
to HMF. Because acid catalysts can facilitate the first step, we suggest that it
is the reason why the highest yield of glucose appeared in the case of
LPMSN-SO3H. In addition, it can also be proposed that the cellobiose-toglucose is the rate-determining step of the three reactions. Therefore, catalysts with stronger acidity (i.e., LPMSN-SO3H and LPMSN) would favor the
production of glucose that was then converted to HMF, resulting high yields
of glucose and HMF.
We further directly used pre-hydrolyzed cellulose as the reactant and
performed the cellulose-to-HMF conversion in ionic liquid system with the
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Figure 1.10
23
Yields of cellobiose, glucose, and 5-HMF converted from cellulose using

a LPMSN-NH2 and LPMSN-SO3 mixed catalyst (Mixed) and a LPMSNBoth catalyst.
presentence of four LPMSN-based catalysts. As shown in Figure 1.9d, the

high yields of glucose and HMF were found in the cases of LPMSN-SO3H
(35.8 and 19.2%, respectively) and LPMSN-Both (36.3 and 14.7%, respectively). It is predictable that LPMSN-SO3H showed the highest eciency
toward cellulosic conversion because it exhibits the strongest acidity that can
facilitate the hydrolysis of cellulose. In fact, several groups have also synthesized SO3H-functionalized ILs for eective cellulosic conversion.70 However, it is surprising to us that the LPMSN-Both also provided high yields of
glucose and HMF, even its acidity is less than LPMSN-SO3H and LPMSN.
Since the cellulosic conversion involves a series of complicated reactions
that need dierent acid and base catalysts in each step, we propose that the
enhanced ecacy of LPMSN-Both could be attributed to the cooperative
catalysis of both acid and base functional groups in the LPMSN-Both. In
order to prove our hypothesis, we used a mixture of LPMSN-SO3H and
LPMSN-NH2 (1 : 1 in weight ratio) as the catalyst for the cellulose-to-HMF
conversion at the same reaction conditions. The reaction ecacy of the
mixed catalyst was compared with that of LPMSN-Both. As shown in
Figure 1.10, the yields of cellobiose, glucose, and HMF for the case of mixed
catalyst were all similar to those for the LPMSN-Both case, indicating that
the acid-and-base mixed catalyst exhibited the same ecacy as acid- and
base-containing catalysts. The results above indeed prove that the unusual
catalytic enhancement is a strong indication of the existence of cooperation
between the acid (SO3H) and base (NH2) groups in our LPMSN-Both system.
1.5 Conclusions
In this chapter, we have demonstrated the successful synthesis of multifunctionalized MSNs as eective, reliable, and re-usable solid catalysts for
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24
Chapter 1
cellulosic biomass conversion. In the enzyme-assisted catalytic system, we

optimized the reaction conditions for cellulase-immobilized solid catalysts
in cellulosic hydrolysis. For the first time, carboxyl-group-functionalized
MSNs with large pore size of 40 nm were synthesized and used to chemically
link cellulase. The proposed cellulase-assisted biocatalyst exhibits a high
cellulose-to-glucose conversion eciency (over 80%) with outstanding stability. In the chemical-assisted catalytic system, we demonstrated the
synthesis of MSNs with both acid and ionic liquid groups. Such bifunctionalized MSN solid catalysts have enhanced the production of HMF
from fructose dehydration in mild conditions using DMSO as a solvent. The
kinetics study has indicated that our bi-functionalized MSN could accelerate
fructose dehydration by reducing the activation energy required. In addition,
we also demonstrated the synthesis of large-pored mesoporous silica
nanoparticles (LPMSN) and functionalization of LPMSN with acid, base, and
both acid and base groups. The functionalized LPMSN-based catalysts have
showed enhanced catalytic ecacy toward cellulosic conversion including
fructose-to-HMF dehydration, glucose-to-fructose isomerization, and cellobiose-to-glucose hydrolysis. The bi-functionalized LPMSN enhanced the
yields of glucose and HMF directed converted from cellulose, indicating the
cooperative catalytic ability. We envisage that the multi-functionalized
LPMSN materials could serve as new selective catalysts for other important
reactions.
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08:23:58.
CHAPTER 2
Mesoporous Silica Supported

Single-site Catalysisy
PRANAW KUNAL AND BRIAN G. TREWYN*
Department of Chemistry and Geochemistry, Colorado School of Mines,
Golden, CO 80401, USA
*Email: btrewyn@mines.edu
2.1 Introduction
Rapid increases in the cost of feedstock chemicals, precious metals, and
recent environmental concerns about chemical waste have caused a shift
from homogeneous catalysis to heterogeneous catalysis where stability and
recyclability are clear advantages. The times of utilizing stoichiometric
reagents for organic chemical transformations to convert starting reagents to
products are long gone. Today, optimized catalysts are critical to maximize
product yield and minimize the thermal and capital expenses that contribute
to increased chemical costs. Many highly ecient and selective catalysts
have been developed in the last three decades establishing the field of
catalysis. Among these, homogeneous catalysts, mainly organometallic,
enjoyed a substantial growth and were used with diverse reactive reagents to
produce a large number of fine chemicals. The significant drawbacks of
homogeneous catalysis include challenging molecular synthesis, diculty in
separating and recycling, and poor thermal stability to name a few. The
advantages of homogeneous catalysis are the feasibility of following
reactions via spectroscopic methods to gain an understanding of the real
y
Electronic supplementary information (ESI) available. See DOI: 10.1039/9781849737494.

28
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Mesoporous Silica Supported Single-site Catalysis
29
active species, transition states, and mechanistic details, good product

selectivity, and single-phase reaction conditions. The sheer volume and
capacity common to the petroleum and chemical industries make utilizing
rationally designed homogeneous catalysts prohibitively expensive; i.e.,
continuous flow reactors, which are often the reactors used in high-capacity
synthesis and cracking systems, are not compatible with homogeneous
catalysts.
Heterogeneous catalysis has been a major factor in the development of
sustainable processes in fuel and fine chemical syntheses. The advantages of
heterogeneous catalysis over homogeneous include easier separation,
recyclability, decreased level of metal contamination in the products and
selectivity based on substrate and structural parameters. One important
example of heterogeneous catalysts is inorganic mesoporous materials.
These materials have been extensively researched for the past two decades as
supports for a variety of dierent active species. The research in the field of
mesoporous silica materials has been ever-growing since the discovery of the
MCM family of mesoporous materials by the Mobil Corporation.1,2 A series
of MCM-type mesoporous silica materials with tunable pore sizes and pore
morphology were developed by varying surfactants as structure-directing
templates. For example, MCM-41-type materials consisting of hexagonal
channels and MCM-48-type materials with cubic pores were synthesized.
Having a high surface area, being easily controllable, and having relatively
uniform and narrow pore-size distributions, these materials were eectively
utilized for various applications such as drug delivery, enzyme encapsulation, catalysis, sensors, and nanoelectronics.310 Over the last decade other
mesoporous silica materials like SBA-, MSU-, FSM-, and MSN-10-type
materials have been developed and have been used for variety of
applications as well.1114
2.2 Synthesis and Structural Aspects of Mesoporous

Silica
Figure 2.1 shows the schematic formation of mesoporous silica in steps. The
acidic or basic medium used for the synthesis of these materials first leads
to the formation of self-assembled micelles (hexagonal array shown in
Figure 2.1), followed by interaction with a silica source during hydrolysis and
Figure 2.1
The formation mechanism of mesoporous silica materials.
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Chapter 2
condensation which leads to an inorganic mesostructured solidsurfactant

composite. The final step involves surfactant removal either by calcination
or acid extraction resulting in the formation of inorganic mesoporous silica
materials.
The synthesis of mesostructured materials can be controlled by varying
the organicinorganic interactions and cooperative assembly of the silica
species and surfactants. The final mesostructures are dependent on the
surfactant liquid-crystal phases or silicasurfactant liquid-crystal-like
phases. Often the critical micelle concentration (CMC) values for a given
surfactant need to be between 0 and 20 mg L1 in order to achieve ordered
mesostructures.15 CMC values between 20 and 300 mg L1 can be strategically reduced to give ordered mesostructures. Surfactants with large CMC
values usually result in cubic mesostructures and it is dicult to form
ordered mesostructures if the CMC values are above 300 mg L1. The final
mesostructures formed from ionic surfactants are explained by using
packing parameter values (g value). The g value can be calculated using
g V/(a0l), where V is the total volume of the hydrophobic chains (tail region)
and cosolvent (organic molecules) between the chains, a0 is the eective
hydrophilic head group area at the aqueousmicelle surface, and l is the
surfactant tail length. Cubic (Pm3n) and 3D hexagonal (P63/mmc) mesostructures have g valueso1/3, 2D hexagonal (p6mm) and cubic bicontinuous
(Ia3d) have g values between 1/3 and 1/2 and lamellar with gE1/2 1.
The hydrophilic/hydrophobic volume ratios (VH/VL) are suggested for the
formation of dierent mesophases involving non-ionic surfactants. Block
copolymers such as F108, F98, F127 and Brij 700 with high VH/VL ratios
usually direct the synthesis of cage-type cubic mesoporous materials with
high topological curvature. Medium hydrophilic/hydrophobic volume ratio
block copolymers such as P123, B50-1500 form mesostructures with medium
curvature like 2D hexagonal or 3D bicontinuous cubic (Ia3d). Tailoring the
pore size of ordered mesoporous materials is one of the most remarkable
features.16 Several methods have been used to control the pore sizes of
mesoporous silica as illustrated in Table 2.1.15
Hydrophobic groups in the surfactants play a large part in controlling the
pore size of the mesoporous materials. Larger pore sizes are observed when
the length of alkyl chains of cationic quaternary surfactants is increased; for
example, when the surfactant chain length is increased from C8 to C22, the
pore diameter derived from the BarrettJoynerHalenda (BJH) method
increases from 1.6 nm to 4.2 nm.17 The pore size of MCM-48 mesostructures
can be tuned by adjusting the carbon chain length in a cationic gemini
surfactant increased from 1.6 nm to 3.8 nm.18 Mesoporous silicas synthesized using block copolymers have larger pore sizes as compared to low
molecular weight surfactant systems. Pore sizes for conventional PEO-PPOPEO triblock copolymers are increased with growing molecular weights of
the hydrophobic blocks rather than those of the copolymers.19 Diblock
copolymers often lead to larger pore sizes than triblock copolymers of
similar molecular weight because the PPO chains of the triblock copolymers
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Table 2.1
31
Pore sizes of ordered mesoporous structures obtained using dierent

methods.
Pore size/nm
Method
25
Surfactants with dierent chain lengths

Quaternary cationic salts and neutral organoamines
Long-chain quaternary cationic salt surfactants
High-temperature hydrothermal treatments
Charged surfactants with the addition of organic swelling agents
such as TMB and mid-chain amines
Non-ionic surfactants
Triblock copolymer surfactants
Secondary synthesis, for example wateramine post-synthesis
High-molecular-weight block copolymers such as PI-b-PEO,
PIB-b-PEO and PS-b-PEO triblock copolymers with the addition of
swelling agents such as TMB and inorganic salts
Low-temperature synthesis
47
58
28
420
411
1027
tend to bend during aggregation. Pore-size tuning of MCM-41 materials can

also be achieved by using a mixture of two surfactants with alkyl chain
lengths ranging from C8 to C22. The range of pore sizes from the resulting
materials obtained is between the pore sizes of the two surfactants when
used individually. Pore sizes increase upon adjusting the fraction of the
surfactant with the larger chain length.17 A good sense of the suitability of a
swelling agent while using a particular surfactant can be made by considering the structure of the surfactant. For instance P123 has B70 wt%
of hydrophobic PPO domains that can accommodate the hydrophobic
swelling agent whereas F127 has only B30 wt% of hydrophobic PPO.16 Large
organic hydrocarbons such as 1,3,5-trimethylbenzene (TMB), dodecane,
triisopropylbenzene (TIPB), tertiary amines, and polypropylene glycol can act
as micelle swelling agents/expanders to increase the pore size.2023
The challenges of using the micelle expanders include the tendency to
reduce the mesoporous structure order or even change the structure type: for
example, changing SBA-15 to mesocellular foam.2025 If the swelling action is
too strong, well-defined large pore structures are not formed and no noticeable pore enlargement occurs if the swelling action is weak.2628 Only a
limited solubilization of swelling agents in the pore-forming micelles leads
to the retention of highly ordered mesoporous structures with a significant
increase in pore size.16 For optimum swelling action, Pluronic P123 should
be used with swelling agents less soluble in pluronic surfactants like TIPB or
cyclohexane; similarly Pluronic F127 should be used with swelling agents
more soluble in pluronic surfactants like xylene, ethylbenzene, and
toluene.2832 For ordered mesostructures, the addition of TMB increases the
pore size to 13 nm for SBA-15-type materials and to 6 nm for MCM-41-type
materials. Trimethylbenzene increases the pore size to 40 nm in acidic
triblock copolymer systems and to 10 nm in basic CTAB surfactant systems.
The addition of sodium dioctyl sulfosuccinate (AOT) and TMB leads to
highly ordered 2D hexagonal mesoporous silicates with 11 nm pores.33
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32
Chapter 2
The pore diameter also expanded when other substances were incorporated
that can be solubilized in the micelle core. For example, super critical (sc)
carbon dioxide was used as a swelling agent for tuning the pore size during
silicate hydrolysis for hexagonal mesoporous silica.34 It was also discovered
that incorporation of a specific concentration of metallic nanoparticles in
the system where P123 was used as the surfactant and tetraethyl orthosilicate (TEOS) as the silica source could also expand the mesochannels.35
Additionally, the pore size can be tailored by changing the initial synthesis
temperature and hydrothermal treatment conditions.27,36 Carrying out the
synthesis at a low temperature (B25 1C) showed that the combination of
pluronic block copolymers with the appropriate swelling agents form
mesoporous silica with an unusually large pore size.37 Lowering the initial
temperature from 2540 1C to 15 1C in the synthesis of FDU-12 templated by
F127 in the presence of TMB led to a doubling of the pore diameter to
27 nm.36 Hydrothermal temperature can significantly aect pore size; the
pore sizes of SBA-15 can be altered from 4.6 nm to 10 nm and from 9.5 nm to
11.4 nm by increasing the hydrothermal temperature from 70 to 130 1C and
by increasing the time from 6 h to 4 days.3841 Similar trends were seen for
mesoporous silicates with body centered cubic Im3m mesostructures and for
cubic bicontinuous Ia3d mesostructures when using F127 and the triblock
copolymer P123 as a template with butanol as a co-solute, respectively.42,43
Increasing the hydrothermal treatment conditions from 45 1C and 24 h to
100 1C and 48 h resulted in SBA-16 with larger mesopores, thinner pore
walls, and reduced intrawall micropores. The pore sizes of mesoporous silica
with Ia3d symmetry could be tuned from 4 to 10 nm by increasing the
hydrothermal temperature from 65 to 130 1C.42
2.2.1
Functionalization Techniques for Mesoporous Silica
There are two common techniques used to functionalize the surfaces of

mesoporous silica with organic moieties for supporting single-site catalytic
groups. The first approach, post-synthesis grafting, is the more popular
method due to fewer synthetic variables that go into the preparation.
As is shown in Scheme 2.1b, either a modified homogeneous catalyst or
a metal-free organic ligand is covalently immobilized on the surface of
presynthesized mesoporous support through a silylation reaction, typically
in a moisture-free environment. The lack of moisture is critical to avoid selfcondensation of organosilanes. While the porous structure stays intact, the
placement of the ligands/catalysts may not be uniform, but focused on the
external surface and near the pore openings. This phenomenon is typically
dependent on the pore size and the freedom of mass transport into the
pores. The reactivity of the surface silanol groups is a diusion-dependent
characteristic and the kinetically most accessible regions are on the exterior
and pore openings.
The other approach, in situ co-condensation, is a direct synthesis method
in which the organic functional group (organoalkoxysilane) is introduced to
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08:23:58.
(a)
(b)
Scheme 2.1
Schematic illustration of the two most common surface functionalization

techniques for mesoporous materials: (a) the in situ co-condensation
method, and (b) the post-synthesis grafting method.
an aqueous solution (acidic or basic) of template-forming surfactant along

with the silanol precursor (i.e. tetraethylorthosilicate, TEOS), illustrated in
Scheme 2.1a. The condensation of both the organoalkoxysilane and TEOS
occurs simultaneously (co-condensation) leading to uniform distribution
of the organic ligand on the surfaces of the mesoporous materials. There
are some limitations to this method: firstly, only water soluble organic
functional groups can be used and they need to tolerate pH extremes since
either acids or bases are catalysts for the silicate hydrolysis; secondly, the
incorporation of bulky organic functional groups is not always successful
because the bulky groups interfere with silica condensation; finally,
the amount of functional group incorporated in the mesoporous material
this way cannot exceed 25% surface coverage without having a negative
eect on the structure integrity. Some ingenious recent publications will
be discussed within this chapter that report chemical methods to measure
the spatial independence of ligands using the in situ co-condensation
method.
2.3 Single-site Heterogeneous Catalysts

The types of supported catalysts can be divided into two major categories:
single-site heterogeneous catalysis (SSHC) and multi-site heterogeneous
catalysis (MSHC). While these are general categories, they are suitable for
this review which focuses on SSHC. Multi-site heterogeneous catalysis, also
called connected-site, is defined as closely packed atoms of reactive metal,
metal oxides, alloys and, rarely, halides. Spatial independence is not a
characteristic of this type of catalyst and strong interactions occur between
active sites, making kinetic and thermodynamic analyses very challenging.
In contrast, SSHC consists of spatially independent active sites and lacks
interactions between active sites, making the interactions between each
supported active site and reactant equivalent. This review will discuss SSHC
supported on various mesoporous materials. We will focus, in detail, on
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34
Chapter 2
several groundbreaking studies that have been recently published in the

peer-reviewed literature. Since the first report by Mazzei et al.44 to immobilize rhodium cationic complexes on clays for carrying out asymmetric
hydrogenation of substituted acrylic acid, a large volume of work has been
published and shared.45 Two important structural features of SSHC are
spatial separation and consistency in the structures of the active sites. This
ensures constant energetic interaction between each active site and the
reactant, thereby minimizing additional variables that frequently complicate
catalytic studies. In many conditions, these catalysts are superior to MSHC
where significant energetic interactions between the active sites lead to
additional phenomena, i.e. oscillatory and chaotic behavior, making the
chemistry tedious to interpret and comprehend even for simple chemical
processes. While characterizing these catalysts remains challenging, computational and kinetic measurements of SSHC are less problematic than
those of close-packed heterogeneous catalysts.4547 One of the remarkable
features oered by these catalysts is spatial restriction in the pores of
mesoporous materials which has been utilized for asymmetric catalysis.48
This review of single-site heterogeneous catalysts will discuss both metalcoordinated and organic-ligand-tethered mesoporous silica nanoparticles as
advanced catalysts.
2.3.1
Examples of Single-site Catalysts
Huang et al. supported two mutually incompatible groups; basic primary

amines and sulfonic acids on the same support by taking advantage of
spatial separation between internal and external surfaces of the mesoporous
silica nanoparticles (MSNs).49 The two surfaces of MSNs were functionalized
independently through synthetic design. The internal surface was decorated
by adding the desired silane in situ along with the silica monomer and the
external surface was decorated by reacting the desired silane postsynthetically prior to removal of the surfactant from the MSNs. Scheme 2.2
below shows the synthesis of one of the acidbase catalysts, which was
prepared by co-condensing the silica monomer, TEOS, and 3-mercaptopropyltrimethoxysilane (MPTMS) in the presence of the pore-templating
surfactant, cetyltrimethylammonium bromide (CTAB), under basic reaction
conditions followed by post-synthetic grafting with 3-aminopropyltrimethoxysilane (APTMS). The presence of CTAB in the mesoporous channels directs the APTMS to the external surface and the concentration of
sulfonic acid was kept equal to the amine group.
Another MSN-based catalyst was synthesized where APTMS was cocondensed and MPTMS was grafted using similar methods to those shown
in Scheme 2.2 to form APMSN-SA. The mesoporous structure was maintained on these synthesized materials with type IV isotherms, high surface
areas and pore volumes, and narrow pore-size distributions. The successful
incorporation of organic functional groups was observed when the product
was characterized using powder X-ray diraction (XRD), nitrogen sorption,
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(CH3O)3Si(CH2)3SH
(STMOS)
+
Si(OCH2CH3)4
35
1) CTAB,NaOH,H2O
(TEOS)
2) APTMOS, toluene
(CH2)3NH2
(CH2)3NH2
3) H2O2,CH3COOH
4) CTAB removal
5) 150 oC, 0.1 mmHg
H2N(H2C)3
H2N(H2C)3
SAMSN-AP
Scheme 2.2
Table 2.2
Synthesis of bifunctional MSN having sulfonic acid groups on the

internal surface and organic amine groups on the external surface.
Cascade reaction consisting of acid-catalyzed hydrolysis and basecatalyzed Henry reaction. Reaction conditions: catalyst, 100 mg
(1.5 mmol); H2O, 1.5 mmol; CH3NO2, 1 ml; 80 1C; 24 h.
OCH3
OCH3
O2N
NO2
CHO
Base
Acid
O2N
H 2O
O2N
CH3NO2
Entry
Catalysta
Bb (%)
Cb (%)
Conv. of Ab (%)
1
2
3
4
5
6
7
8
9
10
SAMSN-AP
APMSN-SA
SAMSN/APMSN
SAMSN
APMSN
SAMSN-AP/AP
SAMSN-AP/PTSA
APMSN-SA/AP
APMSN-SA/PTSA
MSN
2.3
1.9
4.5
100
0
0
100
0
100
0
97.7
98.1
95.5
0
0
0
0
0
0
0
100
100
100
100
0
0
100
0
100
0
a
b
AP: 1-aminopropane, PTSA: p-toluenesulfonic acid.

Conversions and yield determined using gas chromatography (GC).
and 13C and 29Si solid-state NMR spectroscopy. Organic functional group
loading was quantified via elemental analysis. The activity for a one-pot
reaction sequence involving acid-catalyzed hydrolysis of an acetal followed
by a subsequent base-catalyzed Henry reaction was tested as shown in
Table 2.2.
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36
Chapter 2
Both bifunctional materials, SAMSN-AP and APMSN-SA, gave 100% conversion of A and a very high yield of the desired product C by catalyzing the
reaction in a cascade fashion. The catalytic activity for the same reaction was
similar for physically mixed APMSN and SAMSN (see entry 3 in Table 2.2).
However, when a single functionality was incorporated on the MSN surface
(either acid or base) there was a lack of measured product C formation.
SAMSN-AP or APMSN-SA when combined with the homogeneous analogues
of sulfonic acid (PTSA) and propylamine (AP) gave no product C either, since
the free acid and base molecules neutralized the corresponding heterogeneous base or acid. These catalysts were recyclable up to five times with a
negligible decrease in catalytic activity. The kinetics of the catalysts were
studied as well: incorporating both acidic and basic groups introduced by
the co-condensation method showed better reactivity (TOF, turnover
frequency) than the analogous catalysts where grafting was used to tether the
same groups onto the external surface of the MSNs (Figure 2.2a). These
results indicate that diusion limitations during the catalytic cycle might be
minimized and the dispersion or surface coverage of the catalytic sites might
play a role in the activity. To investigate this, a series of catalytic reactions were
run using MSN-based catalysts with five dierent concentrations of amines
(Figure 2.2b). The catalytic activity by measuring TOF decreased steeply as the
surface coverage of the catalysts increased, showing a direct relationship
between the catalysts activity and the catalyst coverage on the MSN surface.
Rothenberg et al. also used MSN to support two antagonistic functional
groups:50 they reported the synthesis of MSN-supported catalysts with
site-isolated amine and phosphotungstic acid groups. Amine groups were
attached to SBA-15 using the grafting method and the resulting material was
then treated with a methanolic solution of the phosphotungstic acid
(H3PW12O40) which led to a bifunctional (acidbase) catalyst as shown in
Scheme 2.3.
This bifunctional catalyst demonstrated high conversion and yield for
the acid-catalyzed deacetalization of benzaldehyde dimethylacetal followed
Figure 2.2
(a) Turnover frequency of the acid and base catalysts located on either
the internal or external surfaces of SAMSN-AP and APMSN-SA. (b) Fitted
curve of base activity versus base concentration on the APMSN surface.
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Scheme 2.3
37
SB
SAB
Synthesis of bifunctional catalyst by grafting APTMS to SBA-15 followed

by controllable immobilization of H3PW12O40 using the NH2 group of
immobilized APTMS.
NO2
1.SAB,CH3NO2
-H2O
OCH3
OCH3
SAB,H2O
-2CH3OH
CHO
NC
CN
2.SAB,CH2CN2
-H2O
Scheme 2.4
One-pot tandem deacetalization followed by (1) a Henry reaction and

(2) an aldol reaction.
by the base-catalyzed Henry reaction between 4-benzaldehyde and nitromethane, and base-catalyzed aldol condensation of 4-benzaldehyde and
malononitrile as shown in Scheme 2.4.
The catalyst activity for the tandem reaction was governed by the tunable
ratio of aminopropyl (AP) groups and phosphotungstic acid (HPW) groups
on the MSN support. When the AP/HPW ratio on MSN was tuned to 2 : 1, half
of the total amine on the MSN surface was used for immobilizing polyacids
whereas a ratio of 1 : 1 stopped the reaction sequence at step 1 with the
formation of benzaldehyde as all the AP groups of the MSNs were used for
polyacid immobilization, leading to only acidic sites being present on the
MSN catalyst surface.
Asefa et al. developed MSN-based bifunctional, highly ecient catalysts
for the Henry reaction.5153 The catalysts were prepared by post-synthetic
grafting of 3-APTMS on MCM-41-type mesoporous silica materials at
elevated temperature in ethanol and toluene and were labeled as AP-E1,
AP-T1, and AP-T2 as described in Scheme 2.5.
The organoamine loading was the highest for AP-T2 (4.3 mmol g1)
followed by AP-T1 (4.1 mmol g1), and AP-E1 had the lowest loading of
1.3 mmol g1. Catalytic studies for the Henry reaction showed that AP-E1
was a superior catalyst to AP-T1 and AP-T2. Taking into consideration the
fact that AP-E1 had the lowest density of catalytically active organoamine
groups of the three catalysts synthesized, it was thought that surface silanol
groups activated the carbonyl group of benzaldehyde to facilitate the
nitroaldol reaction as shown in Scheme 2.6. Grafting additional organic
groups led to significantly reduced catalytic eciency indicating the
importance of well-isolated active sites and silanol groups for improved
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38
Chapter 2
AP-E1
AP-T1,AP-T2
Scheme 2.5
(a)
Reaction scheme for post-synthesis grafting aminopropyl groups in

ethanol at 78 1C (AP-E1) and in toluene at 78 1C (AP-T1) and in refluxing
toluene at 112 1C (AP-T2).
(b)
AP-E1
O
O O O OO
O
Si
Si
Si
Si Si
O
O O
O HO O
O O
O
O
H
O
Si T2
O Si O
Si T3 H
O
H
O
CH2NO2
H
CH2NO2
H
N
+
2
NH3
AP-T1,AP-T2
O O O O O O O Si O
Si
Si
Si
Si
Si
OO
O
O
OO O
O O
O
Si T3
O HO
HO
Si T2 Si T3
Si T2
O
H 2N
H 3N
H2N
H 3N
CH2NO2
HO
HO
O
HO
Scheme 2.6
Proposed reaction mechanism illustrating the enhanced eciency of

(a) AP-E1 in the Henry reaction relative to (b) AP-T1 and AP-T2. The
presence of a significant number of spatially isolated silanol groups in
AP-E1 led to the activation of the carbonyl group of benzaldehyde for
nucleophilic attack.
catalytic eciency. Improved catalytic eciency was demonstrated on

samples with a higher surface area which contributed to lower ligand
loading. The authors also demonstrated that the nature of the solvent used
for grafting played a major role in the spatial distribution of the organoamines on the MSN surface: spatial distribution in ethanol occurred due to
the competition for the aminopropylsilane between ethanol which is a protic
polar solvent and hydrophilic surface silanol groups, whereas for toluene, a
non-polar aprotic solvent, aggregation of aminopropylsilanes occurred and
led to their preferential interaction with the silanol groups.
Bass and Katz used a thermolytic imprinting method to approach
sub-nanometre patterning of mixed organic functional groups within
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O
O
S
O
Si(OEt)3
08:23:58.
N
H
O
S
(EtO)3Si
Figure 2.3
NH
Si(OEt)3
S
(EtO)3Si
Si(OEt)3
S
Si(OEt)3
O
O
N
H
Si(OEt)3
(EtO)3Si
N
H
Si(OEt)3
Molecular imprints used by Bass and Katz for templating sub-nanometre

imprints in MSN. Grafting was used to tether these organic moieties to
the MSN surface followed by thermal deprotection of xanthate group to
thiol and carbamate group to amine resulting in materials termed 1-S,
2-S, 3-S, and 4-S.
discrete active sites on the MSN surface.54 The imprint 1 containing a

xanthate-protected thiol with the ethoxysilane group, which facilitates
grafting on to the MSN surface, was used. Also imprinting was achieved for
mixed functional groups; thermally labile carbamate, and xanthate groups
were simultaneously incorporated in the molecules 2, 3, and 4. Molecule
1 led to a single thiol group after deprotection by thermal treatment whereas
2 led to two thiol groups and one amine group and 3 and 4 both led to one
thiol and amine group each (Figure 2.3).
Solid-state UV-Vis (xanthate absorption seen at 280 nm) and 13C CP/MAS
NMR spectroscopy was used to characterize the molecules tethered on MSN
before and after the deprotection steps. 29Si CP/MAS NMR was used to
determine the degree of imprint condensation with T3/T2/T1 ratios of 25/55/
20 thus implying multiple point connectivity. The quantification of amine
and thiol groups was done by titration with perchloric acid and Ellmans
reagent and ratio of the two groups were found to be close to 1 : 1 for mixed
materials 3-S and 4-S and 2 : 1 for 2-S. The Ellmans reagent selectively
converted thiol groups to a nitrobenzoic acid moiety as shown in
Scheme 2.7; this acidic species showed an absorbance band at 332 nm in
solid-state diuse-reflectance (DR) UV-Vis absorption. The local organization
of functional groups on the imprinted materials was measured using
o-phthaldehyde as a selective probe for thiolamine pairs. Fluorescent
isoindole species were formed due to the reaction of o-phthaldehyde with one
thiol and one amine group, this species was confirmed by observing its
absorbance peak at 330 nm in solid-state DR UV-Vis spectra as well as a
fluorescence emission peak at 410 nm. The absolute amount of thiolamine
pairing was estimated by comparing the solid-state DR UV-Vis absorption
spectra of chromophore 7 with 6 (Scheme 2.7). The highest value of pairing was
observed for materials imprinted with thiolamine bifunctional moiety 4 as
compared to the materials prepared by grafting a 1 : 1 molar ratio of 3-MPTES
and 3-APTES and by grafting a 1 : 1 molar ratio of the corresponding xanthate
and carbamate silanes and thermally deprotecting them after grafting.
The reaction of o-phthaldehyde with thiolamine pairs was also used to
characterize the site isolation of imprinted sites. Carbamate imprint 2 was
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40
Chapter 2
(a)
NH2
(b)
SH
NO2
S
O2N
COOH
HOOC
08:23:58.
Si
O O OH
S
Si
HO O O
3-S
O
HOOC
COOH
O2N
O2N
S
S
S
S
Si
OH
Si
O
HO O O
Scheme 2.7
NH2
N
S
Si
O O OH
Si
Si
OH
HO O O O O
(a) Derivatization of thiol groups on 3-S using Ellmans reagent

yielded nitrobenzoic acid 6 bound to the surface. (b) Derivatization
of thiolamine pair by using o-phthaldehyde yielded fluorescent
chromaphore 7.
grafted onto the surface of two dierently functionalized MSNs, 8 and 9, but
with the same surface distribution and active sites; the uniformity between
the two surfaces was achieved by the synthesis of 9 directly by thermal
deprotection of 8. An increase in thiolamine pairing was seen in material 10
over 11 which has contributed to a greater tendency of carbamate silane
precursor 2 to condense on the MSN surface next to xanthate silane
precursor 1 as compared to the condensation of 2 next to tethered
mercaptopropyl groups (formed after thermal deprotection of 1 on the surface) as illustrated in Scheme 2.8. In contrast, the condensation tendency
shown by xanthate silane 1 next to carbamate silane 2 and primary amine
(formed by thermal deprotection of 2 on the surface) was the same. Thiol
amine pairing was also dierent based on the sequence of grafting, material
with 1 grafted first followed by 2 showed dierent pairing as compared to
the case when 2 was grafted before 1. Such dependences indicated a nonrandom distribution of imprints on the surface possibly driven by kinetic
phenomena or specific interactions between the surface species.
Cooperative heterogeneous catalysis is a remarkable concept; supporting
dierent functionalities on a heterogeneous support which may work
together in a cooperative way either to alter the reaction characteristics or to
assist in performing several steps of a reaction sequence. One of the reactions where this concept has been applied is the synthesis of bisphenols.
Bisphenol A (BPA) and bisphenol Z (BPZ) are important feedstocks in the
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:1
S
S
(EtO)3Si
NH
O
O
S
NH
S
O
O
S
NH
O
O
SH
NH2
N2, 250 oC
NH
SH
NH2
NH2
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
10
N2,250oC
O
O
HS
O
NH
HS
SH
(EtO)3Si
HS
NH
HS
SH
NH
Si
Si
Si
Si
NH
Si
Si
Si
Si
Scheme 2.8
HS
Si
Si
Si
NH2
HS
o
N2, 250 C
HS
NH2
SH
NH2
Si
Si
Si
Si
Si
Si
11
Interactions during condensation between carbamate 2 and immobilized xanthate 1 and mercaptopropyl species on
homologous surfaces 8 and 9 influenced the distribution of species on the final surfaces 10 and 11.
41
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42
Chapter 2
OH
OH
HO
HO
+
OH
o, p' isomer
08:23:58.
Bisphenol A
(p, p' isomer)
HO
OH
HO
OH
+
+
OH
Bisphenol Z
(p, p' isomer)
Scheme 2.9
o, p' isomer
Syntheses of bisphenol A (top) and bisphenol Z (bottom) utilizing

phenol and either acetone or cyclohexanone as starting materials.
plastics industry especially due to their use as monomers in polycarbonate

materials and epoxy resins. They are synthesized using an acid-catalyzed
condensation reaction between a ketone and a phenol leading to a p, p 0
isomer (desired product) and a o, p 0 isomer (byproduct). A schematic
representation for the formation of bisphenols is shown in Scheme 2.9.
The addition of thiols as cocatalysts has been shown to improve the
kinetics of the reaction for the formation of bisphenols as well as the
selectivity of the p, p 0 isomers.55,56 Davis et al. reported a novel route for
the synthesis of acid/thiol-paired heterogeneous catalysts by designing an
organosilane precursor which could be tethered to the support at two points
using the grafting method and could be cleaved later to deprotect the
catalytic sites.57 The bis-silane precursor having a disulfide group and an
aryl sulfonate ester group separated by two methylene groups was synthesized using the procedure outlined in Scheme 2.10.
To demonstrate that bis-silane 3 could be incorporated into MSN to form
an organic-inorganic hybrid material, the authors used SBA-15 as the starting material due to its high surface area, large pore diameter, and framework
rigidity and grafted the bis-silane (SBA-g3). A deliberate low loading
of B0.2 mmol g1 was achieved to ensure that the eect of pairing could be
observed. The XRD pattern of SBA-g3 showed three characteristic peaks of
hexagonally ordered mesopores. Complete nitrogen sorption results are
shown in Table 2.3 but, in particular, the surface area reduced to 230 m2 g1
from 860 m2 g1 and the pore size reduced to 5.8 nm from 6.3 nm after
grafting the large bis-silane. Such a large decrease in the surface area could
not be explained solely by the presence of organic surface groups, it was
likely that some pore openings were blocked by organic species making
them inaccessible to the adsorbent. The tethered organic fragment was
confirmed using 13C CP/MAS NMR spectroscopy, the 13C CP/MAS spectrum
of the grafted molecule matched well with the solution phase spectrum of
bis-silane 3 confirming the presence of intact bis-silane 3 after grafting. The
presence of T1, T2, and T3 sites from 29Si CP/MAS NMR analysis correspond
to the bis-silane 3 indicating its attachment to the surface at one, two, and
three points, respectively. Of these, T2 sites were the largest suggesting
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OH
OH
S
08:23:58.
SH
1
EtO
OEt
OEt
Si
SH
O
S
S
OH
S
O
S
S
EtO
OMe
Si
OMe
MeO
Si OEt
OEt
EtO
Table 2.3
Si OEt
OEt
Si
MeO
Bis-silane
Scheme 2.10
Cl
O S O
OMe
OMe
Synthesis of disulfide silane 2 and bis-silane 3 acid/thiol functional

groups used in the synthesis of MSN catalysts used for the formation
of selective bisphenols.
Catalyst characterization data.
Material
SBETa/m2 g1
Dpb/nm
SBA-15
SBA-g3
SBA-A
SBA-AT-p
SBA-AT-r
SBA-T
860
230
6.3
5.8
430
6.0
H1 c/mmol g1
0.20
0.21
0.13
SHd/mmol g1
SH/H1
0.19
0.12
0.32
0.90
0.92
Specific surface area, calculated using the BET method.

Average pore diameter, calculated from adsorption isotherm using the BJH method.
c
Acid loading, measured by ion exchange/titration.
d
Thiol loading, measured by reaction with Ellmans reagent.
b
that silanes are covalently bound to the surface at two points. The
confirmation that both the trialkoxysilane groups of 3 are attached to the
surface was deduced by the absence of T0 peaks, which would have appeared
at 41 ppm. Thermogravimetric analysis (TGA) in air was used for the
quantitative determination of the organic content of SBA-g3. After the
introduction of bis-silane 3 to the silica surface, deprotection was carried out
in one step using aqueous tris(2-carboxyethyl)phosphine hydrochloride
(TCEP HCl) leading to SBA-AT-p (Scheme 2.11).
The success of the deprotection step was confirmed using 13C CP/MAS
NMR spectroscopy. A comparison of 29Si CP/MAS NMR spectrum of SBA-AT-p
with SBA-g3 showed an increase in T3 signal due to further condensation of
alkoxysilane moieties in the aqueous condition used for deprotection, but T2
still remained the most intense peak. The surface area of SBA-AT-p increased
to 430 m2 g1 from 230 m2 g1 for SBA-g3 probably due to the removal of
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44
Chapter 2
O
S
S
08:23:58.
EtO
Si
O
SH
TCEP.HCl
H2O
O
HO
OMe
Si
EtO
Si
O
O
S
O
Si
OMe
O
SBA-g3
Scheme 2.11
SBA-AT-p
SBA-AT-p synthesized by deprotection from grafted disulfide/sulfonate

ester intermediate SBA-g3.
mercaptoethanol and also unblocking of some blocked pore openings. SBAAT-p was characterized for acid content and thiol content and the values are
shown in Table 2.3. Notably, the acid/thiol ratio was close to 1 in support of
this co-catalyst functionalization method.
For catalytic studies, catalysts containing (i) only thiol (SBA-T), (ii) only
arylsulfonic acid (SBA-A), and (iii) randomly distributed arylsulfonic acid and
thiol groups (SBA-AT-r) were also prepared as illustrated in Scheme 2.12.
The catalytic activity of various materials was tested for the synthesis of
bisphenols A and Z. For bisphenol A, the catalysts having both the thiol and
acid groups in close proximity on the same silica support for both organized
(SBA-AT-p) as well as randomly distributed (SBA-AT-r) exhibited similar activity but a remarkable advantage of the paired catalyst over the randomly
distributed catalyst was the selectivity (isomer ratio of 19.3 versus 15.2).
SBA-T was inactive for the catalysis of bisphenol A synthesis as there was no
acid group present, SBA-A showed some activity but low selectivity due to
absence of thiol sites, a physical mixture of SBA-A and SBA-T demonstrated
low activity and selectivity as the acid and thiol groups are unable to interact
except at the outer catalytic sites whereas PTSA was able to interact with
surface bound thiols by entering the pores. For bisphenol Z, a similar trend
was seen but the selectivity using SBA-T-p was more than three times higher
than the selectivity observed for SBA-AT-r. These data suggests that catalytic
cooperativity for the synthesis of bisphenol Z was more dependent on
acid/thiol distance than for bisphenol A.
The thermolytic molecular precursor (TMP) method is a unique and
ecient approach to attain single-site catalysts developed by Tilley et al. This
method was first used to synthesize non-mesostructured homogeneous
mixed elemental oxides, for example ZrO2 4SiO2 was prepared by thermally
decomposing Zr[OSi(OtBu)3] with the elimination of alkene and water as
shown in the following equation:58
D
ZrOSiOt Bu3 4 ! ZrO2 4SiO2 H2 CCMe2 6H2 O

A further development was made when mesostructured homogeneous
mixed elemental oxides were synthesized using a mixture of the molecular
precursors and toluene solutions of various block polyalkyne oxide copolymers. This was an important step forward as the synthetic solvent used
here was non-polar (toluene) which inhibited metal aggregation unlike
View Online

SH
SH
SBA-15
Toluene
Si OMe
MeO OMe
HO
08:23:58.
MPTMS
Si
O
O
SBA-T
O
O S O
O
O S O
OH
O S O
TCEP.HCl
H2 O
SBA-15
Toluene
MeO
45
Si
OMe
OMe
HO
Si
O
O
HO
SBA-g4
O
O S O
S
S
S
S
SBA-15
Toluene
Si
O
O
SBA-A
O
O S O
OH
O S O
HS
TCEP.HCl
H2O
Si
OMe
MeO OMe
Scheme 2.12
MeO
Si
OMe
OMe
HO
Si
O
O
HO
SBA-g2,4
Si
O
O
HO
Si
O
O
HO
Si
O
O
SBA-AT-r
Synthesis of SBA-T, SBA-A, and SBA-AT-r. Top: grafting 3-mercaptopropyltrimethoxysilane (MPTMS) onto SBA-15 generated SBA-T, containing only thiol sites. Middle: grafting sulfonate ester precursor 4
generated intermediate SBA-g4, which was hydrolyzed to SBA-A, containing only acid sites. Bottom: grafting both disulfide 2 and sulfonate
ester 4 generates intermediate SBA-g2, 4 which was deprotected to
form SBA-AT-r, containing randomly distributed acid and thiol sites.
aqueous solvents.59 Tilley et al. also covalently attached well-defined oxygenrich organometallic molecular precursors onto the mesoporous silica
support using post-synthetic grafting; this approach not only controlled the
structure of the catalytic site on the molecular level but also led to an
excellent spectroscopic model for the catalytic active sites.6065 Tilley and
Rioux et al. recently reported Pd(II) centers supported on mesoporous silica
using the TMP method,66 where two novel tris(t-butoxy)siloxy palladium(II)
complexes of the form (4,4 0 -di-tert-butyl-2,2 0 -bipyridyl)Pd-[OSi(OtBu)3](R)
(where R OSi(OtBu)3 for complex 1 and R CH3 for complex 2) were
synthesized as shown in Scheme 2.13.
The structures of the complexes 1 and 2 were characterized using 1H, 13C,
29
Si NMR spectroscopy, and X-ray analysis: the latter showed that both
structures were found to have slightly distorted cis square planar geometry
around the Pd center. The thermal decomposition behaviors of the complexes were studied using TGA and dierential scanning calorimetry (DSC).
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46
Chapter 2
Cl
Pd
Cl
08:23:58.
2KOSi(O Bu)3
CH2Cl2, 25 C,16 h
-2KCl
N
Pd
N
OSi(O Bu)3
t
OSi(O Bu)3
(1)
N
Pd
N
CH3
I
+ 2HOSi(OtBu)3
+ Ag2O
PhMe, 25 C,3 d (dark)

-AgI, -AgOH
Pd
N
CH3
t
OSi(O Bu)3
(2)
Scheme 2.13
Synthesis of supported organometallic complexes 1 and 2 utilized by

Tilley and Rioux et al.66 for catalysis.
Under inert atmosphere, at about 195 1C, complex 1 condensed to form

(tBu2-bpy)Pd SiO2. Continued temperature increases led to the formation of
Pd SiO2, suggesting that ligand loss occurred beyond 195 1C. These results
were confirmed by decomposition of 1 under vacuum at 250 1C for 2 h
and identification of volatile elimination products such as HOSi(OtBu)3,
t-butanol, isobutene, and water (1.1, 0.3, 0.2, and 0.2 equiv., respectively)
using 1H NMR and the residual black decomposition product was identified
as Pd0 using powder XRD. Under an oxygen atmosphere, decomposition of 1
was fast and exothermic caused by Pd-catalyzed combustion of organic
byproducts leading to PdO formation. Under inert atmosphere, compound 2
decomposed at 195 1C leading directly to Pd black formation. Decomposition
of 2 under vacuum at 250 1C led to 0.4 equiv. of HOSi(OtBu)3 along with small
amounts (o0.1 equiv.) of t-butanol, isobutene, water, and methane with the
formation of Pd0. Under O2 atmosphere; the decomposition behavior of 2 was
the same as that of 1, resulting in the formation of PdO.
Precursors 1 and 2 were supported on a SBA-15 silica surface using the
grafting method in benzene under N2 atmosphere resulting in materials
labeled Pd(1)SBA15 and Pd(2)SBA15. The wt% of Pd was measured to be
1.89 wt% and 1.90 wt% for Pd(1)SBA15 and Pd(2)SBA15, respectively, which
corresponded to 0.16 Pd nm2 for each. Low concentrations of 1 and 2 were
used to ensure a high spatial dispersity of Pd centers on the silica surface.
Scheme 2.14 shows the synthesis of these SSHC.
The grafting reaction of complexes 1 and 2 with SBA was monitored using
solution 1H NMR spectroscopy. Protonolysis of the PdOSi bond by the
surface silanol groups resulted in elimination of HOSi(OtBu)3. A reaction
between excess 1 and SBA-15 in benzene-d6 produced 0.94 equiv. of
HOSi(OtBu)3 with a maximum Pd loading of 5.0 wt% and, for complex 2,
0.97 equiv. of silanol was observed per equiv. of 2 reacted with 5.1 wt% Pd
loading. Nitrogen sorption analysis of Pd(1)SBA15 and Pd(2)SBA15 showed
type IV isotherms which indicates that mesoporosity was maintained after
grafting. The narrow pore-size distribution of SBA-15 was preserved upon
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47
+ HOSi(OtBu)3
N
N
08:23:58.
Pd
25 C, 16 h
+ SBA-15
R
t
Pd
OH
R
OH OH
OSi(O Bu)3
R = OSi(OtBu)3 or CH3
Scheme 2.14
Table 2.4
Grafting of 1 (R OSi(OtBu)3 and 2 (R CH3) onto the surface of

SBA-15.
Nitrogen porosity and palladium loading data for the PdSBA15 materials.
Material
Pd content (wt%)
[ICP-OES]a
Pd coverage/
nm2
SBET b/
m2 g1
rP c/
nm
Vpore, avg d/
cm3 g1
SBA15
Pd(1)SBA15
Pd(2)SBA15
1.89
1.90
0.16
0.16
666
458
467
2.8
2.8
2.8
0.685
0.500
0.504
Average value of triplicates with relative standard deviations o4% in all cases.
Specific surface area using the BET method.
c
Average pore diameter.
d
Average pore volume.
b
(A)
(A)
(B)
(B)
Figure 2.4
(1) DR UV-Vis spectra for (A) complex 1 and Pd(1)SBA15, and (B) complex
2 and Pd(2)SBA15. (2) XANES (A) and extended EXAFS (B) region of Pd
K-edge for complex 1 and Pd(1)SBA15 at room temperature.
grafting and the grafted materials exhibited reduced surface areas and
pore volumes as compared to SBA-15. The properties of the two catalysts and
SBA-15 are shown in Table 2.4.
FTIR spectroscopy showed several analogous peaks contributed to the
t
Bu2-bpy ligand structure for both the Pd(1)SBA15 and Pd(2)SBA15 materials
suggesting intactness of the (tBu2bpy)Pd core after grafting. DR UV-Vis
analysis for the surface structure (Figure 2.4) showed strong high energy
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08:23:58.
48
Chapter 2
absorption below 320 nm and weak, broad, low-energy absorption centered

at 350 nm assigned to a p-p* transition for coordinated tBu2bpy and charge
transfer between Pd(II) and the tBu2bpy. The spectra showed similar maxima
positions and shape of absorption bands for 1, 2, Pd(1)SBA15, and
Pd(2)SBA15, which suggests a small electronic eect on the surface structure
even when the ligand moiety was changed from OSi(OtBu)3 to CH3 as well
as suggesting that the coordination environment around the metal centers
remained the same after grafting. X-ray adsorption spectroscopy (XAS) of
precursor 1 and Pd(1)SBA15 examined in the solid state provided further
structural information. Both the XANES and EXAFS regions of the Pd centers
showed similarity (Figure 2.4); the XANES region showed that the Pd centers
in 1 are divalent pre- and post-grafting. An extended region of the spectrum
indicated the number and identity of the immediate neighbors, so the oxidation state of the Pd remained 2 and the coordination number remains
B4 for both 1 and Pd(1)SBA15.
The stability of silica-supported Pd centers was analyzed by TGA. A similar
trend was observed for onset temperatures for the precursor 1 and
Pd(1)SBA15, and 2 and Pd(2)SBA15; a gradual weight loss suggests that the
supported Pd centers were more thermally stable than the corresponding
molecular precursors. In situ FTIR spectroscopy with heating under inert
atmosphere also indicated that MSN-supported Pd centers were stable at
temperatures near the decomposition temperature of the precursors. The
nature of the supported metal center was further analyzed by XAS for decomposition at lower temperatures. EXAFS spectra for Pd(1)SBA15 suggested
that with the increase in temperature, PdX bonds (X C, O, and N)
dissociated and PdPd bonds formed which led to Pd aggregation. After
exposing Pd(1)SBA15 to 200 1C under He, 92% of the Pd was in the 2
oxidation state whereas at 300 1C, 60% of the Pd remained as Pd21.
A comparison of MSN-supported Pd centers and molecular precursors was
made by testing them for catalytic hydrogenation of 1-phenyl-1-propyne to
(Z)-1-phenyl-1-propene. MSN-supported Pd centers exhibited better selectivity and stability but slower kinetics. The improved selectivity of Pd(1)SBA15
and Pd(2)SBA15 was attributed to the increased stability of the supported
metal centers against particle aggregation as well as the preservation of the
supported Pd centers. Also, no leaching of Pd was observed during the
reaction.
Stack et al. reported the incorporation of Fe(II) centers on a heterogeneous
system in a site-isolated fashion for enhanced selectivity and catalytic activity for olefin epoxidation reactions.67 They used site isolation for creating
metal coordination environments with labile exogenous ligands on the MSN
support; these are otherwise not accessible in homogeneous medium. Using
a metal-templating (metal-exchange) approach on mesoporous silica, Stack
et al. created a derivatized Fe(II)-bis(1,10-phenanthroline) which contained
additional labile ligands. The formation of stabilized Fe(II)-bisphen, which
is only transiently stable in homogeneous solutions, was supported by
spectroscopic and catalytic oxidative reactivity studies. Thiol derivatives of
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49
Si(OEt)3
S
O
N
08:23:58.
Figure 2.5
Phenanthroline derivatives used by Stack et al.67

Si(OEt)3
S
O
Scheme 2.15
[Cu(CH3CN)4]PF6
CH3CN
Cu12 +
SBA-15,70 oC
Overnight
N
N Cu
N
N OTf
II
Fe
N
Fe
OTf
N
CuI
Metal-templating method used by Stack et al.67
phenanthroline 1 and 2 were used for elemental tagging for ligand identification via ICP analysis (Figure 2.5).
Trialkoxysilyl groups enabled immobilization to mesoporous silica for
ligand 1. Ligand 1 was tethered on SBA-15-type mesoporous silica using two
methods: metal templating and random ligand grafting. The materials were
named T, CuIIT, FeIIT, G, CuIIG and FeIIG where T is the material prepared by
metal-templating method (discussed below) and G stands for materials
prepared by random ligand grafting. Procedures shown in Schemes 2.15 and
2.16 outline the preparation steps of dierent materials studied.
1. Metal templating. This was achieved using the following steps and is
shown in Scheme 2.15.
(a) Formation of thermodynamically stable [Cu12]1.
(b) Covalent attachment to mesoporous silica using post-synthetic
grafting method.
(c) Removal of Cu atom template using EDTA.
(d) Metalation of immobilized metal templated 1 with Fe(OTf)2 to form
the final catalyst.
2. Random ligand grafting. It involves two steps as shown in
Scheme 2.16.
(a) Covalent attachment of ligand 1 on SBA-15.
(b) Metalation of immobilized grafted ligand.
An equal loading of ligand 1 was achieved by both the random ligand
grafting and metal-templating methods. As shown in Table 2.5, the template
material proved better in that it achieved a 2 : 1 ratio of ligand : metal as
calculated by ICP analysis, thus ensuring the presence of active catalytic
species in the desired form. The ligand : metal ratio was 2.9 : 1 for FeIIcoordinated grafted materials, implying the formation of either a highly stable
FeII-(tris-1) complex or loss of loosely associated FeII ions upon washing.
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50
Chapter 2
Si(OEt)3
N
S
08:23:58.
O
N
SBA-15, 70 C
Table 2.5
CH3CN, Overnightt
Fe(OTf)2
OTf
OTf
MeOH,Overnight
Scheme 2.16
Fe
Random ligand grafting method used by Stack et al.67
Concentration of metal and ligand in the materials synthesized by Stack

et al.67
Material
Loading of ligand
1/mmol g1] ( 0.01)
Metal loading/mmol
g1 ( 0.002)
Ratio of ligand : metal
T
CuIIT
FeIIT
G
CuIIG
FeIIG
0.11
0.11
0.11
0.10
0.10
0.10
0.001
0.052
0.055
0.00
0.055
0.035
2.1 : 1
2.0 : 1
1.7 : 1
2.9 : 1
Table 2.6
Results of epoxidation reactions catalyzed by FeIIT, FeIIG, and

[Fe23](OTf)2.
Substrate
Epoxide yield [%] (selectivity [%])

FeIIT
FeIIG
[Fe23](OTf)2
Vinylcyclohexane
1-Octene
Allyl acetate
2-Cyclohexen-1-one
85
80
25
15
60 (65)
65 (80)
15 (40)
o5 (o5)
(90)
(95)
(70)
(85)
60 (65)
75 (95)
20 (45)
0 (0)
The copper coordination environments in CuIIT, CuIIG, and [Cu22](OTf)2

was studied using X-band EPR spectroscopy studies.68 The spectrum of
[Cu22](OTf)2 is more similar to CuIIT than to CuIIG indicating that the
geometry and coordination environments around CuII center of [Cu22](OTf)2
more closely matches the templated material. The catalytic reactivity studies
for epoxidation reaction of olefin while using peracetic acid as the oxidant
showed that mesoporous silica supported with templated FeII-(bis-1) species
showed no noticeable induction period and was found to be the best
catalyst. It showed the highest TOF, selectivity and yield of all the catalysts
tested (Table 2.6).
More recently, Stack et al. reported a much more robust and superior
catalytic system by using MSN-supported [MnII(Phen)2]21 as the epoxidation
catalyst and peracetic acid (PAA) as the oxidant.69 The purpose of this study
was to overcome the main drawbacks frequently found in homogeneous
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51
Si(OEt)3
S
SBA-15
N N
O
O
08:23:58.
[Mn(CF3SO3)2]
Covalent
attachment
Cu
Grafted Material
G
Cu
Cu
Dematalation
Mn
MnIIG
Mn
Templated Material
T
Scheme 2.17
Mn
Mn
Random grafting
Mn
MnIIT
Schematic representation of the covalent attachment of Ligand 1 to

SBA-15 silica via random grafting and metal-templating methods to
form MnIIG and MnIIT, respectively.
catalysts i.e. the requirement of 2 equiv. of PAA (the oxidant), degradation of

the electron-rich olefins in the catalytic reaction condition and formation of
partially isomerized trans-epoxide products from cis-olefins. A comparison
of catalytic results was made between the metal-templating method, grafting
method and the homogeneous Mn complex. Scheme 2.17 illustrates a
stepwise procedure for the two methods.
Calculations were completed to estimate the maximum ligand loading,
which would allow for site isolation for the materials having a surface area of
600 m2 g1 using the following equation:
!!
2
A
2 surface area
g
s
distance to nearest neighborA

:
molecules
p
ligand loading
g
Knowing that 20 is twice the distance between the silicon atom and
center of two coordinating N atoms of the ligand in an extended alkyl chain
conformation, a ligand loading of greater than 0.30 mmol g1 was calculated
to be unfavorable for site isolation.
Metal templating with ligand loadings of 0.3, 0.11 and 0.025 mmol g1 led
to a ratio of 2 : 1 of S (from ligand) : metal whereas for grafted ligand
materials the ratio varied randomly. The coordination environments of
CuIIG and CuIIT complexes were analyzed using X-band EPR spectroscopy
which showed that coordination environments of templated materials
(CuIIT) were more similar to the organometallic complex in the
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52
Table 2.7
Chapter 2
II
Epoxidation reactivity of Mn catalysts with vinylcyclohexane (loading

values are for ligands).
Mn
PAA
08:23:58.
Catalyst loading/mmol g1
Yield ( 3%)
Selectivity ( 3%)
[MnII(Phen)2]21
[MnII(Phen)1]21
[MnII(2)2]21
[MnII(2)1]21
MnIIT (0.30)
MnIIT (0.11)
MnIIT (0.025)
MnIIG (0.30)
MnIIG (0.11)
MnIIG (0.025)
95
72
80
73
97
98
98
80
83
72
72
72
85
73
97
98
98
84
83
72
homogeneous state than the grafted materials (CuIIG). For catalytic activity
examination, epoxidation of vinyl cyclohexane was used as a test reaction
and all the catalysts and controls were tested for it (Table 2.7).
The most reactive and selective catalyst was MnIIT. The reactivity and selectivity of MnIIT did not vary with ligand loading. A lower epoxide selectivity
for MnIIG was observed and it was similar to the homogeneous catalyst when
1 equiv. of 2 or 1,10-phenanthroline (phen) for 1 equiv. of MnII was used for
the catalyst synthesis. The kinetics while using similar MnIIT loading was
much faster (approx. 5 times) than MnIIG for epoxidation of 1-octene. Results
indicate that both catalysts, MnIIT and MnIIG, have a broad substrate scope
for the epoxidation reaction: a high yield was demonstrated for trisubstituted
electron-rich olefins for both whereas [MnII(2)2]21 completely oxidized trisubstituted olefins. Also, MnIIT led to no isomerization of cis-olefins and a
very ecient formation of epoxides a, b-unsaturated ketones and esters.
With ecient heat control of the reaction, MnIIT could be recycled five
times without any significant change in the percent yield, the amount of
oxidant needed and the Mn content of the catalysts. However, in the random
grafting sample, MnIIG showed that the ligand content attached to the solid
support remained the same but metal leaching occurred which led to a loss
of reactivity.
Stack et al. reported the synthesis of mesoporous silica functionalized
with azide groups with various loadings, which could be easily controlled
by varying the ratio of 3-azidopropyltriethoxysilane (3-AzPTES) added
during the synthesis using the co-condensation method.70,71 The idea of
using the co-condensation method was to avoid clustering of the ligand
sites. The hybrid azidopropyl mesoporous silica were labeled SBA-15-N3-x
(x is the mole percentage of the 3-AzPTES used during the synthesis; the
sum of the total mole percentage with TEOS is 100). Four strategically
important alkyne-terminated organic compounds were attached using
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53
R
08:23:58.
N3
N
N N
N3
Si(OEt)3 + Si(OEt)4
(100-x %)
(x %)
SBA-15-N3-x
R
Click
SBA-15-N3-x
N
Fe
R=
Scheme 2.18
Fc
Pyrene
TPA
N
Cl
Fe
Ph
Ph
Ph
FeTPP
Synthesis of surface-modified mesoporous silicas, SBA-15-R-x, reported by Stack et al.67
copper-catalyzed azide alkyne cycloaddition (CuAAC) which could provide

insight into the packing of molecules on the surface and variation in
nearest neighbors as the surface loadings varied. Functionalized materials
were also tested for catalytic activities and the information about surface
coverage and site isolation were used to further explore the reaction
mechanism. Acidic media synthesis using non-ionic surfactant as the
template, TEOS as the silica source and 3-AzPTES as the functionalizing
agent was used to synthesize the materials which were further modified
via CuAAC using excess (220 equiv.) ethynylferrocene, 1-ethynylpyrene,
ethynylTPA and Fe-ethynylTPPCl to form SBA-15-R-x materials as shown
below in Scheme 2.18.
X-ray diraction and nitrogen sorption analysis were used to determine
the ordered mesoporous structures of all the materials synthesized. Additionally, CP-MAS 13C solid-state NMR was used to confirm the organic
functionality in SBA-15-N3-8 and SBA-15-R-x materials. The quantification of
immobilized functional groups was done by ICP analyses and UV-Vis
spectroscopic analyses of digested samples.
This study was significant mainly because it reported and discussed
methods for determination of ligand distribution and ligand density
utilizing numerous MSN surface functionalizations.
1. SBA-15-pyrene-x monomer/excimer fluorescence. The fluorescence of
surface attached pyrene is dierent depending on if the species is in
a monomeric or excimeric form: monomeric pyrene is observed at
400 nm and the excimer has a fluorescence maximum of 480 nm. At
low pyrene loading (xr0.2 mmol g1), fluorescence was primarily observed at 400 nm mainly due to the existence of monomeric pyrene
species. Higher pyrene loading led to greater intermolecular pyrene
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54
Chapter 2
Figure 2.6
Fluorescence spectra of (a) SBA-15-pyrene-x with dierent loadings.

A figure showing color changes upon oxygenation of SBA-15-TPA-4 and
SBA-15-TPA-0.5 with [CuI(MeCN)](SbF6) and the characteristic colors of
intermediates is available as ESI.y
interaction and an increase in excimer fluorescence. A direct dependence of increased loading with increased excimer detected was observed (Figure 2.6).
2. SBA-15-TPA-x dioxygen adduct monomer/dimer of CuTPA complexes.
Oxygenation of [CuI(TPA)]1 in homogeneous solutions generated
uniquely colored species depending on the dioxygen adduct formed.
The monomeric superoxo complex was green whereas the dicopper
complex, formed by rapid oxidation of [CuI(TPA)]1, was purple. CuTPA
complexes supported on SBA-15 were treated with dioxygen and the
results were compared with that of the analogous homogeneous complexes. Similar results were observed for supported CuTPA complexes
and the site-isolated loadings on heterogeneous support led to the
formation of stable reactive monomeric species; these monomeric
species were highly unstable in the homogeneous state. The variously
loaded SBA-15-[CuI(TPA)]1-x showed dierent results. Materials with
high loading turned purple due to densely packed complexes leading
to the formation of trans-peroxo complexes whereas materials with
low loading, where adequate site isolation was possible, showed the
formation of green copper superoxide complexes.
2.3.2
Surface Distribution of Immobilized Species
Three idealized surface distributions of functionalized species on the surface

of MSN particles were proposed in this study:
(a) Clustered distribution. In this situation, dense condensation of
functionalized monomers occurred during MSN synthesis. Since no
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08:23:58.
(a)
(b)
Figure 2.7
55
(c)
Graphical representations of theoretical surface distributions: (a) clustered, (b) uniform, and (c) random.
excimer fluorescence at low loadings was observed, this arrangement

was found to be less likely (Figure 2.7a).
(b) Uniform distribution. This arrangement would minimize the object
overlap and maximize the interspecies distance of pyrene attached to
mesoporous silica. Excimer fluorescence in this situation would be
expected only when the loading exceeds the overlapping limit
(B0.2 mmol g1). However, significant excimer fluorescence was
observed for SBA-15-pyrene materials with 0.10 mmol g1 and loading
0.19 mmol g1 implying that uniform distribution also was not likely
(Figure 2.7b).
(c) Random distribution. The nearest-neighbor method gave an estimate
of theoretical random distribution using the Poisson distribution
function as a function of surface loading.72,73
Probability density function: f(r) 2pdr exp(dpr2)
Cumulative distribution function: F(r) 1 exp(dpr2)
p
Mean distance: r 1=2 d
where r is 30 , which was the distance between the centroids of two
objects as 15 was the length of each surface immobilized pyrene
entity, and d is the average surface loading. The percentage of site
isolation was calculated by the following equation:
% site isolation 100exp(dpr2).
The nearest-neighbor method was used to obtain the trend between
the percent of pyrene present in monomeric form and the loading of
pyrene molecules functionalized on the MSN surface. The theoretical
trend of randomly distributed objects matched very well with the
experimentally observed trend of decreasing ratio of Imonomer/Iexcimer
with increasing surface loading of the pyrene molecules. This led
to the conclusion that pyrene and, hence, the organoazides
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Chapter 2
supported on mesoporous silica, were randomly distributed as shown

in Figure 2.7c.
08:23:58.
Two dierent types of catalytic reactions were tested using these

materials.
1. Epoxidation of 1-octene. The SBA-15-TPA-x materials with
Mn(CF3SO3)2 were evaluated as catalysts for the epoxidation of
1-octene. A 10-fold excess of ligand with respect to Mn concentration
gave the maximum percentage yield. All SBA-15-TPA-x materials were
tested as catalysts for epoxidation at 0.1 mol% MnII salt and 1 mol%
ligand to see the eect of ligand loading on the catalytic activity. The
percentage yields of epoxides decreased with increasing surface
loading. SBA-15-TPA-0.5 was the best catalyst leading to B85%
epoxide conversion in 2 min. Both pyrene fluorescence and Cu(TPA)
dioxygen adduct formation indicated the site isolation of a majority of
species on SBA-15-R-0.5. An insight into the reaction mechanism
was provided by comparing yields obtained with SBA-15-TPA-0.5 and
TPA-Tz-tBu ligands under identical concentrations which ruled out
the existence of Mn(TPA) dimers in the catalytic cycle; similar ligand
turnover numbers shown by SBA-15-TPA-0.5 and its homogeneous
analogue TPA-Tz-tBu also implied that at this surface loading and in
solution, Mn(TPA) dimerization was not the major cause of ligand
deactivation.
2. Carbene insertion. Homogeneous FeTPPCl catalyzing carbene insertion yielded greater than 95% conversion and the heterogeneous
SBA-15-FeTPP system provided similar high yields; however, the reaction duration was twice as long. Carbene insertion involved mild
reaction conditions, occurred at a slower rate and used the highly
stable FeTPP as a catalyst. Hence, under these conditions, the eects
of metal lability, ligand decomposition and site accessibility were
minimal and no significant dependence between surface loading and
reactivity was observed.
2.4 Conclusion
In this review, we outlined the common strategies of surface functionalization of mesoporous silica materials and summarized recent developments in single-site heterogeneous catalysis. Single-site heterogeneous
catalysis is defined as using supported active catalysts that are independent
and have no measurable interaction with one another. We focused on a
limited number of recent publications that have been central to the development and understanding of the physical characteristics of these
catalysts. Herein, we described publications that used clever molecular
designs to control the amount of space between the supported active
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57
species and novel methods to measure the ligandcatalyst interaction. We

reviewed publications that reported catalyst analysis utilizing new X-ray
adsorption methods that give additional physical characterization data on
supported SSHC which previously was only possible with molecular catalyst
species. We envision that further development in SSHC will lead to catalysts with increased stability and recyclability which will be active for important chemical reactions including the oxidation of methane and fine
chemical syntheses.
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08:24:02.
CHAPTER 3

for Green Reactions
K. HARA,a H. KOBAYASHI,a T. KOMANOYA,b S.-J. HUANG,c
M. PRUSKId,e AND A. FUKUOKA*a
a
Catalysis Research Center, Hokkaido University, Kita 21 Nishi 10, Kita-ku,

Sapporo, Hokkaido 001-0021, Japan; b Graduate School of Science,
Hokkaido University, Kita 12 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0012,
Japan; c State Key Laboratory of Catalysis, Dalian Institute of Chemical
Physics, Chinese Academy of Sciences, Dalian 116023, China; d U.S. DOE
Ames Laboratory, Ames, Iowa 50011, USA; e Department of Chemistry,
Iowa State University, Ames, Iowa 50011, USA
*Email: fukuoka@cat.hokudai.ac.jp
3.1 Introduction
Supported metal catalysts have played numerous significant roles in the
chemical industry. The current global environmental and resource problems
are motivating further research and development of supported metal catalysts. The typical general requirements expected for ideal catalysts nowadays
include high activity, selectivity, durability, recyclability, compatibility with
practical reaction conditions, broad applicability as well as cost, safety and
environmental benignness. Regardless of the presence of such multiple requirements, a number of supported metal catalysts were recently developed
and applied to a wide range of reactions.
The recent developments in supported metal catalysts were significantly
enhanced with the aid of newly established methodologies in novel materials synthesis as well as those in spectroscopy, microscopy and model
61
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Chapter 3
systems. One of the biggest contributions to the synthesis of novel materials

was brought about by the establishment of versatile and general procedures
to prepare metal nanoparticles.1 Another contribution came from the appearance of various new support materials which were introduced by finding
novel zeolitic and/or mesoporous materials or by the functionalization of
conventional support materials.
In light of such developments in the related methodologies, supported
metal catalysts recently accomplished remarkable progress in meeting the
multiple requirements mentioned above. Many eorts were dedicated to
lower metal loading by introducing novel catalyst structures presenting
unique metalsupport interactions or by using naturally more abundant
metals. Another noteworthy recent area of progress in supported metal
catalysts is the extended scope of their applications. These are not only in
catalytic reactions for conventional petrochemical processes, but numbers
of new applications of supported metal catalysts were also reported in
other fields such as fuel cell-related catalysis, photocatalysis, fine organic
synthesis and bioindustry.
This chapter focuses on the following selected topics from recent advances
in supported metal catalysts:
1) Recent developments in supported metal catalysts for bioindustry;
2) Mechanistic aspects in preferential oxidation of carbon monoxide in
excess hydrogen (PROX reaction); and
3) Surface-selective functionalization of mesoporous silica.
Topic 1 reviews recent progress in supported metal catalysts for the direct
and indirect conversion of biomass to chemicals and fuels. As one of the
recent advances in biomass conversion with supported metal catalysts is the
production of hydrogen, the next important process for fuel cell applications
is the purification of the hydrogen produced, which can be conducted
through catalytic preferential oxidation of carbon monoxide in excess
hydrogen (PROX reaction). Topic 2 thus focuses on the recent mechanistic
findings in a PROX reaction catalyzed by Pt nanoparticles on mesoporous
silica. Topic 3 deals with surface-selective functionalization of mesoporous
silica as a fundamental example in tailor-made functionalization of conventional support materials.
3.2 Recent Developments in Supported Metal

Catalysts for Bioindustry
3.2.1
Conversion of Biomass to Chemicals and Fuels
One of the most notable recent developments in supported metal catalysts is

their extended application towards bioindustry. The techniques and knowledge obtained through the previous development of supported metal catalysts were applied to the direct and indirect conversion of biomass to
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Supported Metal Catalysts for Green Reactions
63
chemicals and fuels. The newly established methodologies for catalyst

preparation also brought significant progress in these areas.
The current largest biomass conversion is bioethanol production, which
was initially derived from food crops such as corn, wheat, sugar cane and
sugar beet. After confronting a serious competition between food and fuel
over utilization of the edible biomass, non-food biomass became the next
target to be converted to fuels and chemicals. Among non-food biomass,
lignocellulose, the main components of wood and grass, has been attracting
significant attention as a promising carbon resource because of its
huge abundance in nature. Lignocellulose consists of cellulose (4050%),
hemicellulose (2040%) and lignin (2030%).
3.2.2
Catalytic Conversion of Cellulose
Cellulose is a polymer of glucose linked by b-1,4-glycosidic bonds, which

shows dierent stereochemistry from that of starch (amylose), linked by
a-1,4-glycosidic bonds. Cellulose molecules have linear structures fixed by
intra-molecular hydrogen bonds, and they are closely packed by intermolecular hydrogen bonds. These hydrogen bonds of cellulose bring its high
chemical stability and insolubility in water. Therefore, the conversion of
cellulose into its monomers or other useful chemicals remained a challenge.
Figure 3.1 shows an overview of the typical initial pathways to chemicals
and fuels starting from cellulose. The hydrolysis of cellulose to its monomer,
glucose, has been extensively investigated. Although sulfuric acid has been
commonly applied in this reaction,2,3 this process involves critical problems
such as the corrosive property of sulfuric acid and neutralization requirement for product separation. As another frequently studied method,
OH
Hydrolysis
Cellulose
OH
Hydrogenation
O
HO
HO
OH
OH
Sorbitol
OH
OH
OH
OH
HO
OH
Gassification
Dehydration
HO
OH
CO, CH4, H2
OH
OH
O
Glucose
Hydrogenolysis
OH
Isomerization
& dehydration
Oxidation
HO
OH
OH
Sorbitan
OH
HO
OH
Ethylene
glycol
Figure 3.1
O
OH
OH
Propylene
glycol
OH
HO
OH
HO
5-Hydroxy
methylfurfural
OH
OH
Gluconic acid
Typical initial pathways of cellulose conversion into chemicals and fuels

by supported metal catalysts.
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Chapter 3
cellulase enzymes can be utilized, where cellulose selectively converts to

glucose under ambient conditions.4 However, the high cost of the enzyme
limits the utilization of this strategy. Application of sub- and super-critical
water to the hydrolysis of cellulose5 was also investigated, resulting in
decreased yields and selectivity of glucose due to further degradation of
glucose by high reaction temperatures. Supported metal catalysts thus have
the potential to overcome these problems.6,7
3.2.3
Hydrolytic Hydrogenation of Cellulose by Supported

Metal Catalysts
One pioneering study on the conversion of cellulose with supported metal

catalysts can be found by going back to the 1950s, when Balandin et al.
obtained sorbitol and sorbitan from cellulose using supported Ru catalysts
in the presence of mineral acids under 7 MPa H2.8 In this methodology, the
in situ hydrogenation of glucose to the sugar alcohols prevents the decomposition of relatively unstable glucose.
The next challenge was to find solid catalysts which function in the absence of soluble mineral acids. After three decades, in 1989, a related patent
was filed by Jacobs, where conversion of starch to sorbitol using Ru/USY was
reported.9 This catalyst consists of two catalytic functionalities: USY as a
solid acid to hydrolyze soluble starch and Ru for reduction of glucose to
sorbitol.
The first conversion of cellulose to sugar alcohols using only a solid catalyst
was accomplished by Fukuoka et al. in 2006, when sorbitol and mannitol were
obtained from cellulose by Pt/g-Al2O3 under 5 MPa H2.10 Supported Ru catalysts also converted cellulose eectively to these sugar alcohols. The solid
catalysts were easily separated from the products by simple filtration.
In addition to catalytic activity, the durability of a catalyst is also an important factor. The catalytic activity of Pt/g-Al2O3 was not retained in the
reuse experiments, which is due to the crystalline phase transformation in
Al2O3 from parent g-Al2O3 to boehmite [AlO(OH)] during the reaction.11 This
phase change caused the destruction of its pore structures and the burial of
Pt particles. The screening of water-tolerant catalyst supports such as TiO2,
ZrO2 and carbon showed that the Pt catalyst supported on commercially
available carbon black (BP2000, Cabot) converts cellulose into the sugar alcohols without loss of its activity in at least three reuse experiments. Detailed
kinetic studies for hydrolytic hydrogenation of cellulose over Pt/BP2000 revealed a two-step reaction mechanism: the first slow hydrolysis of cellulose to
glucose via oligosaccharides followed by the fast hydrogenation reaction of
glucose to sorbitol. The Ru catalysts supported on other carbon supports,
including activated carbon (AC) and carbon nanotube (CNT), were also applied in the cellulose conversion to exhibit good activities and reusability.12,13
Notable practical advantages were found in cellulose hydrolytic hydrogenation using Ru/AC catalysts.14 Even under a hydrogen pressure as low
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as 0.8 MPa, the formation of sugar alcohols was realized eciently,

while most of the other supported metal catalysts require much higher
pressure, typically more than 2 MPa. Furthermore, in the presence of
2-propanol as a reducing reagent, the Ru/AC catalysts can be utilized for
cellulose hydrolytic hydrogenation even without H2 pressure application.
A detailed characterization of the Ru/AC catalyst suggested that the Ru
species on AC were in a form of RuO2 2H2O with a diameter of 12 nm
before the reaction.15
The metal particle-size dependence on the catalytic performance was
systematically studied in hydrolytic hydrogenation of cellobiose, a model
molecule for cellulose, by using a series of Ru/CNT catalysts, which indicates
that the optimal Ru particle size for the CNT support is 9 nm.16 The smaller
Ru particles (2.4 nm) were found to aord a fast reaction rate; however, they
also prompt side reactions to lower the selectivity. In contrast, the larger Ru
particles (12 nm) have less catalytic activity, which also results in a low
selectivity due to decomposition of intermediate glucose.
The recent global trend to seek for alternative metals to previously
developed noble metals brought about another phase of development in
supported metal catalysts. For example, Ni2P/AC catalyst was applied in the
hydrolytic hydrogenation of cellulose, which demonstrated its high catalytic
activity, although low durability in the reuse experiments showed its drawback.17 A high durability was found with the reshaped Ni crystal catalysts on
the carbon nanofibers formed on Al2O3 (Ni/CNF).18
3.2.4
Hydrolytic Hydrogenation of Hemicellulose by

Depolymerization of hemicellulose proceeds more rapidly than that of cellulose, yielding C5 sugars which are useful as sweeteners and potential
precursors to ethylene glycol and propylene glycol, although being more
reactive than glucose. After a patent claiming the hemicellulose conversion
via a three-step process including hydrolytic hydrogenation over RANEYs
Ni,19 one-pot hydrolytic hydrogenation of hemicellulose was recently accomplished by using a Ru/AC catalyst under 5 MPa H2, where arabitol was
obtained in a high yield from beet fiber.20 However, the catalyst durability in
the reactions using real biomass still remains as a problematic issue.
Pre-treatment to remove the deactivating components from real biomass is
thus necessary at the moment. Another recent application is the conversion
of bleached birch kraft pulp into sugar alcohols by Pt/MCM-48 catalyst.21
3.2.5
Catalytic Conversion of Cellulose to Ethylene Glycol

and Propylene Glycol
The conversion of cellulose catalyzed by NiW2C/AC and NiW/SBA-15 was

reported to produce ethylene glycol by Zhang et al.22,23 A modified catalyst
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Chapter 3
without using Ni was later developed by high dispersion of tungsten carbide

on three-dimensional interconnected mesoporous carbon support.24
This modified catalyst can maintain its catalytic activity over three runs
and the slightly reduced activity later observed can be recovered in part by
H2 reduction. An application with real biomass was demonstrated by using
NiW2C/AC to eciently convert milled woody biomass to ethylene glycol,
propylene glycol, and 1,2-butanediol together with the formation of guaiacyl
propane, syringyl propane, and their hydroxylated analogs, the latter half of
which are derived from the lignin part.
Several pathways from cellulose to propylene glycol using supported metal
catalysts were also reported recently. In addition to a Pt/HZSM-5 catalyst,25
Ni/ZnO was found to be a good catalyst,26 where the C3 unit seems to be
formed via a retro-aldol reaction of fructose generated by isomerization of
glucose. A dierent catalyst system using a combination of WO3/Al2O3 and
active carbon to produce ethylene glycol and propylene glycol was established by Liu et al., who proposed a reaction mechanism in which structurally stable crystalline WO3 promotes both the hydrolysis of cellulose to
glucose and the selective cleavage of the CC bonds in sugar molecules,
while active carbon isomerizes glucose to fructose by its basicity.27 NiW2C/
AC was utilized for the selective production of propylene glycol from real
biomass, Jerusalem artichoke tuber, which contains inulin as its carbohydrate storage.28 The propylene glycol formation here is reasonable because inulin predominantly consists of linked fructose units terminating in
a glucose unit.
3.2.6
Hydrolysis of Cellulose to Glucose
The selective and ecient hydrolysis of cellulose to glucose is a challenging

reaction because of the relatively unstable chemical structure of glucose in
spite of its high potential as a precursor to a number of chemicals
(Figure 3.1). In 2008, hydrolysis of cellulose to oligosaccharides and glucose
using a sulfonated carbon prepared from cellulose and fuming sulfuric acid
was demonstrated by Hara et al.29 It was reported that this catalyst is
reusable up to 25 times without loss of activity. They mentioned that the
important feature of this catalyst is the combination of sulfonic, phenolic
and carboxylic groups on the small graphene sheets, which might give high
activity and durability. Sulfonic acid catalysts prepared from a commercial
active carbon and a silica/carbon nanocomposite were also eective.30,31
In addition, a mesoporous carbon CMK-332 treated with concentrated
sulfuric acid produced a high yield of glucose.33 The high catalytic performance observed here might be due to the facilitated interaction between
the surface acid sites and the substrate within the mesoporous structure.
Supported metal catalysts have also been investigated for cellulose hydrolysis. For example, 10 wt% Ru/CMK-3 catalyzed the hydrolysis of cellulose
to glucose in 31% yield.34 Ru/CMK-3 catalyst showed a higher catalytic
activity than the corresponding catalysts of Rh, Ir, Pd, Pt and Au. In addition,
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CMK-3
Cellulose
67
Ru
Oligomers
O
HOOC
HO
HO
O
O
08:24:02.
OH2
Figure 3.2
Glucose
O
O
Ru
Ru
HO
Surface functional groups
OH2
OH2
O
Ru
O
OH2
OH
Ru
O
OH2
H
OH2
RuO2 2H2O
Main roles and possible active sites of Ru/CMK-3 catalyst for the
hydrolysis of cellulose.
the Ru/CMK-3 catalyst kept its high catalytic activity in at least five successive
reused experiments and gave no leaching of the Ru species. The Ru species
on Ru/CMK-3 catalyst before the reaction was revealed to be RuO2 2H2O,
which is produced by the reduction and re-oxidation of supported RuCl3.
The high valence of Ru species might be the origin of high catalytic activity
(Figure 3.2). Regarding the role of the carbon support, CMK-3 without Ru
gave a 16% yield of glucose and a 22% yield of oligosaccharides in the hydrolysis reaction, which indicates that the carbon support itself promotes
the hydrolysis as do the Ru species.
As described above, a mesoporous carbon CMK-3 can hydrolyze cellulose,34 which suggests that the weak acid sites such as carboxylic (pKa 4)
and phenolic groups (pKa 10) on the carbons are also eective for the
reaction. Katz et al. recently reported that silanol groups (pKa 7) on silica
can catalyze the hydrolytic reaction by attaching cellulose chains onto a
silica surface to induce strained conformations.35,36
3.2.7
Valorization of Lignin by Supported Metal Catalysts
Lignin is one of the major components of abundant biomass resource and

its uniqueness as a chemical resource lies in the presence of aromatic
functionalties. Using such a promising and unique biomass resource via
valorization over heterogeneous catalysts has been investigated for more
than half a century. The hydrogenation of hardwood lignin was tested with a
copperchromium oxide catalyst in 1938 to produce propylcyclohexanols
and methanol.37 After catalyst improvements over the following three decades, significant studies on lignin hydrodeoxygenation started by using Co
Mo and NiMo type catalysts, which were originally developed for catalytic
removal of sulfur and nitrogen in conventional petro-based processes.
Weckhuysen et al. recently reported a systematic review on the catalytic
valorization of lignin, which covers from the initial studies just mentioned to
nonconventional catalysts developed in the last decade.38 Examples of the
recently reported catalysts include NiW/SiO2Al2O3 catalyst for lignin
hydrocracking,39 Ru/C and Pd/C catalysts for full hydrogenation of the aromatic rings of model compounds and lignin,4042 NiCu/ZrO2 for selective
hydrodeoxygenation of a model aromatic compound with retention of its
aromaticity,43 Pt/Al2O3 for lignin depolymerization process44 and Ni/MgO
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Chapter 3
45
08:24:02.
catalyst for lignin gasification. Oxidative conversion of lignin or its model

compounds has been also investigated by using supported metal catalysts
such as Pd/Al2O3 for production of aldehydes from extracted lignin46 and
Pt/TiO2 for photocatalytic lignin degradation.47
3.2.8
Direct Formation of Syngas or Pure Hydrogen from

Biomass
The direct formation of syngas (CO and H2) has been investigated by using
supported metal catalysts. Supported Ni catalysts were utilized for the
degradation of cellulose at ca. 900 K in the presence of water vapor to
obtain CO, H2, CH4, and CO2 with small amounts of C2 compounds.48
However, catalyst deactivation due to carbon deposition was observed. The
catalyst durability was improved by using Rh/CeO2/SiO2 catalyst, which
aorded complete conversion of cellulose to gaseous C1 products and H2 in
the presence of air and steam even at a lower reaction temperature of
773 K.49 The optimization of the reactors is also important in producing
syngas from biomass, which was shown in an example using a dual-bed
reactor for gasification of actual lignocellulosic biomass.50 Supported
metal catalysts have also been developed for the direct formation of pure
hydrogen from biomass. In order to utilize the obtained hydrogen for
polymer electrolyte fuel cells (PEFCs), it is necessary to restrict CO formation to less than 10 ppm. One accomplishment was brought about by a
Ni/TiO2 catalyst in the presence of a stoichiometric amount of NaOH,
where cellulose was directly converted to pure H2 with CO and CO2 concentrations of less than 30 ppm.51
3.3 Mechanistic Aspects in Preferential Oxidation

of Carbon Monoxide under Excess Hydrogen
(PROX Reaction)
3.3.1
Preferential Oxidation of Carbon Monoxide in Excess

Hydrogen (PROX Reaction)
As just described in the previous section, one of the recent advances in

biomass conversion with supported metal catalysts is the production of H2.
In order to utilize the produced H2 for PEFCs,52 the next important process is
purification of the H2 by removing small amount of CO, which is poisonous
for Pt anode PEFCs even at low concentration levels (o10 ppm). The elimination of such a small amount of CO can be conducted through the preferential oxidation of CO in excess H2 (PROX reaction) by using various types
of supported metal catalysts.53 Accompanying the extensive research and
development seeking active catalysts for the PROX reaction, a mechanistic
understanding of the catalytic reaction has also been developed. It has been
proven that the properties of support materials have significant eects on
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54
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catalytic performances. However, unprecedented support eects were recently found in the PROX reaction catalyzed by Pt catalysts supported on
mesoporous silicas, which are generally regarded as inert materials. This
chapter focuses on this promotional eect of mesoporous silica as one of the
recently found mechanistic aspects in the PROX reaction.
3.3.2
PROX Reaction by Pt Catalysts Supported on

Mesoporous Silica
Mesoporous silicas have been widely used as catalyst support materials

since their discovery in the 1990s5558 due to their high specific surface
area and well-defined pore geometry. The amorphous nature of the wall
structure leads to the general understanding that mesoporous silicas act as
inert materials in catalytic cycles. In contrast to this understanding, one
surprising catalytic eect was found in PROX reaction using Pt catalysts
supported on mesoporous silica. The platinum catalysts supported on
mesoporous FSM-16 or MCM-41 showed approximately 100% CO conversion over a wide range of reaction temperatures (298423 K), while the
platinum catalysts supported on amorphous silica showed sluggish
activity.59 Isotope tracer experiments indicated that the surface silanol
groups on the Pt/FSM-16 catalyst can oxidize the adsorbed CO on Pt in the
absence of O2. The successive work revealed that the dierence in the pore
diameter of support FSM silica has a significant eect on the catalytic performances of the Pt catalysts.60 In particular, Pt/FSM-22 catalyst, having 4 nm
pore diameter, exhibited the highest CO conversion (entry 3 in Table 3.1),
whereas the Pt/FSM-10 catalyst, having 1.8 nm pore diameter, resulted in
a lower conversion (entry 1). Such a pore-size eect might be due to
the dierent micro-reactive environment at the Ptmesoporous silica interface.
In order to achieve an image of the reactive interface of the Pt/mesoporous
silica, two model Pt/MCM-41 catalysts were employed in the mechanism
study.61 Starting from the same pristine as-synthesized materials, two types
of MCM-41 supports were prepared by using dierent procedures at the
surfactant removal steps: one-step calcination for MCM-41-A and two-step
Table 3.1
Entry
1
2
3
4
5
6
a
Catalytic performancesa of Pt nanoparticles supported on mesoporous

silicas.
Catalyst
Pore
diameter/nm
Conversion (%)
at 298 K
CO
O2
1 wt% Pt/FSM-10
1 wt% Pt/FSM-16
1 wt% Pt/FSM-22
1 wt% Pt/FSM-22
5 wt% Pt/MCM41-A
5 wt% Pt/MCM41-B
1.8
2.7
4.0
7.0
2.9
2.8
42
95
100
96
100
10
25
56
100
55
100
5
Reaction conditions: 0.20 g catalyst, flow rate 40 ml min1, CO 1%, O2 1%, N2 5%, H2 93%.
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Chapter 3
(a)
(b)
OH OH
Si
08:24:02.
Figure 3.3
Si
Pt
OH
Si
O
Si
Pt
O
Si
Si
Si
OH
O
Si
Si
Si
Models of the interface on Pt catalyst supported on mesoporous silica:

(a) active Pt/MCM-41-A and (b) inactive Pt/MCM-41-B for PROX reaction.
extractioncalcination for MCM-41-B, respectively. The resulting two

Pt/MCM-41 catalysts displayed strong similarities in Pt morphology, particlesize distribution, electronic states, support architecture, and pore-size
distribution, and thus isolate the interferences from these apparent physicochemical parameters in the mechanism study. These two model Pt catalysts
showed a dramatic dierence in catalytic activity: ca. 100% CO conversion
with Pt/MCM-41-A versus 10% with Pt/MCM-41-B at 298 K (entry 5 vs. 6).
Based on the isotope tracer experiments, it is revealed that the surface
silanol groups at the interface of Pt/MCM-41-A ignite the CO oxidation.
These active interface silanols were regenerated in situ by the dissociation
combination of O2 and H2, which in turn sustains the entire catalytic cycle
for the PROX reaction. The absence or shortage of interface silanols on
Pt/MCM-41-B not only impeded the CO oxidation in the initial stage but also
hindered the activation of O2 (Figure 3.3). This image of the micro-reactive
environment also proved that the catalytically relevant silanol groups are
only a small portion of the total number of silanol groups.
3.4 Surface-selective Functionalization of

Mesoporous Silica
3.4.1
Novel Types of Functionalized Support Materials
As mentioned in the Introduction, the recent developments in supported

metal catalysts were significantly enhanced with the aid of newly established
methodologies in materials synthesis, which includes the appearance of
various new support materials. Recent advances in inorganic synthesis
introduced numbers of novel zeolitic and/or mesoporous materials as
available catalyst components.6266 In contrast, many types of purely organic
materials, such as functionalized polymers and dendrimers, were also developed as promising support materials for the preparation of metal catalysts.
Another approach to the synthesis of functional materials is a combination of
inorganic and organic materials synthesis, which produces hybrid materials
consisting of an organic functionality and an inorganic structure framework.
The most commonly used inorganic component here is mesoporous silica,
which is focused on in the following last part of this chapter.
3.4.2
Surface-selective Modification of Mesoporous Silica
Numerous examples of surface functionalization on mesoporous silicas

for the preparation of supported metal catalysts have been reported.67
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71
The functionalization of mesoporous silica with an organic functionality can

be done by treating parent mesoporous silica with modification reagents.
However, special attention should be paid if precise dierentiation is
necessary between the exposed external surface and the internal pore
surface. For example, whether deposition of active metal species is realized
on the external surface or on the internal pore surface can make a significant
dierence in the catalytic property in some cases.6870
One solution for such spatial control of functionalization is the
preparation of targeted functional mesoporous silicas by co-condensation
using the corresponding functional silica precursors. This method realizes
the homogeneous incorporation of functional groups predominantly inside
the pores.71 Lin et al. successfully demonstrated linear alkyne polymerization within the mesopore by depositing an active Cu catalyst on the
internal surface of a functionalized mesoporous silica prepared by the
co-condensation method.72
An alternative method, called the post-synthesis method, generally allows
more versatile functionalization. This method utilizes selective grafting on
the external surface of as-synthesized mesoporous silica, followed by the
removal of the structure-directing agent and subsequent functionalization of
the internal pore.73,74 Such an approach has been used to prepare several
supported metal structures with definite spatial control.7578 However,
finding the optimum conditions for the synthesis of such complex materials
is not always straightforward.
Recently, detailed structural and quantitative analyses of the selective
surface silylation of MCM-41 were conducted by using the silylating reagents
shown in Table 3.2.79 The selective silylation of the external surface was
tested by the reaction of as-synthesized MCM-41 and one of the silylating
reagents, followed by extraction of the surfactant (Figure 3.4). The pore-size
Table 3.2
External surface modification of mesoporous silica MCM-41 with

dierent silylating reagents.
Silylating reagent
DFT pore
diametera/nm
Silylation
densityb/mmol g1
TMSOTf
4.6
0.31 ( 0.05)
TMCS
4.6
0.06 ( 0.01)
BSA
4.6
0.09 ( 0.01)
MeSi(OEt)3
4.2
1.04 ( 0.10)
a
b
Derived from DFT analysis of nitrogen adsorption measurement.

Derived from solid-state 1H NMR analysis by using hexamethylbenzene as an external reference.
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72
Chapter 3
Figure 3.4
External surface modification on mesoporous silica.
distributions after the silylation shown in Table 3.2 were determined by

nitrogen adsorption experiments using density functional theory (DFT).
Clearly, MeSi(OEt)3, the most commonly used silylating reagent, resulted in
a narrower pore size, indicating that part of the internal surface was also
silylated.8083 In contrast, the pore distributions with the other reagents
tested in this study showed exclusive modification on the external surfaces.
Solid-state NMR techniques8486 gave precise and quantitative evaluation of
the silylation eciencies, which indicates that TMSOTf gave the highest
loading among the three surface-selective silylating reagents. In addition,
the solid-state NMR measurements were found to be powerful methods to
detect the presence of unwanted organic impurities which can be incorporated during the functionalization of mesoporous silica.79
3.5 Conclusions
Increasing demand from society has been promoting continuous advances
in supported metal catalysts. Such developments include extensive applications in bioindustry as well as the utilization of novel catalyst components
to exhibit uniquely required catalytic performances. These accomplishments
were achieved with the aid of advances in related areas of research such as
materials synthesis, spectroscopy, microscopy and model systems. However,
many challenges remain unsolved by the catalyst systems developed so far.
Apart from the conventional methodologies, a completely new design of
catalyst might be necessary for the further development of supported metal
catalysts in the near future.
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08:24:04.
CHAPTER 4
Zeolites in the 21st Century

KAb AND JIR
EJKA*a
I C
WIESLAW J. ROTH,a DAVID KUBIC
a
J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the

Czech Republic, v.v.i., Dolejskova 3, CZ-182 23, Prague 8, Czech Republic;
b
Research Institute of Inorganic Chemistry UniCRE-RENTECH,
Chempark Litvnov, 436 70, Litvnov, Czech Republic
*Email: jiri.cejka@jh-inst.cas.cz
4.1 Introduction
Zeolites are of great interest because their ordered microporous structures
combined with strong acid activity, capacity for selective sorption, thermal
and chemical resistance, and other beneficial qualities proved very useful for
practical applications with significant commercial impact.14 The ability of
zeolites to discriminate molecules based on size and shape expanded
the concept of molecular sieving and in more detail the so-called shape
selectivity. Zeolites have been used commercially as selective catalysts, e.g.
for many hydrocarbon conversions in refineries and chemical industry,
selective sorbents and ion exchangers.5,6 Zeolites have a framework
molecular structure constructed as an extended network of corner sharing
TO4 tetrahedra, with TSi, optionally substituted with heteroatoms such as
Al, which imparts strong acid character, as well as B, Fe and others.
The network is 4-connected with maximum framework density below ca.
1921 T atoms per 1 nm3.7 As elaborated below, zeolites were first recognized
as aluminosilicate minerals about 250 years ago but since about the 1940s
they have been extensively studied and developed as diverse synthetic
materials including aluminophosphates and other compositions. Recently,
novel classes of zeolites, such as mesoporous single crystals, hierarchic
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materials and two-dimensional zeolites extensively enlarged the area of

zeolitic materials.
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4.2 History of Zeolites

The history of zeolites dates back to the middle of the 18th century when
Swedish mineralogist Cronsted described an aluminosilicate mineral, now
believed to be stilbite, which released water upon heating.8 This material
was called a zeolite based on the Greek zeo (boiling) and lithos (stone). In
due course, several dozens of zeolite minerals were identified and described
in the literature.9,10 Even recently, a few new zeolite minerals were identified.
Remarkably, one of them, mutinaite, is isostructural with the synthetic,
highly profitable and versatile zeolite MFI, while gottardite and tschernikite
have the topology of previously synthesized zeolites NU-87 (NES) and beta
(BEA*). In the 19th century some useful properties of zeolites were recognized including the reversible adsorption of water and gases, and ion exchange.11 Around the 1940s, further interest in the extraordinary properties
of zeolites was initiated by Barrer resulting in the first successful discoveries
of useful synthetic zeolites. The last 60 years experienced a fast increase in
the number of zeolites synthesized as well as in findings of some new zeolite
minerals. At present, we recognize over 200 dierent structural types of
zeolites (or zeotypes defined as non-Si-based compositions, e.g. aluminophosphates) and more than 60 natural zeolites.7 The number of synthetic
zeolites is steadily increasing each year. The ensuing advances include both
new compositions and structures with novel pores dimensions. While
natural zeolites possess medium- or large-pore systems with low Si/Al ratios
(usually below 5), some of their synthetic analogs were prepared as more
siliceous materials having extra-large pore channels. The eort in zeolites
inspired the discovery and extensive study of related novel classes like
mesoporous materials,12,13 zeolite lamellar solids,14,15 and metalorganic
frameworks (MOFs).16 There is also a significant and growing interest in
zeolites as structured products like membranes.
4.3 Conventional Zeolites

Zeolites attracted particular attention because of their frequently shown
superiority in comparison with other functional solids, such as clays,
amorphous or organic materials, in terms of high activity, stability, ordered
structure and/or other properties considered useful.17 The conventional
zeolites are recognized as those with an extended 4-connected periodic
framework in three-dimensions (3D). There was an implicit assumption of
their direct formation in 3D and structure immutability, i.e. the impossibility
of post-synthesis modification except for partial or complete degradation. In
fact, a partial degradation (dealumination) of zeolite FAU is used at
the industrial level to prepare the most important zeolite catalyst for oil
cracking. Recently, desilication of high-silica zeolites has been extensively
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investigated aiming at the formation of mesopores and the increased

accessibility of active sites through the removal of silicon atoms and part of
the framework.
As nature and human ingenuity usually find ways to expand beyond rigid
definitions, new materials are continually added to the area of interest under
the zeolite umbrella. For this reason we will present the conventional
zeolites according to the above formal definition and later on separately
discuss selected non-conventional ones as an integral part of the
continually expanding zeolite field.
4.3.1
Structures
The molecular structure of zeolites, also referred to as topology, is an

intrinsic property identifying and defining dierent zeolite types and
determining their usefulness because of the pore size(s), shape and
connectivity (one-dimensional 1D or higher dimensionality) of channels
for the diusion of guest molecules. The composition, especially the Si/Al
ratio, influences activity and often is limited by the framework type itself.
wensteins rule forbids neighboring Al atoms, hence the atomic Si/Al ratio
Lo
cannot fall below 1. In the opposite direction, purely siliceous forms of
dierent structural types of zeolites were reported, although even they most
likely contain Al inclusions at ppm or ppb levels. In general, a higher Al
content translates into greater overall acidity but sometimes it is oset by
lowered stability, in the extreme resulting in degradation and reduced
practical usefulness.
The number of possible 4-connected networks is theoretically infinite and
hence the respective number of possible zeolites in terms of structures is
unlimited. As mentioned above, more than 200 unique topologies have been
formally recognized by the IZA structural commission and assigned a 3-letter
code, the so-called Framework Type Code (FTC). The naming convention,
adopting the designation used by an inventor, underscores the lack of
systematic classification of these topologies. The structures define a specific
unit cell and hence manifest themselves in a characteristic, indexable X-ray
diraction pattern. In line with the presumed immutability of the
conventional extended 3D zeolites, it is expected that as-synthesized and
activated, i.e. calcined, products show analogous peak positions in their
X-ray diraction patterns. As will be highlighted later, the observed
dierences in X-ray diraction patterns of as-synthesized and calcined
zeolites led in some cases to the identification of layered zeolite precursors
and new insights into the synthesis mechanisms.
Zeolite structure is most often described in terms of pore sizes and
connectivity/dimensionality as it reflects the practical potential. The useful
measure of pore size is in terms of the number n of T atoms in the
circumference of the channel, defined as the n-ring. In catalysis, the large
pore, i.e. 12-ring, and medium-pore, 10-ring, zeolites have been by far
dominant and useful. This is exemplified by the two most commonly used
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and profitable zeolites: FAU, 3D (channel connectivity) 12-ring and MFI, 3D

10-ring. The others, such as BEA* (3D, 12-ring), FER (2D, 10-ring 8-ring),
MOR (2D, 12-ring 8-ring), MWW (2D, 2 10-ring with supercages),
reinforce the dominance of the large and medium-pore zeolites in synthesis
and applications. The attempts to expand zeolites above 12-ring resulted in
successful synthesis of several 14-ring frameworks or even larger pores but to
date no promising practical benefits have been identified for them. This is
mainly connected with the high cost of structure-directing agents (SDAs)
used for the synthesis, the low concentration of acid centers and the possible
lower stability of these extra-large-pore zeolites. At the lower pore size end,
the small, i.e. 8-ring, zeolites initially demonstrated a great value for sorption
and ion-exchange applications embodied by zeolite A, LTA, while apparently
having little benefit for catalysis. This could be attributed to general
diusion problems in pores of that size but in selected non-trivial
applications the value of an 8-ring zeolites proved exceptional, e.g. methanolto-olefin (MTO) over CHA zeolite/zeotype and related zeolite types. The most
industrially relevant zeolite structures are provided in Figure 4.1.
The frameworks, which are networks of T atoms bridged by oxygen atoms,
contain various combinations of rings. The smallest ones, i.e. 3-ring, are very
Figure 4.1
Schematic structures of the most industrially relevant zeolites MFI,

BEA*, MOR, and FAU, figures used from the website of the International
Zeolite Association.
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rare (although the number of zeolites with this secondary structural unit
increased in the last years) while 4, 5 and 6 dominate and through dierent
arrangements circumscribe the bigger n-rings. A useful concept distinguishes secondary building units (SBUs), some of which were believed to
be involved in the assembly of zeolite structures during synthesis. This is
now regarded as an unlikely event in most situations since structure
building by smaller entities, mainly by addition of monomers, is considered
the predominant process. One should not rule out the possibility of a
framework assembly by bigger/extended units and in fact such a process has
been recently identified in our laboratory (vide supra).
The above general outline of concepts and issues associated with zeolite
molecular structure ought to be followed by some discussion of specific cases
or classes. However, we feel that the subject is continuously addressed in diverse reviews and the reader will be better served by being referred to these
publications.1820 Instead, we will focus here on selected aluminosilicate
structures, which we find intriguing and worth mentioning for some particular
reasons (vide infra) i.e. TUN, IMF (see Section 4.3.3 below), MSE and MCM-71.
MCM-71 is notable as one of the most recent new zeolites obtained by
an inorganic route, without a template. It is a high-Al material with onedimensional 10-ring channels having elliptical cross-sections. Its structure is
interesting as being predicted by Breck and complementing the series he
designed.17,21
MSE is the first 12 10 10-ring zeolite. Its first synthesis was attributed
to a specially designed dipositive rigid template.22 Since this first synthesis
other less elaborate and more cost eective SDAs have been identified to
aord this structure. The intersecting 12- and 10-ring channels can be
viewed as combining the pore features and high Al concentration of the most
catalytically valuable zeolites to date, i.e. FAU and MFI. Pore characteristics
of zeolites used commercially, mainly in catalysis, are given in Table 4.1
(based on ref. 23).
4.3.2
Synthesis
While structures represent the most significant conceptual side of zeolites,

the synthesis is the most important practical one. Only a fraction of the
possible frameworks have been synthesized before now. The synthesis has
played a role well beyond the traditional supply of high quality materials for
testing and practical use. It has been the driver of innovation and source of
breakthroughs both technical and fundamental. The discovery of zeolite
LTA, synthetic FAU, MFI, MWW and mesoporous molecular sieves, to name
a few, are examples of landmarks resulting in expanded eort and new
directions in zeolite science and technology.1
All zeolite syntheses are carried out by essentially one type of process,
mostly batch-wise at all scale levels from small laboratory to commercial
one.19,24,25 The synthesis entails a hydrothermal reaction of a mixture
comprising sources of silica and alumina, a mineralizer, in most cases
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Table 4.1
Chapter 4
Pore properties of synthetic zeolites used commercially.
Zeolite
IZA codea
Channel
dimensionality
Pore
opening
Pore dimensions2/nm
A
Y
ZSM-5
Beta
Mordenite
Ferrierite
MCM-22, UZM-8
SAPO-11
SSZ-13, SAPO-34
EU-1
L
ZSM-48
ZSM-23
ZSM-12
Rho
Theta-1, ZSM-22
LTA
FAU
MFI
BEA*
MOR
FER
MWW
AEL
CHA
EUO
LTL
*MRE
MTT
MTW
RHO
TON
3D
3D
3D
3D
2D
2D
2D
1D
3D
1D
1D
1D
1D
1D
3D
1D
12
12
10 10
12
12 8
10 8
2 10
10
8
10
12
10
10
12
8
10
0.41 0.41
0.74 0.74
0.53 0.56; 0.51 0.55
0.66 0.67; 0.56 0.56
0.65 0.7; 0.26 0.57
0.42 0.54; 0.35 0.48
0.55 0.40; 0.41 0.51
0.40 0.65
0.38 0.38
0.41 0.54; side pockets
0.71 0.71
0.53 0.563
0.45 0.52
0.56 0.60
0.36 0.36
0.46 0.57
Bold: zeolites with known 2D layered precursor.
soluble hydroxide and, optionally, organic SDA(s) promoting formation of a

particular structural type, known or unknown (the latter if trying a new
synthesis mixture combination). Dierent insoluble crystalline products are
obtained, including mixtures, depending on the composition and synthesis
conditions. The most critical quantitative compositional variables are the
ratios Si : Al : OH : water. The nature of the cation has a dominant eect in
most cases on the structure of materials produced and the kinetics of the
synthesis. Less critical factors like the nature of the raw materials and
certain additives may also influence the outcome of preparation, but in
general their eect can be moderated. The examples relevant to the latter
may be substituting an expensive source with a more economical one.
The products obtained by synthesis must be identified because even in
well-known systems unexpected reactions may take place for various
reasons. In most cases, X-ray powder diraction is the first and adequate
tool for that purpose. Additional initial characterization may be obtained by
SEM (crystal size and habit) and elemental composition with the Si/Al ratio
as the primary descriptor. The crystalline product can be rarely used as is
and must undergo activation, especially for catalytic applications. A typical
activation process entails a series of calcination and ion exchanges to
remove organic templates and cations with simultaneous introduction of
protons generating acidity and open pores. Some degree of dealumination
may occur during this process. It depends on the properties of particular
crystals and is generally considered undesirable although interaction
between undamaged Brnsted acid sites (framework preserved) with extraframework Al due to defects is believed to enhance acid activity. Regarding
activation, there are in most cases additional steps required for larger-scale
commercial catalytic applications.23 Zeolite crystals are combined with a
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binder, very often with alumina, and formulated into larger particles. This
process is usually omitted in laboratories as it requires larger quantities
of material and specialized equipment. This is often not considered
in publications comparing the performance of laboratory samples with commercial catalysts while the dierences may be quite dramatic. As discussed in
ref. 26, the extrusion of platelet zeolite crystals, MCM-22, with alumina afforded an entire range of special crystal orientations with many fractured
fragments edge-on. On the other hand, unformulated crystals have a tendency
to agglomerate and usually expose flat surfaces when imaged in microscopy.
It must be appreciated that zeolite synthesis/formation occurs spontaneously and without human intervention when appropriate composition
and conditions are established. Arguably, the process is driven by some
self-controlling mechanism but, alas, our knowledge and understanding of
it is practically non-existent. This has not been an obstacle to impressive
expansion in both fundamental understanding and applications as well as
diversity of structures. In the long run, a greater reliance on the fundamental
knowledge of zeolite formation, especially quantitative, may be necessary to
better understand opportunities as well as limitations of zeolite synthesis.
This lack of understanding is surprising after many decades of development especially since some basic tenets are quite clear zeolite formation
begins with the nucleation of viable nuclei, i.e. ones that can grow
spontaneously. Then, as established empirically in many cases, the growth
follows the McCabe law,27 i.e. individual crystal size increases with a
constant linear rate until availability of nutrients becomes the rate limiting
factor. Initial attempts to elucidate zeolite formation focused on rationalizing the long-range order,24 which some assumed could not arise from the
attachment of small, e.g. silicate, aluminate fragments. In fact, the opposite
is the prevailing opinion right now. The nature of the nucleus has not been
resolved and is rarely considered.24,28 Some detailed proposals have often
been structure-specific and not necessarily applicable to other structures.
Ideally, one would want to relate the kinetics of crystallization to
composition, which might enable predictions including new species.
4.3.3
Role of Organic Structure-directing Agents
The addition of organic polar molecules, mainly amine-based, has been

found to modify properties of the synthesis gel and induce crystallization of
new zeolite frameworks or novel crystal forms in terms of size and/or habit.
The early examples of this new strategy include tetraalkylammonium
cations: tetramethyl, tetraethyl, and tetrapropyl, which produced lower Al
zeolite A, zeolite beta and ZSM-5, respectively. Many more organic compounds have been tried and a plethora of novel structures were discovered
including ones with pores larger than 12-ring, which were the largest with
non-organic preparations. Initially the role of the organic additives was
rationalized as templating i.e. organizing inorganic species around the
template in an early stage of the zeolite synthesis. An alternative name, i.e.
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structure-directing agent (SDA), is also commonly used. In general, it is not

possible to predict either the structure or what size and dimensionality
of pores a particular template may produce. The chief strategy uses a
trial-and-error approach together with experience in the design and selection
of SDAs. The area has been extensively reviewed from the standpoint of
various templates and the structures they produce.29 Here, we will present
selected examples indicating some influence extending beyond simple pore
filling and occlusion.
The formation of the same structure by dierent templates is such a case,
indicating more than a pore-filling eect. These SDAs often also template
dierent structures. Initially, the zeolite MFI was frequently invoked as
having many templates but it can be also produced from a purely inorganic
system. Recently, the structure of MWW zeolite, which is represented by
MCM-22, MCM-49, EMM-10 and considered isostructural with SSZ-25, ITQ-1
and other materials, was found to be formed with structurally diverse
templates.30 They include cyclic amines, especially hexamethyleneimine,
diquaternary penta- and hexamethonium ions, asymmetric diquaternary,
sparteinium and trimethyladamantamonium ions. The same templates
produce other frameworks upon changing Si/Al, basicity or another synthesis parameter. There is also the possibility of first crystallizing one zeolite
and then recrystallizing into another (MCM-22 precursor to TNU-9).31
As an alternative to the discovery of new zeolites using complicated
organoammonium SDAs, a very eective approach has been designed at UOP
referring to charge-density matching.32 This design has several conceptual
components: mixtures of smaller templates and a relatively high Al content
to enable organics coming close together; and low content of alkali cations
to reduce competition with organic cations. Initially, an apparently homogeneous mixture of silica, alumina and some of the SDAs is prepared with a
positive-charge deficiency. Then another template is added and the hydrothermal synthesis is carried out to crystallize a zeolite phase. This technique
aorded some new frameworks and compositions exemplified by UZM-4
(BPH) and UZM-5 (UFI). On the other hand, it had a great impact on
identifying simple organic templates for the synthesis of zeolites that were
previously obtained with quite complex and not readily available SDAs.
The best illustration is provided by the synthesis of zeolite ZSM-18.33 It
required a trisquaternary ammonium compound, 2,3,4,5,6,7,8,9-octahydro2,2,5,5,8,8-hexamethyl-1H-benzo[1,2-c:3,4-c 0 :5,6-c00 ]tripyrrolium (Scheme 4.1),
and was presented as exemplifying true templating, i.e. an exact match
between the channel system of the zeolite and the size and shape of the SDA.
The equivalent structure, UZM-22 was obtained with choline as SDA and Sr21
and Li1 as additional essential components in the synthesis mixture,
thus complicating the ZSM-18 formation rationale.34 More recently, the
already-mentioned zeolite MCM-68 was claimed to be replicated with a much
more convenient template: dimethyldipropylammonium hydroxide.35
Some new medium-pore zeolites were obtained recently with a
flexible linear diquaternary alkylammonium cation composed of two
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Scheme 4.1
N-methylpyrrolidinium groups connected by a tetra- or pentamethylene chain.

They include TUN and IMF and a high-silica analog of stilbite (STI) designated
TNU-10 with a Si/Al ratio of about 7 : 1.36 Their structure and properties are
typically compared to MFI as the most prominent and, in catalysis, the best
performing medium-pore zeolite. The projection of TUN down the b-axis is
similar to that of MFI but the channel connectivity in the third direction is
rather complex. Zeolite IMF has formally a 3D 10-ring channel system but its
connectivity is complicated. It is considered to be eectively a 2D pore system
with restricted diusion. The properties connected with shape-selective
characteristics are quite dierent from those of MFI.
It is a bit of a paradox that in spite of the enormous success of SDA use in
the discovery of new zeolites and crystals, the preferred synthesis approach
would ultimately be to reduce procedures to non-organic mixtures. The cost,
handling and environmental issues associated with the use of SDAs present
a significant burden in larger-scale implementation. The achievement of
non-organic syntheses may be dicult to envision in every case but nonetheless some promising examples may be mentioned. Okubos group
showed that some zeolites made originally with an SDA can be synthesized
without organic templates.37 The working hypothesis of the zeolite synthesis
without the presence of SDA is based on the utilization of some common
composite building units in dierent zeolite structural types. A noteworthy
example of successful template-free synthesis is the recent report on
hexagonal faujasite, i.e. EMT.38
4.3.4
Role of Inorganic Species
Inorganic cations accompany the greatest part of zeolite preparations,

mainly in the form of added hydroxides as mineralizers. Even in the absence
of addition on purpose, the presence of inorganic cations is to be expected as
an adventitious impurity, just as with Al in the case of silica-based preparations. The nature of the inorganic cation is not irrelevant and may induce
alternative structures too, for example, Na, which is the most common alkali
used. The presence of inorganic cations is ultimately critical for the successful preparation of some zeolites (e.g. UZM-2232), but in other cases
should be reduced to a minimum. For example, sodium cations usually limit
the incorporation of Ti in the synthesis of TS-1.39 Sometimes the direct
synthesis of proton forms of zeolites, through preparation with organic
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Chapter 4
cations only, can be preferred to avoid the necessary ion exchange of sodium
forms to protonic ones followed by the treatment of wastewater solution.
Entirely dierent eects have been observed with inorganic species that
are supposed to be part of the framework. There is always the possibility of
isomorphic substitution, like B, Ga, and Fe for Al, or Ge for Si. The first
group of atoms carries a 3 charge and generates a negative charge of the
framework, introducing acidic properties to zeolites.17,40 The second and
particularly fruitful area resulting in numerous novel, usually extra- or largepore, structures arose from the synthesis of Ge-based zeolites.18,19 As
discussed in ref. 19 there are practical problems with Ge-based materials,
one of them being cost and availability of Ge, which is almost prohibitive
unless a really high-value application can be found. Nonetheless, the
Ge-zeolites set a new standard/frontier for more traditional compositions to
advance. The chemistry of germanosilicates in combination with appropriate SDAs oers new possibilities to synthesize novel zeolites. Another issue
with the Ge-zeolites is lower thermal and hydrothermal stability often
resulting in significant degradation upon standard treatments or activation.19
However, this apparent adversity has been turned into an opportunity
that resulted not only in novel-type materials but also the demonstration of
a new process: a 3D to 2D transformation, which will be discussed in the
following section.
4.4 From 2D to 3D Zeolites and Vice Versa

2D solids are recognized as lattices with strong bonding in two crystallographic directions and a much weaker one in the third with the capability
of easily severing these connections. These solids are considered to be
composed of rigid layers with an interlayer region that can be spatially and
compositionally modified by intercalation and pillaring, and ultimately
delaminated into individual lamellae.41,42
Zeolites, as lattices defined by their 3D connectivity, seemed outside the
2D concept but nonetheless their crystal formation was considered to entail
growth through layers.43,44 No doubt the appearance of zeolite structures in
some projections as compact layers with much less dense SiOSi bridges
reinforced this notion. Zeolite MCM-22 reported in the early 1990s
demonstrated the formation of its 3D framework via a definitely layered
intermediate designated the layered MCM-22 precursor, MCM-22P, which
was the final product from the hydrothermal synthesis.45,46 Its conventional
post-synthesis processing including calcination produced a complete 3D
framework material MCM-22/MWW. The layered nature was further confirmed and exploited in practice by intercalation with surfactants resulting
in a swollen MCM-22. It was an inorganicorganic layered composite comprising MWW monolayers, 2.5 nm thick, separated with surfactant bi-layers,
2.53 nm thick. As the first case of exfoliated layered zeolite it was transformed by treatment with TEOS (tetraethylorthosilicate), hydrolysis and
calcination into pillared material, designated MCM-36. The latter had layers
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permanently separated by ca. 2.5 nm and combined micro- and meso-pores

of size 3 0.5 nm with strong acid activity typical of zeolites. Later on, the
swollen product was subjected to sonication aording eventually, after
calcination, a delaminated zeolite designated ITQ-2.47 Another delaminated
MWW zeolite was obtained earlier by direct synthesis and designated
MCM-56 but exhibited a standard BrunauerEmmettTeller (BET) surface
area of 400500 m2 g1 compared with the ITQ-2 BET surface area of around
800 m2 g1. The dierence was attributed to house-of-cards vs. deck-of cards
architecture for ITQ-2 and MCM-56.48 While special, MCM-22 proved not to
be unique and other frameworks were found to exhibit the 3D2D lamellar
duality and were found to form by two pathways (at least) direct 3D and
indirect 2D. The number of known lamellar zeolites is so far limited to about
10, but it is believed to be possible that all 3D frameworks can have a
lamellar counterpart.49,50 This is reinforced by the recent remarkable
invention of layered zeolite synthesis by the design of appropriate SDAs.51
The authors used long-chain surfactant molecules with one end templating
the appropriate zeolite structure while the long tail prevented the initiation
of a new layer in close proximity. Based on this principle any zeolite structure
may be viewed as possible to make via such an inorganicorganic composite.
The framework MWW continues to aord novel structures resulting from
various packings of the layers and bonding arrangements directly or through
additional linkers. Particularly noteworthy are the so-called interlamellar
expanded zeolites (IEZ), which are simply the layered precursors stabilized in
their expanded form (i.e. not condensing into the standard 3D framework
upon calcination) by appropriate treatment, like silylation. The interlayer
pore openings are eectively enlarged by two SiO units.52 New types of
materials, sometimes unexpected, are constantly added to the layered zeolite
families. These developments have been expressed as a formal 2D concept of
the variability of zeolite structures with one dimension being the various
frameworks and the second their dierent architectures arising from layer
packings.53
The area of 2D zeolites may have a great potential for practical use but
in the realm of applications these new materials have to compete with
established zeolites not only in performance but also cost and ease of
implementation. Claims of improved performance are quite abundant,49,50,54
including examples of those under commercial conditions, like MCM-56 in
liquid alkylation. The actual industrial use is sometimes hard to confirm as
proprietary but it is possible that the mentioned use of UZM-8,25 an MWW
zeolite with apparently disordered layer structure, may be one of the first
examples of commercialized 2D zeolites.
Another new development in the area of 2D zeolites has been the transformation of an existing frameworks structure into a lamellar precursor (of a
then unknown zeolite) by selective chemical degradation.55 It was contingent
on particular features of the initial structure, i.e. layers supported by cubic
D4R entities composed mainly of readily hydrolyzable Ge. The product,
prepared by a top-down approach, was designated IPC-1P (P precursor)
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and was shown to undergo transformations typical for layered precursors:

swelling, pillaring and IEZ stabilization.55
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4.5 Adsorption
Zeolites have a leading role in industrial selective adsorption and separation
processes. Their benefits rely in particular on their large specific surface area
and easy modifiability through ion-exchange and molecular-sieving properties. Consequently, zeolites have found application in many industries,
particularly refining, petrochemical and chemical industries. Adsorption on
zeolites can follow several dierent pathways including ion exchange, shape
selectivity and, most importantly, equilibrium-selective adsorption.56 From
another point of view, zeolite-based adsorption applications can be divided
into impurity removal and separation processes.
The main application of zeolite ion-exchange adsorption is as additives
in laundry powders/detergents using sodium forms of zeolite A or P.57,58
Zeolites act as water softeners replacing sodium tripolyphosphate, which
was previously used but proved to be an environmentally unacceptable
component. By ion exchange, the calcium and magnesium cations, which
are responsible for water hardness hindering washing eciency and
leading to formation of carbonates,59 are removed. The ion-exchange
principle is also used in environmental remediation applications, such as
radioactive or heavy metal removal from soil and ground water. The shapeselective adsorption principle is the key to separation of n-alkanes from
i-alkanes using 5A zeolites (CaA60). Due to the suitable pore dimensions of
5A, n-alkanes readily enter the pore system, while the branched isomers are
too bulky and cannot enter the pores to be adsorbed.
Most of the zeolite adsorption applications are based on dierences in the
equilibrium selectivity of various sorbates with the adsorbent.56 Concerning
the contaminant removal, water (as moisture) is the primary concern in
many industrial applications. The activated, i.e. dehydrated, zeolites A or X
are typically used as the chosen desiccants. Generally, water removal is
operated as a pressure swing adsorption (PSA), i.e. water is removed at
elevated pressure in one adsorbent bed, while in the other bed the pressure
is decreased to regenerate the adsorbent. Very low residual humidity
(o1 ppm) can be achieved for a wide range of gases (CH4, N2, O2, H2, CO2,
SO2, H2S, NH3, HCl).61,62 Other gaseous impurities that can be removed by
using zeolites A, X or mordenite include CO2, SO2, H2S, HCl and NH3.
Table 4.2 lists characteristic applications of zeolites in adsorption and
separation processes.
Zeolites are commonly used in separations of permanent gases and
hydrocarbons. The industrial separation of permanent gases uses PSA processes and the most important ones include air separation to produce N2
and O2 (CaX, LiX, LiCaX63,64) and H2 separation from refinery o-gases (NaX,
NaA).65 The most important process, besides separation of n-alkanes from
i-alkanes due to the shape selectivity of zeolites, is isolation of p-xylene from
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Table 4.2
89
Separation and adsorption processes using zeolites.
Zeolite (IZA code)
Industrial application
A (LTA)
O2/N2 separation
H2 separation from o-gases
CO2 removal
Natural gas drying
Drying of industrial gases
n-/iso-Paran separation Sorbex (Molex)
Mordenite (MOR)
O2/N2 separation
Removal of SO2
Removal of HCl
Trapping Hg vapors
Acid gases drying
X, Y (FAU)
O2/N2 separation
H2 separation from o-gases
CO2 removal
CO2/CH4 separation
Natural gas drying
Xylenes separation Sorbex (Parex)
Olefin separation Sorbex (Olex)
Removal of dioxins
the mixture of xylenes and ethylbenzene using cationic forms of zeolites X

and Y (e.g. process Parext).66,67 Other examples of industrial separations
include separation of olefins from parans (process Olext, CaX) or fructose
separation from glucose (process Sarext, Ca Y68).
4.6 Catalysis
Zeolites are now indispensable in many industrial catalytic processes,
particularly in the petroleum refining and petrochemical industries where
their application facilitated significant innovations. They have acquired this
position thanks to their unique properties including a tunable acidbasic
character, shape selectivity, ion exchangeability and large specific surface
area. Among more than 200 zeolite structures that have been discovered and
synthesized, about 20 are utilized as commercial catalysts.25 In this group,
zeolites Y (FAU), ZSM-5 (MFI), beta (BEA*), mordenite (MOR) and MCM-22
(MWW) are most extensively used. From the industrial catalysis point of
view, the most important zeolites and the processes they are applied in are
summarized in Table 4.3.
Fluid catalytic cracking (FCC) is the single most important catalytic
process using zeolites. It is consuming more zeolite volume than all
other processes altogether.5 The FCC together with hydrocracking is the key
process in a modern refinery for the conversion of vacuum distillates, i.e.
heavy oil fractions, into light products, mainly gasoline and diesel fractions.
The catalyst used in FCC has a very complex composition but the development of zeolite Y, in particular its steam pretreatment aording ultrastable
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Table 4.3
Chapter 4
Industrial catalytic processes using zeolites and zeotypes.
Zeolite or zeotype (IZA code)
Catalytic process
Beta (BEA*)
Benzene alkylation
Acylation
BaeyerVilliger reaction
Erionite (ERI)
Selectoforming
Ferrierite (FER)
n-Butene skeletal isomerization
L (LTL)
Alkane aromatization
MCM-22 (MWW)
Benzene alkylation
Mordenite (MOR)
Light alkanes hydroisomerization

Dewaxing (cracking)
Aromatics alkylation and transalkylation
Olefin oligomerization
SAPO-11 (AEL)
Dewaxing (long-chain alkane hydroisomerization)
SAPO-34 (CHA)
Methanol to olefins
Y (FAU)
Fluid catalytic cracking

Hydrocracking
Aromatics alkylation and transalkylation
Olefin/paran alkylation
NOx reduction
Acylation
ZSM-5, TS-1, Silicalite (MFI)
Fluid catalytic cracking

Dewaxing (cracking)
Methanol to gasoline/olefins
Olefin cracking and oligomerization
Benzene alkylation
Xylene isomerization
Toluene disproportionation and alkylation
Aromatization
NOx reduction
Ammoxidation
Beckmann rearrangement
ZSM-12 (MTW)
Aromatics alkylation
ZSM-22, Theta-1 (TON)
Dewaxing (long-chain alkane hydroisomerization)

Olefin skeletal isomerization
zeolite USY, has made it so that rare earth (RE)-exchanged USY is the
key component of FCC catalysts. A fresh FCC catalyst contains typically
2040 wt% of USY, the other components being matrix (includes catalytically
active binder consisting of alumina and amorphous aluminosilicate, clay)
that is responsible for pre-cracking of large feed molecules which could
not enter into USY pores, and various promoters. The role of promoters is
three-fold: protection of USY structure from vanadium, environmental protection (SOx, NOx and CO abatement) and product selectivity adjustment.
The last one may be aimed at increasing the yield of propylene, a desired
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petrochemical raw material. FCC has now become the second most
important source of propylene supplying about one third of the world propylene production. This has been enabled by the use of zeolite MFI, typically
in amounts equaling 0.53 wt% of the total FCC catalyst loading.
At the core of the FCC catalyst, there is the zeolite FAU characterized by its
unit cell size (a0) being a measure of framework aluminium content and
determining the acid site density and strength, a key property of the zeolite
for FCC.69,70 Catalyst activity as well as product yields, coke formation and
product quality (e.g. gasoline octane number) depend directly on the unit
cell dimension. The maximum activity for gas oil cracking was observed
when all framework Al atoms in the faujasite structure were isolated, i.e. at a
framework Si/Al ratio of 58 (a0 2.4362.440 nm). So far, zeolite USY with a
framework Si/Al ratio 45 was not synthesized by direct synthesis and the
dealumination of the parent zeolite Y with Si/Al of about 2.8 is the only
alternative to prepare the optimum catalyst. The dealumination helps not
only to adjust the Si/Al ratio to the optimum value range, but also aects the
catalyst performance by creating secondary mesopores and forming extraframework Al species (EFAL).71 Moreover, the dealumination of FAU zeolite
by steaming aords the ultrastable Y zeolite (USY) that has substantially
better hydrothermal stability than the parent zeolite FAU. This is essential,
particularly for the catalyst regeneration by burning o coke at temperatures
above 700 1C in the presence of steam.69 A further improvement of the
zeolite FAU stability is achieved by introducing rare earth (RE) metals, such
as lanthanum, by ion exchange. Currently, the limited availability of these
metals has led to an increased demand for low RE metals catalysts.
Besides the optimized strength and density of acid sites, shape selectivity
plays an important role in FCC catalysts that are designed accordingly. To
prevent deactivation of the active sites in zeolite Y channels that are
responsible for the optimum selectivity to light products, the catalyst
consists of an active matrix where pre-cracking takes place and where heavy
metals such as vanadium and nickel are deposited. Consequently, instead of
blocking zeolite Y pores by large feed molecules the pre-cracked molecules
enter the channel system and are further converted to gasoline and a range
of gaseous hydrocarbons. With the current shift in the demand for FCC
products, the yield of propylene is being maximized by adding a ZSM-5
additive allowing only a small range of gasoline molecules into its pores;
these are further cracked to yield gaseous products, mainly propylene and C4
olefins. Moreover, the 10-ring system of ZSM-5 eciently suppresses the
formation of carbonaceous deposits as the condensation intermediate
formation is sterically prohibited. To achieve sucient stability of ZSM-5, it
is typically treated with phosphoric acid and steaming at 800 1C to create
aluminiumphosphate complexes in the phosphorus-stabilized ZSM-5.69
Zeolite USY is at the heart of the hydrocracking process, which is another
important industrial process aimed at upgrading heavy fractions from crude
oil distillation. Unlike in FCC, this catalytic cracking is combined with deep
hydrotreating and hydrogenation. As a result the products are sulfur- and
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Chapter 4
nitrogen-free and have a significantly reduced aromatic content. The

advantage of hydrocracking over FCC in bottom-of-the-barrel processing is
the superior quality of the products, particularly where middle distillates
quality is concerned. The type of catalyst depends on the feedstock and
the technology solution; nonetheless the catalyst is bifunctional, the
hydrogenation function being provided by metal sulfides, such as NiW
sulfides, or by Pt and Pd. The choice depends obviously on sulfur concentration in the euent from the hydrotreating stage. The necessary acidity
is delivered either from amorphous silicaalumina or USY. The acidity
and mesoporous character is adjusted again by the ultra-stabilization
procedure. The presence of mesopores ensures facile molecular trac
leading to suppressed secondary cracking reactions and hence to better
selectivity to middle distillates (kerosene, diesel). An optimized 5-step
ultra-stabilization procedure consisting of three ion-exchange and two
steam-calcination steps provides a highly ultrastable zeolite Y (VUSY) with a
unit cell size of 2.432 nm (Si/Al 9.6).69 Other zeolites and mesoporous
molecular sieves have been studied for hydrocracking (MOR, LTL, omega,
BEA* and MCM-41);70 however, their commercial application has not been
confirmed.
In addition to processes focused on enhancing the quantity of light
products (gasoline and middle distillates), zeolites are extensively used in
refining processes with the objective of improving the fuel properties of the
light fractions. Typical examples are catalytic dewaxing and light-paran
isomerization.69,70 Catalytic dewaxing is a process used either for middle
distillates or lube oils which aims to remove n-alkanes having high melting
points. Two catalytic approaches are possible: selective cracking of n-alkanes
into smaller molecules, and catalytic isomerization to iso-alkanes exhibiting
better flow properties at cold conditions due to lower melting points. To
achieve this, bifunctional catalysts are applied, the hydrogenation/
dehydrogenation component being typically platinum and the isomerization
or cracking function being provided by Brnsted acidity of zeolites. The
isomerization option should be preferred as it ensures higher yields of
desired products. An important feature of the zeolites to be used is their
shape-selective properties which ensure that only n-alkanes can enter the
zeolite channel system to be isomerized or cracked, while multi-branched
alkanes that are more reactive than n-alkanes are denied access to active
Brnsted acid sites and over-cracking is hence avoided. The following
zeolites fulfill the criteria on shape selectivity and acidity: MFI, TON, MTT
and zeotype AEL. An excellent example of shape selectivity is the comparison
between ZSM-22 and ZSM-23. The very small dierence in their pore openings (TON: 0.46 0.57 nm, MTT: 0.45 0.52 nm) results in large dierences in diusivity (12 orders of magnitude larger diusion coecient for
methylnonanes in TON than in MTT) and a larger Henry coecient in TON
than in MTT (about two orders of magnitude). As a consequence, MTT
shows lower branching in n-octadecane isomerization (dewaxing).7275
An important aspect is also the concentration of active sites on the
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external surface; the lower it is, the higher the selectivity of the isomerization
to monobranched alkanes.
The main objective of light paran (C5, C6) isomerization is to maximize the
octane number of the light naphtha cut. In contrast to dewaxing, a maximum
degree of branching is desirable. The key parameter is the strength of acid
sites, as stronger acidity allows operation at lower reaction temperatures
which is beneficial from the thermodynamics point of view. Zeolites, typically
Pt/MOR, have to compete with other catalytic systems, such as chlorinatedalumina- or sulfated-zirconia-supported platinum catalysts which can be
applied at temperatures o200 1C. The operating window for Pt/MOR is around
250 1C.5 Pt/MOR has the maximum strength of Brnsted acid sites providing
the maximum isomerization activity and has a Si/Al ratio of about 10. The
dealumination of MOR decreases diusional limitations and coking rate. The
overall strength of Brnsted acid sites can be further increased by an introduction of controlled amounts of extra-framework Al by steaming and acid
leaching, which interact with Brnsted acid sites.76 While the activity of the
zeolite-based catalyst is low, resulting in a lower gain in research octane
number (ca. 10 for Pt/MOR vs. ca. 14 for Pt/chlorinated alumina), it outperforms the non-zeolite catalysts in terms of sensitivity to contaminants such
as water and small amounts of sulfur and regenerability.5 The lower activity of
Pt/MOR can be addressed by integrated separation of n- and iso-parans
using, e.g. CaA as discussed above. The process is called the total isomerization process.77 Light parans, generally C6 and C7, are alternatively
also commercially converted over a modified bifunctional zeolite L to aord
aromatics by dehydrocyclization. Typically, Pt/K-LTL or Pt/KBa-LTL zeolites are
used in processes, such as Platforming (UOP) or AROMAX (Chevron Philips).78
Unlike in isomerization, it is essential to remove any sulfur and acidity.79
Apart from the cracking process, zeolites are indispensable catalysts
for the petrochemical transformation of aromatics, in particular for the
isomerization, disproportionation and transalkylation of alkyl aromatics
(C7C9) and for the alkylation of benzene. The primary objective of the first
group of processes is to maximize the production of p-xylene and benzene,
while alkylation is targeted for the production of ethylbenzene and cumene.
The choice of catalyst for isomerization of C8 aromatics depends on the
treatment of ethylbenzene. If it is to be isomerized to xylenes (and ultimately
to p-xylene) then Pt/MOR or Pt/EU-1 (EUO) are applied; if selective dealkylation of ethylbenzene is the aim then dealuminated Pt/MFI is used.5,6 The
selectivity over Pt/MOR is generally improved by avoiding any mesoporosity
and by partial ion exchange by Na or Ca cations to decrease Brnsted acid
sites density.80 The decreased density of Brnsted acid sites limits the extent
of disproportionation reactions leading to undesired by-products, such as
trimethylbenzenes. When Pt/MFI is used as a xylene isomerization catalyst,
the formation of trimethylbenzenes is suppressed due to its transition-state
shape selectivity. The product shape selectivity of MFI to p-xylene, originating from a higher diusivity of p-xylene in comparison with m- and o-xylene
from inside zeolite pores, can be further improved by using larger zeolite
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Chapter 4
crystals, deactivating active sites on the external surface of these crystals and
reducing the size of pore windows, e.g. by coke or inorganic species
depositions.4,6
The shape selectivity of MFI in favor of the para-isomer is the key catalyst
feature used in toluene disproportionation to aord a high yield of
p-xylene.77 The intrinsic selectivity of MFI is further enhanced by suitable
catalyst design as discussed above. Toluene can be alternatively utilized as
the feedstock for transalkylation with heavier alkylaromatics (C9 and C10).
Several processes were developed (Tatoray, PX-Plus, PX-Plus-XP by UOP);
however, catalyst details were not disclosed.65
The most important processes of aromatics alkylation are the syntheses of
ethylbenzene (an intermediate of styrene production) and cumene (an intermediate of phenol production).4,81,82 Two principal technology solutions were
developed for ethylbenzene production: a vapor-phase process using MFI
catalyst (Mobil Badger process) and liquid-phase processes using MWW or
BEA* (EBMAX, Exxon Mobil and Polimeri Europa, respectively). The main
advantages of the liquid-phase process include a lower excess of benzene
needed and lower reaction temperatures.5 Nearly exclusive by-products are
diethylbenzenes that can be either recycled to the feed (gas-phase processes)
or fed into a second (transalkylation) reactor with benzene where they are
converted to ethylbenzene over the same catalyst as in the alkylation reactor.
The production of cumene by alkylation of benzene with propene is analogous
to ethylbenzene production. Several processes using dierent zeolites
are applied commercially: dealuminated mordenite (Dow), beta (Eni) and
MCM-22 (ExxonMobil).79,8183 Moreover, the dealuminated MOR (3-DMM) is
highly active and the alkylation can be operated at low temperatures, which
is beneficial for minimizing the formation of n-propylbenzene, a highly
undesirable by-product.5
Another important class of industrial technologies using zeolites or zeotypes is related to methanol as the cornerstone of C1 chemistry, which is an
alternative to the FischerTropsch synthesis (FTS) starting directly from
synthesis gas. Both FTS and methanol conversion process allow the utilization of other carbon containing feedstocks (natural gas, coal or biomass)
for the production of products obtained currently as a result of petroleum
processing. The main conversion processes include methanol-to-gasoline
(MTG), methanol-to-olefin (MTO) and methanol-to-propylene (MTP). ZSM-5
is the catalyst of choice for MTG84 and MTP77 processes, while SAPO-34
is used in the MTO process as its structure is optimal for the selective
formation of ethylene and propylene.84
4.7 Summary
Zeolites may be viewed as embodying the ultimate best of natural and synthetic inorganic compounds through a fundamental elegance and diversity
of structures combined with exceptional practical usefulness while being
environmentally benign and eventually relatively easy to manufacture. Over
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the years their properties and selective uses have been perfected to such
levels that they are hard to beat, including by other new zeolites. They provided inspiration for innovation leading to related materials like ordered
mesoporous materials, metalorganic frameworks and recently expanding
into the area originally thought to be the contradiction of zeolites i.e. 2D or
layered zeolites, which now appears to be an integral part of the family. Few
other areas of science seem to prosper so well in both improvements of the
known and advancements of the new and unknown.
Acknowledgements
This work was supported by the Czech Science Foundation Grant No. P106/
12/G015 (Centre of Excellence).
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2010.
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CHAPTER 5
Enzyme Immobilization on
Mesoporous Silica Supports
CHENG-YU LAI* AND DANIELA R. RADU
Delaware State University, 1200 N. DuPont Highway, Dover, DE 19901, USA
*Email: cylai@desu.edu
5.1 Introduction Biocatalysis and Porous Silica

Materials
The application of porous silica in biocatalysis involves enzyme (biocatalyst)
immobilization on solid supports, which integrates enzymatic catalysis with
heterogeneous catalysis.
Biocatalysis could be defined as the use of biological entities with catalytic
properties (biocatalysts) for industrial synthetic chemistry. Biocatalysts include: enzymes, whole-cell catalysts, catalytic antibodies and nucleic-acidbased enzymes (ribozymes and DNAzymes). Enzymes are the predominant
category of biocatalysts due to their historical use in biochemical processes
which drove comprehensive studies directed to their fundamental understanding. They are highly eective and versatile biological catalysts, and
display high chemo-, stereo- and regioselectivity while operating under ambient conditions (physiological temperature and pH, atmospheric pressure).
When enzymes are used as catalysts, no activation or protection/deprotection
of functional groups which are typically required in organic synthesis are
necessary. Furthermore, synthetic catalysts often demand harsh chemical
conditions and multi-step processes, leading to excessive energy consumption
and the generation of much waste. In contrast, due to their operation mostly in
100
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Enzyme Immobilization on Mesoporous Silica Supports
101
water as solvent, enzymes generate less waste. Due to their high selectivity,
shorter synthetic routes are achieved through enzymatic catalysis in comparison to traditional organic synthetic routes. Enzymatic processes can now
be carried out in organic solvents1 as well as aqueous environments, so that
non-polar organic compounds as well as water-soluble compounds can be
modified selectively and eciently. As the use of biocatalysis for industrial
chemical synthesis becomes easier, several chemical companies have begun to
increase significantly the number and sophistication of the biocatalytic processes used in their synthesis operations2 and, thus, the use of enzyme biocatalysis for industrial synthetic chemistry is on the verge of significant growth.
However, the use of enzymes in their native form is often hampered by
several limitations such as high costs, low operational stability and diculties
in recovery and reuse. Fortunately, there are many techniques available that
permit enzyme performance to be improved, involving areas of science that
have undergone impressive developments in recent years: microbiology, protein engineering, chemistry of proteins, etc. Additionally, enzyme immobilization, albeit considered old-fashioned, is a very powerful tool to improve
almost all enzyme properties, if properly designed: e.g., stability, activity, specificity and selectivity, and reduction of inhibition. Moreover, product contamination with enzymes can be minimized or completely avoided, which is
particularly critical for applications in the pharmaceutical and food industries.
Immobilization techniques have been recently revamped as new developments
within material science have highlighted the potential of a variety of organic
and inorganic materials for use as supports for enzyme immobilization.
Many catalytic supports such as resins, polymers, electropolymerized
films, solgel materials, inorganic solids such as solid and porous silica etc.,
have been explored with regard to enzyme immobilization and comprehensive reviews have been published.38
Here we outline recent advances in the area of mesoporous silica involved in
enzyme immobilization development. Mesoporous silica supports provide a
set of the most attractive features toward overcoming enzyme stability drawbacks both in biotechnology and biocatalysis applications.9 Mesoporous silica
materials are structurally robust, chemically stable over a broad pH and temperature range and benefit from flexible synthetic conditions that enable tailoring of their properties for a plethora of hostguest chemistry applications.
The large surface area and pores with an adjustable pore size, typically in
the size range of 2 to 40 nm, make them suitable for accommodating large
biomolecules, including enzymes.
5.2 Types of Porous Silica Support Utilized in Enzyme

Immobilization
5.2.1
Introduction
The immobilization of enzymes on a solid support is a methodology designed to overcome enzymes limitations, such as low long-term stability
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Figure 5.1
Chapter 5
Porous supports vs. solid supports for enzyme encapsulation the porous
support protects enzyme from interacting with inactivation promoters
(illustrated: gas bubbles).
Reproduced with permission from ref. 13.
and poor reusability. Their immobilization within the pores of porous

silica permits the full dispersion of enzyme molecules without the
possibility of interacting with any external interface. Thus, the immobilization provides a gate-keeping eect by stabilizing the enzyme against
interaction with molecules from the enzymatic extract, and preventing
aggregation, autolysis or proteolysis by proteases from the reaction extract.
Moreover, the immobilized enzyme molecules are not in contact with any
external hydrophobic interface, such as air bubbles originated by supplying
the required gases or promoted by the strong stirring which necessary to
control pH in industrial catalytic processes. Gas bubbles are known to
induce enzyme inactivation of soluble proteins.1012 Pore-immobilized
enzymes, however, are protected from gas bubbles which cannot reach into
pores and thus, cannot induce enzyme inactivation, as illustrated in
Figure 5.1.13
Since the reporting of MCM-41 mesoporous silica materials in 1992 by
Beck et al.,14 the family of porous silica materials has experienced continuous growth as a myriad of templates from surfactants (ionic and nonionic) to nanoparticles have been used in a continuous quest to control and
optimize particle morphology and pore-size distribution toward applications
that demand properties like pore uniformity, easy pore access, selective
functionalization, large-molecule accommodation, and controlled particle
size and morphology. In biocatalysis, porous silica oers an ideal platform
due to the flexibility in tailoring both the particle size and pore-size distribution for each enzyme of interest.
The ideal support in each application is process- and enzymedependent. Figure 5.2 presents a useful flow chart that helps in support
selection.15
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Figure 5.2
103
Systematic approach for selection of mesoporous particles (MPs), the

immobilization method, and study of enzymeMPs system.
Two major groups of porous silica have been studied for enzyme immobilization applications, classified based on porosity order: (i) hexagonally
ordered porous silica materials (Section 5.2.2), and, (ii) hierarchically
ordered porous silica materials (Section 5.2.3). Details of both categories of
enzyme supports are presented.
5.2.2
Enzyme Immobilization/Encapsulation in Hexagonally

Ordered Porous Silica Materials
Templating surfactant materials that are capable of forming cylindrical

micelles, which further organize in hexagonal arrays, are at the foundation
of forming mesoporous silica with hexagonal arrays of pores (upon
providing a silica source). Most representative members of the hexagonally
ordered porous silica materials group are MCM-, SBA- and FSM-type
materials, as indicated in Table 5.1.6
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Table 5.1
A summary of characteristic properties of various mesoporous silica materials employed for encapsulating enzymes. Reprinted
with permission from ref. 6.
Mesoporous materials
Silica source
Template
1
TEOS, sodium silicate
CnTMA (n 1218)
MCM-48
TEOS, silicate sodium
FSM-16
Polysilicate kanemite
SBA-1
TEOS
SBA-15
TEOS, sodium silicate
SBA-16
MCF
TEOS, TMOS
TEOS
HMS
TEOS
CTAB,
C16H33(CH3)2N(CH2)(C6H5)
Gemini Cm-12-m
CnTMA1 (n 1218)
CnH2n11 N(C2H5)3X
(n 1218), 18B4-3-1
Cns1 (n 1218)
Pm, Pas, P6s, 8501500
(B01oE016),
Brij97(C1aHl5E01ol
F127, F108, or F98
F127 (EOul6PO70EO106) with
TMB
CmH2m11NH2 (m 822)
MSU-X
TEOS, TMOS
CmEOn (m 1115)
IBN-X
TEOS
PMOs
(RO3Si-R 0 -Si(OR)3
C8PhEOn, EO13P030EO13
F108, F127, P65, P123 with
FC-4 and TMB
CTAB, OTAB, CPS, P123,
F127, Brij 56, Brij 76
Pore diameter/nm
20 hex.
channels
Bicontinuous
210
24
20 hex.
channels
30 cubic
mesostructure
B4
20 hex.
channels
530
Spherical cages
Cellular foam
530
1050
Disordered
mesostructure
Disordered
mesostructure
Nanoparticle
210
520
20 or 30 hex.
220
23
215
Chapter 5
MCM-41
Description
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MCM-41, FSM-16 and SBA-15 have 2D hexagonal channels and could be

developed into particles typically spherical with controlled particle-size
distribution. Their pore size is directed by: (i) the templating agents utilized
in the synthesis of the materials: cationic surfactants for MCM-41-type materials, and non-ionic, block-copolymer type for SBA-15,14,16 and (ii) the silica
source: tetraethyl orthosilicate (TEOS), sodium silicate and polysilicate.
Thus MCM-41-type materials feature an average pore size of 210 nm,
FSM-16 B4 nm, whereas SBA-15 could achieve much larger pores, typically
530 nm.16 The larger range for MCM-41 is due to the demonstration of pore
expansion, utilizing pore-enhancement molecules.17
Synthetic conditions could be optimized toward tailoring the particle
morphology of mesoporous materials. Lin et al. demonstrated the first
mesoporous silica nanosphere (MSN),18 functionalized with amine groups,
opening new avenues in mesopores: silica-based heterogeneous catalysis by
controlling the size of nanoreactors inside MSNs, which led to a dramatic
improvement in control of reaction kinetics.
A large group of enzymes have been reported as immobilized into ordered
mesoporous silica.19 The pore size is critical for enzyme packing and,
consequently, the accessibility to the active sites (Figure 5.3).20 As a
consequence, MCM-41, MSN and FSM-16 structures are restricted to the
immobilization of enzymes with relatively small size (with diameters below
pore size diameter).
In addition, relatively low enzyme loadings (typicallyo10 wt%) and slow
enzyme immobilization rates are observed, in spite of the fact that these
materials have surface areas as high as B1000 m2 g1.2123
More recently, improved enzyme loadings have been reported for SBA-15
materials (pore sizes in the range of 515 nm.)24 However, the correlation
between enzyme size and pore size is not a linear one. Takahashi et al.
reported on the catalytic behavior of three silica mesoporous materials
FSM-16, MCM-41, and SBA-15 with various pore diameters from 2.7 to
9.2 nm when they were used to adsorb horseradish peroxidase (HRP) in a
single immersion method.22 The study of thermal stabilities and enzymatic
activities in an organic solvent revealed that, surprisingly, FSM-16 and
MCM-41 showed a larger amount of adsorption of HRP than SBA-15 or silica
gel when the pore sizes were larger than the 5 nm. The increased enzyme
adsorption capacity was attributed to the surface characteristics of FSM-16
and MCM-41 that may be related to the methods used for their synthesis, in
which cationic alkyltrimethylammonium salts were used as template for the
synthesis, while SBA-15 materials were prepared by using a non-ionic
surfactant. Furthermore, the immobilized HRP on FSM-16 and MCM-41 with
pore diameters B5 nm showed the highest enzymatic activity in toluene
and thermal stability in aqueous solution at the temperature of 70 1C.
This finding led to the conclusion that surface character and size matching
between pore sizes and the molecular diameters of HRP are important in
achieving high enzymatic activity in organic solvent and high thermal
stability.22
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(a)
(d)
(b)
(e)
(c)
(f)
(g)
Figure 5.3
5.2.3
Schematic illustration of how protein packing varies as a function

of pore diameter in MCM-41 and SBA-15 and enzyme diameter: (a)
close-packed, (b) 3d/2 interval, (c) 2d interval, (d) separated singlemolecular adsorption, (e) separated double-molecular adsorption, (f)
separated triple-molecular adsorption and (g) interdigitated triplemolecular adsorption.
Enzyme Immobilization/Encapsulation in
Hierarchically Ordered Mesoporous Silica Materials
Recent studies revealed that mesoporous silica spheres with hierarchical

structure, which usually implies bimodal mesoporous structure (BMS),
having pore ranges in the 23 nm and 1040 nm range, show faster immobilization rates and significantly improved enzyme-immobilization capacity
compared to similar particles with smaller mesopores. Caruso and coworkers verified the enzyme immobilization capacity of the BMS spheres by
the color variation of the particles following exposure to enzyme solutions.7
Cytochrome C and catalase solutions show a red and browngreen color,
respectively. The white BMS and SBA-15 particles turn deep red after exposure to cytochrome C solution, whereas a control experiment utilizing
mesoporous silica with a 2 nm pore diameter showed very small color
change.
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Bernal et al. showed that hierarchical porous silica, particles or monoliths,

synthesized by the polycondensation of sodium silicate in the presence of
cetyltrimethylammonium bromide and ethylacetate at dierent concentrations under hydrothermal conditions have been able to immobilize
b-galactosidase from Kluyveromyces lactis by adsorption.25 The enzyme
loading capacity (higher than 50 mg (g support)1) and the retention ability
(lixiviation less than 20% after 72 h of catalysis) of these supports are
explained as a function of the hierarchical porosity, mesopore sizes of
1040 nm, macropore sizes of 0.0720 mm, and the presence of ionized
silanol groups on the surface. The optimum pH value and temperature for
the maximum activity of the obtained hybrid biocatalyst indicated that the
three-dimensional structure of the enzyme was not significantly aected
during the immobilization process. The stability under extreme conditions
was improved in comparison with the homogeneous solution of lactase.
Furthermore, the porous supports exhibited morphology and porous stability under the immobilization and catalytic processes. These results show
that the obtained materials are good candidates for the immobilization of
large enzymes.
5.3 Enzyme Immobilization Strategies in Porous

Silica
5.3.1
Introduction
General enzyme immobilization methods may be subdivided into three

general classes according to the forces involved: physical adsorption, where
hydrogen bonding, and electrostatic and hydrophobic interactions between
support and enzyme exist; covalent attachment, where covalent bonds are
formed with the enzyme; and cross-linking which leads to self-immobilization as illustrated in Figure 5.4.26 The advantages and disadvantages of each
strategy are highlighted in Table 5.2.
(a)
Figure 5.4
(b)
General enzyme immobilization techniques.

(c)
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108
Table 5.2 Advantages and disadvantages of the dierent immobilization methods.

Immobilization
method
Physical adsorption
Chemical (covalent)
binding
Entrapped CLEAs/
encapsulation
Advantages
Disadvantages
Cheap, simple and rapid experimental

procedure
(Mostly) no functionalization of support is
required
No toxic solvents are required
No conformational changes of the enzyme
No destruction of the active site of the enzyme
No leaching of enzymes from the support
Tight binding of enzyme to the support
Wide choice of organic linkers is available
Established methods of functionalization/
modification of supports
Leaching of enzymes from the support during the

catalytic reaction due to changes in reaction
conditions (e.g. temperature, pH) or through
mechanical shear forces
Chapter 5
Stabilization of multimeric enzymes

Stabilization towards harsh reaction
conditions (e.g. extreme pH)
High purity of enzyme is not required
No leaching from the support
Dierent enzymes can be co-immobilized
(tandem-system)
No or minimal conformational changes of
the enzyme
Size of the CLEAs is restricted by the cage size
Most complicated and expensive

immobilization method
Functionalization/modification of support surface
is necessary
Use of toxic chemicals (e.g. glutaraldehyde)
Reduction or even loss of catalytic activity resulting
from conformational changes of the enzyme
Complicated experimental process (more than two
steps are necessary)
Use of toxic chemicals (e.g. glutaraldehyde)
Decreased diusion rate of substrates/products due
to reduced pore volume
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This general methodology translates to porous silica in physical adsorption, chemical adsorption and encapsulation or self-immobilization,
shown in Figure 5.4c. Cross-linked enzyme aggregates (CLEAs) were recently
explored as a combined cross-link/encapsulation approach. Specifically,
Mateo et al. demonstrated that a mild cross-linking upon enzyme encapsulation generated CLEAs from several enzymes (penicillin G acylase,
hydroxynitrile lyase, alcohol dehydrogenase, and two dierent nitrilases) by
precipitation and subsequent cross-linking using dextran polyaldehyde inside the silica pores.27 In most cases, higher immobilization yields were
obtained using the latter cross-linker as compared with the commonly used
glutaraldehyde. Active site titration of penicillin acylase CLEAs showed that
the higher activity originated from a significantly lower loss in active sites
using dextran polyaldehyde as a cross-linking agent. It is proposed that
macromolecular cross-linkers are too large to penetrate the protein active
site and react with catalytically essential amino acid residue.
5.3.2
Non-covalent Binding of Enzymes on Porous Silica

Supports Adsorption
Non-covalent immobilization (physical adsorption) of an enzyme onto a

solid is probably the simplest way of preparing immobilized enzymes. The
method relies on a non-specific physical interaction between the enzyme
protein and the surface of the matrix, achieved by mixing a concentrated
solution of enzyme with the solid. A major advantage of adsorption as a
general method of insolubilizing enzymes is that usually no reagents and
only a minimum of activation steps are required. As a result, adsorption is
cheap, easily carried out, and tends to be less disruptive to the enzyme
protein than chemical means of attachment. The binding is by hydrogen
bonds, multiple salt linkages, and van der Waals forces.
In this respect, the method is similar to actual biological membranes and
has been used to model such systems. A disadvantage is the weakness of
the adsorptive binding forces; adsorbed enzymes are easily desorbed by
temperature fluctuations and even more readily by changes in substrate
concentration and ionic strength.28
As indicated in Figure 5.2, surface characteristics must be accounted for
prior to the immobilization process. In the case of favorable electrostatic
enzymesupport interactions, the actual immobilization process consists of
dispersing the porous silica material in an enzyme solution for a determined
period of time to allow the enzyme to diuse in the pores. For materials with
antagonistic properties, i.e. hydrophobic silica and hydrophilic enzyme, the
pore surface is further functionalized with hydrophilic groups to match the
enzyme surface properties.
In addition to the traditional procedure described above, other innovative
approaches have been developed, mostly to address weak electrostatic
enzymepore interactions. To prevent enzyme leaching several reports refer
to physical entrapment, for example by solgel coating or polyelectrolyte (PE)
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Chapter 5
multilayer entrapment, where a layer of protective encapsulant is added on

the surface of the silica particle to sequester the enzyme that was previously
adsorbed. Caruso et al. reported the encapsulation of several enzymes
(catalase, peroxidase, lysozyme) in mesoporous silica spheres by physical
adsorption, followed by stabilization through deposition of multilayered
polyelectrolyte shells on to the enzyme-loaded silica and demonstrated that
encapsulation resulted in enhanced enzyme properties.7
5.3.3
Covalent Immobilization of Enzyme onto Porous Silica

Supports
The most intensely studied immobilization technique is the formation of

covalent bonds between the enzyme and the support matrix. The functional
groups of proteins suitable for covalent binding under mild conditions
include (i) the a-amino groups of the chain end and the epsilon amino
groups of lysine and arginine, (ii) the a-carboxyl group of the chain end and
the b- and g-carboxyl groups of aspartic and glutamic acids, (iii) the phenol
ring of tyrosine, (iv) the thiol group of cysteine, (v) the hydroxyl groups
of serine and threonine, (vi) the imidazole group of histidine, and (vii)
the indole group of tryptophan. Covalent bonding should provide stable,
insolubilized enzyme derivatives that do not leach enzyme into the
surrounding solution.
Furthermore, covalent immobilization must consider the positioning of
active sites in respect to the substrate. The choice of single-point or multipoint enzyme anchoring depends on the enzyme conformation, and enzyme
stability in the process condition. Multipoint anchoring confers rigidization,
which would be correlated with high enzyme stability. A schematic of the two
strategies is illustrated in Figure 5.5.
Figure 5.5
Single vs. multipoint immobilization of enzymes on the pore surface.

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Enzyme stability is tremendously improved by the covalent attachment of

enzymes in mesoporous silica. In a recent study, three SBA-15 functionalized
materials, prepared by a typical process and grafted with 3-aminopropyltrimethoxysilane (ATS), 3-glycidoxypropyltrimethoxysilane (GTS) and with
3-aminopropyltrimethoxysilane and glutaraldehyde (GA-ATS), respectively,
were used for the immobilization of chloroperoxidase and glucose oxidase
and the resulting biocatalysts were tested in the oxidation of indole. It
was found that enzymes anchored to the mesoporous host by the organic
moieties can be stored for weeks without losing their activity. Furthermore,
the covalently linked enzymes are shown to be less prone to leaching than
the physically adsorbed enzymes, as tested in a fixed-bed reactor under
continuous operation conditions.
The activity of the immobilized enzymes inside the pores is often dierent
from that of the free enzymes, and an important challenge is to understand
how the immobilization aects the enzymes in order to design immobilization conditions that lead to optimal enzyme activity. A complete understanding of active enzyme conformation will lead to controlling the type of
linkage (single-point vs. multipoint).
A recent work reported by Bernal et. al. demonstrates this concept.23
Hierarchical meso-macroporous silica (average mesopore diameter: 20 nm)
was synthesized and chemically modified to be used as a support for the
immobilization of lipases from Candida antarctica B and Alcaligenes sp. and
b-galactosidases from Bacillus circulans and Aspergillus oryzae. The catalytic
activities and thermal stabilities of enzymes immobilized by multipoint
covalent attachment in silica derivatized with glyoxyl groups were compared
with those immobilized in glyoxyl-agarose, assessing the biocatalysts performance under non-reactive conditions in an aqueous medium. In the case
of A. oryzae, b-galactosidase and Alcaligenes sp. lipase, an additional step of
amination was needed to improve the immobilization yield. The specific
activities of lipases immobilized in glyoxyl-silica were high (232 and
62 IU per gram, for C. antarctica B and Alcaligenes sp. respectively); thermal
stabilities were higher than those immobilized in glyoxyl-agarose. Although
in the case of b-galactosidases from B. circulans and A. oryzae, the specific
activities (250 and 310 IU per gram, respectively) were lower than the ones
obtained with glyoxyl-agarose, expressed activities were similar to values
previously reported. Thermal stabilities of both b-galactosidases immobilized in glyoxyl-silica were higher than when glyoxyl-agarose was used as the
support. Results indicate that hierarchical meso-macroporous silica is a
versatile support for the production of robust heterogeneous biocatalysts.
The immobilization of Mucor miehei lipase onto mesoporous silica materials using supports with dierent pore diameters show the substrate used
in the reaction acting as an enzyme activator. The lipase uses the fatty
substrate as lipophilic interface required for the opening of the active site of
the enzyme. IR spectroscopy was used to determine the adsorption isotherms in dierent pH conditions. The biocatalyst was tested for the
methanolysis of colza oil. The production of methyl esters was monitored
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over time by gas chromatography coupled to a mass spectrometer. By using a

ratio lower than the stoichiometry, the methanol conversion was complete
and high transesterification yields could be obtained even in the absence of
non-polar solvents (i.e. hexane).29
5.4 Characterization of Catalytic Activity for Enzyme

Immobilized in Porous Silica
5.4.1
Introduction
A detailed characterization of porous silica materials involves a large

spectrum of analyses. Transmission electron microscopy (TEM), scanning
electron microscopy (SEM), physisorption, small angle X-ray scattering
(SAXS), and solid-state NMR (13C and 29Si) are used to determine particle
morphology, pore structure, pore size and pore-size distribution, specific
surface area and pore volume of the materials. We will not present a detailed
description of all the characterization techniques relevant to mesoporous
silica, as they are well-established analytical methods, well-documented for
porous silica materials. We will focus on characterization techniques that
measure the enzymatic activity post-immobilization and on quantitative
determination of enzyme loading.
The immobilization parameters are directly related to the activity and
stability of the enzyme. Therefore, the percentage of enzyme immobilized
and the enzyme activity remaining after immobilization are stated together
with the experimental conditions used for their determination. Enzyme activities for immobilized enzymes are defined in the same way as for free
enzymes i.e. the katal is the recommended unit. This information is used for
comparing immobilization methods.
The percentage of enzyme immobilized is usually calculated by measuring
the amount of enzyme remaining in the supernatant after immobilization
and subtracting this from the amount originally present. The absolute enzyme activity remaining on the support after immobilization is more dicult
to determine and an apparent activity is usually measured which takes into
account mass transfer and diusional restrictions in the experimental
procedure. The other critical performance indicator is the stability of the
immobilized enzyme with respect to time, temperature and other storage
conditions.
5.4.2
Determination of Enzyme Concentration in Porous

Silica
5.4.2.1 UV Absorption
UV-Vis spectrometry is a widely used method for measuring concentrations
of proteins. Proteins have characteristic absorption peaks at 200 nm and
280 nm. All peptide bonds absorb UV light at 200 nm whereas the aromatic
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amino acids tryptophan and tyrosine absorb UV light at 280 nm. The absorbance at 200 nm is mainly due to the many peptide bonds in a protein.
However, many other substances also absorb light in this area and 200 nm is
therefore not a suitable wavelength for estimating the concentration of
proteins. Therefore measurements are normally performed at 280 nm, thus
one should be aware of the possible interference by contaminating nucleic
acids (and possibly other substances) that absorb strongly at 260 nm.
5.4.2.2
Colorimetric Assays
Colorimetric assays are also used to determine protein concentration.

Well-known examples are the Lowry assay,30 the BCA (bicinchoninic acid)
assay,31 and the Bradford assay.32 These assays are all based on a color shift
of an extrinsic molecule in the presence of a protein.
A recent review of physicochemical properties of immobilized enzymes
approaches both characterization methods and challenges.33 The authors
summarize methods that can be used to understand how material properties
can be linked to changes in enzyme activity. Real-time monitoring of the
immobilization process and techniques that demonstrate that the enzymes
are located inside the pores are discussed by contrasting them with the
common practice of indirectly measuring the depletion of the protein concentration or enzyme activity in the surrounding bulk phase. A new methodology, based on pore filling (pore volume fraction occupied by proteins) is
proposed as an accurate standard for comparing the amount of immobilized
enzymes at the molecular level. The article introduces methods to detect
changes in enzyme structure upon immobilization and to study the microenvironment inside the pores.
5.4.2.3
Infrared Spectroscopy (IR)
IR can be used to obtain information about enzymesubstrate (ES) complexes. In ES complexes there are well-organized binding modes, which are
quantifiable using infrared methods. In analyzing infrared data, it is possible to identify binding modes and heterogeneity of ES complexes.
5.4.2.4
Other Techniques
More recently, spherical aberration (Cs) correlation scanning transmission

electron microscopy (STEM) has elucidated the presence of enzymes inside
the pores. In the current manuscript we report a detailed characterization
based on spherical aberration (Cs) cor. STEM of enzyme (lipase)-loaded
ordered mesoporous silica (SBA-12) at an accelerating voltage of 80 kV.
The extremely high-resolution images combined with electron energy loss
spectroscopy (EELS) analysis have allowed a complete and unambiguous
detection of enzyme presence inside the pores.34
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Enzymatic Activity
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The following spectroscopic techniques are the most utilized to determine

immobilized enzyme activity: fluorescence spectroscopy and UV-Vis
spectroscopy.
5.4.3.1
Fluorescence Spectroscopy
Fluorescence spectroscopy reveals the existence of ES complexes and what

they are made of. Substrate fluorescence is measured and compared to the
product fluorescence and the dierence is reflecting enzyme activity. However, many impurities found in fluorescent compounds, when exposed to
light, interfere with the spectroscopy, making this technique more sensitive
than other assays.
5.4.3.2
UV-Vis Spectroscopy
The activity of the enzymes immobilized in various materials is typically

evaluated by UV-Vis spectrometry. The MichaelisMenten equation is one of
the simplest and best-known models of enzyme kinetics. The model takes
the form of an equation describing the rate of enzymatic reactions (eqn
(5.1)), by relating reaction rate v to [S], substrate concentration:
v
dP
Vmax S
dt
Km S
(5:1)
where v is the velocity of the reaction, Vmax is the maximum (theoretical)

velocity, and Km is the Michaelis constant, (k1 kcat)/k1.
The maximum theoretical velocity, Vmax, is the velocity when the substrate
binds to all of the active sites on all the enzymes, when it is totally saturated. This is impossible because there will always be some free enzyme
available; the reaction to produce product and free enzyme is always going
on. The Michaelis constant Km is numerically equal to the substrate
concentration [S] that produces a velocity v Vmax/2. Vmax can be roughly
estimated from plots of v vs. [S], and then Km can be obtained from the value
of [S] at Vmax/2 on the plot.
Km and Vmax provide very important information about an enzymatic
reaction, and are among the very first things that scientists try to determine
or verify for an enzyme they are using. One of the reasons that Km is important is that it provides an idea of the anity, the binding strength, of
the enzyme for the substrate. With Vmax and the actual molar concentration
of the enzyme, the reaction rate, kcat, can be calculated. This is also called
the turnover number, the number of substrate molecules transformed to
product per unit time by a single enzyme molecule under maximal conditions. This provides a good measure of the speed and eciency of an
enzyme.
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5.5 Conclusions
Porous silicas are suitable supports for the immobilization of enzymes. The
immobilization strategy must be chosen based on the enzyme and the targeted application. Physical adsorption, encapsulation, covalent binding and
recently cross-linking are the predominantly employed routes that possess
certain advantages and drawbacks. The use of tailor-made silica supports
with optimized particle size and morphology, pore diameter and surface
properties as detailed in the flowchart in Figure 5.2 will result in biocatalysts
with increased activity, higher stability and reusability. Novel surface-functionalization strategies for modification of the support properties are constantly being developed. However, until now, industrial applications exploring
the specific features of porous silica supports have not been disclosed.
Combining the knowledge generated from all presented methodologies
will aid in rationally designing biocatalyst based on enzymes immobilized in
mesoporous materials.33
References
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2. A. Schmid, J. S. Dordick, B. Hauer, A. Kiener, M. Wubbolts and
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14. J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge,
K. D. Schmitt, C. T. W. Chu, D. H. Olson and E. W. Sheppard, J. Am.
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21. H. H. P. Yiu, P. A. Wright and N. P. Botting, Microporous Mesoporous
Mater., 2001, 4445, 763768.
22. H. Takahashi, B. Li, T. Sasaki, C. Miyazaki, T. Kajino and S. Inagaki,
Chem. Mater., 2000, 12, 33013305.
23. C. Bernal, P. Urrutia, A. Illanes and L. Wilson, New Biotechnol., 2013, 30,
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R. A. Sheldon, Biotechnol. Bioeng., 2004, 86, 273276.
28. R. A. Messing, Immobilized Enzymes for Industrial Reactors, Academic
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29. J. Jacoby, A. Pasc, C. Carteret, F. Dupire, M. J. Stebe, V. Coupard and
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08:24:08.
CHAPTER 6
Heterogeneous Catalysts for

Biodiesel Production
DANIELA R. RADU*a AND GEORGE A. KRAUSb
a
Department of Chemistry, Delaware State University, Dover,

DE 19901, USA; b Department of Chemistry, Iowa State University, Ames,
Iowa 50011, USA
*Email: dradur@desu.edu
6.1 Introduction
Biodiesel is a renewable fuel that can be generated from plant oils,
rendered animal fats and industrial waste oils.1 It has evolved into a
significant industry in the midwestern United States and in Europe. In the
United States biodiesel is prepared primarily from soybean oil; in Europe,
biodiesel is generated mostly from rapeseed oil. Biodiesel has a number of
advantages over diesel fuel. Although the National Biodiesel Board
has listed a number of benefits, the most significant ones are that biodiesel
is a renewable fuel that is non-toxic, biodegradable and free of sulfurcontaining impurities.2 Biodiesel also has significant lubricity compared
to petrochemical fuels. These qualities make biodiesel especially useful
in places such as national parks, harbors and other environmentally
sensitive areas. Biodiesel is commonly sold as a mixture with petroleum
fuels: for example, B20 is a mixture of 20% biodiesel and 80%
petroleum fuel.
Biodiesel, also known as fatty acid methyl esters (FAME), is one of
the most promising alternative biofuels and is currently produced by a

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O
O C R
O
O C R
O
O C R
OH
NaOH
3 CH3OH
R = C14 ~ C24 Hydrocarbon Chain
Scheme 6.1
O
R C O CH3
OH
OH
Biodiesel
Base-catalyzed transesterification of triglycerides to biodiesel.
base-catalyzed transesterification reaction with triglycerides and methanol

as illustrated in Scheme 6.1. Biodiesel is a mixture of compounds because
it is produced by transesterification of triglycerides found in soybean oil.
Triglycerides contain mixtures of esters of dierent chain lengths
and some chains have alkenes or epoxides. The most common alcohol
used in the transesterification of soybean oil is methanol, in large part
because it is less expensive than other alcohols. For many decades the
transesterification reaction was conducted by heating soybean oil, an excess of methanol and a few percent of a homogeneous catalyst such as
sodium hydroxide or sodium methoxide for several hours and then neutralizing the catalyst and separating the biodiesel from the glycerol.
Although catalysts such as sodium methoxide aord excellent yields of the
transesterification product, a methyl ester, the catalyst must be neutralized
with an acid when the transesterification reaction is complete. This
neutralization produces a salt which often winds up as an impurity in the
glycerol, reducing its value. Additionally, the production of biodiesel
using homogeneous catalysts has a large water footprint. For every liter of
biodiesel produced, almost four liters of water are utilized. Moreover, the
free fatty acids present in feedstocks such as rendered animal fats and
industrial waste oils would neutralize the basic catalyst. Therefore, a pretreatment step which converts the free fatty acids into esters using an acid
catalyst is required for feedstocks that contain significant amounts of free
fatty acids.
When this work began in 1999, the use of heterogeneous catalysts for the
generation of biodiesel was not yet employed on an industrial scale. Certain
acidic materials such as zeolites and ion exchange resins had been reported
to catalyze the transformation.3 They have the advantage that any free fatty
acids present in the feedstock would be esterified. However, the rate of the
transesterification using acidic catalysts is much slower than the reaction
employing basic catalysts. Certain metal oxides have been used for the
transesterification reaction.4 However, many metal oxides are somewhat
soluble in methanol. Also, free fatty acid impurities would react with the
metal oxides. The ideal catalyst for the transesterification reaction would be
economical, recyclable, stable to fatty acid impurities, and would eliminate
the costly aqueous work-up step.
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6.2 Previous Work using Mesoporous Materials

In recent years there have been a number of reports of demonstrating the
ability of heterogeneous catalysts to promote the preparation of biodiesel.
The reports have been collated in timely reviews by Basumatary5 and by Ma
and Hanna.6 Melero and coworkers recently utilized mesoporous arenesulfonic acids to convert crude palm oil containing approximately 6% free
fatty acids into biodiesel.7 Chang and coworkers studied mesoporous
carbonsilica composites and found these sulfonic acid catalysts to be
eective for the production of biodiesel.8 Zuo and coworkers showed that
mesoporous silica functionalized with alkyl sulfonic acids gave good yields
of biodiesel with soybean oil contaminated with 20% oleic acid.9 Mar and
Somsook synthesized a propyl sulfonic acid-functionalized mesoporous
catalyst that could esterify oleic acid and was superior to Amberlyst 15.10
Mesoporous materials have received much attention in the past decade
because of their ease of formation and their ease of functionalization. This
has permitted an extensive study of structureactivity relationships among
catalysts. They have larger pore sizes compared to zeolites, allowing larger
organic molecules to enter.
6.2.1
StructureActivity Studies of Mesoporous Sulfonic Acids
Shanks and Mbaraka have studied mesoporous silica with dierent sulfonic
acids at dierent surface concentrations.11 Chen and coworkers have studied
dual-functionalized mesoporous silica containing both sulfonic acid groups
and disulfide groups.12 Dhainaut and coworker prepared macroporous
mesoporous SBA silicas via dual templating. They cite rate enhancements for
the transesterification of bulky esters.13 Chen and coworkers utilized
mesoporous sulfonic acids with short channels and high acid capacities.
They found that these catalysts were superior to Amberlyst 15 resin.14
Yadav and Sharma used a mesoporous sulfonic acid catalyst treated with
lanthanum chloride to convert fructose into 5-hydroxymethylfurfural in good
yield.15 Karimi and coworkers utilized a phenylene-bridged mesoporous
silica catalyst to produce biodiesel.16 They attributed the enhanced yield to
the hydrophobic character of the bridged catalyst. Tang and coworkers
produced mesoporous silicas having both platinum and sulfonic acid
groups. They utilized this catalyst for a novel one-step hydrogenationesterification of acetic acid and acetaldehyde.17 Karimi and Mirzaei evaluated
a number of mesoporous sulfonic acid catalysts and correlated the improved
yields of hydroxymethylfurfural with lower surface hydrophobicity.18
6.2.2
Catalysis of Organic Reactions
Mesoporous silicas functionalized with sulfonic acids have been eective in

a number of widely used organic reactions. Bossaert and coworkers have
utilized mesoporous sulfonic acids to catalyze the synthesis of
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19
monoglycerides. Clark and coworkers have used mesoporous sulfonic

acids as substitutes for environmentally hazardous Lewis and Bronsted
acids.20 Macquarrie and coworkers have used perfluorinated sulfonic acids
immobilized onto mesoporous silica to catalyze FriedelCrafts acylation reactions.21 Shanks and Bootsma have evaluated the hydrolysis of cellobiose
using mesoporous silica catalysts.22 Chen and coworkers studied the synthesis of bisphenol A using dual-functionalized catalysts.23 Davis and coworkers also synthesized bisphenol A employing a novel thiol/sulfonic acid
paired catalyst.24 Castanheiro and coworkers have evaluated mesoporous
silica sulfonic acids for the successful methoxylation of a-pinene.25
Shi and coworkers studied the transformation of xylose into furfural using
mesoporous SBA-15 catalysts.26 Lopez-Sanz and coworkers used mesoporous
sulfonic acids to prepare a library of quinolines.27 Thiel and coworkers used
acidbase bifunctional mesoporous silica nanoparticles to achieve a clever
one-pot deacetalizationaldol reaction.28 Peng and coworkers created acid
base bifunctional mesoporous catalysts by in situ cleavage of a sulfonamide
bond. They employed this novel catalyst in several solvent-free Knoevenagel
condensation reactions.29 Agirrezabal-Telleria and coworkers studied the
reaction of mesoporous sulfonic acids with xylose as a function of sulfonic
acid load and temperature. In their optimized reaction conditions, they
obtained a 82% yield of furfural at 170 1C.30 Hakki and coworkers found that
co-condensation of orthosilicates in the presence of titania aorded a
superior catalyst for the photocatalytic conversion of aromatic nitro
compounds into a variety of quinolines.31 Jun and coworkers utilized a
magnetically recyclable mesoporous catalyst for tandem acidbase reactions.32 Zhang described a mesoporous acid catalyst for the Mukaiyama
aldol reaction in aqueous media.33
6.2.3
Lin Group Contributions
The Lin group had developed mesoporous silica nanomaterials with welldefined geometries. Mesoporous silica nanospheres (MSNs), as they were
named by Lins group in 2001, benefit from a facile synthetic methodology
as well as potential for tailoring their structural properties. The MSN synthesis requires the condensation of a silica source around a template. The
most studied templating reagents are cationic surfactants, which render
materials with porosities in the range of 25 nm and block co-polymers,
generating 530 nm porosities. The interior of these materials resembles a
honeycomb, with parallel channels running throughout the nanospherical
particle. The channel diameter could be fine-tuned to accommodate a large
variety of molecules, from simple organic compounds to macromolecules.
These interior structures led to the idea of converting the pores in nanoreactors, which engaged the group in a large eort toward altering pore
functionality with catalytic groups. The functional groups in the channels
could be added through either post-synthesis grafting or by in situ addition
of an organo-functionalized silane, a method also called co-condensation.
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The dierence between the two methods is highlighted in Figures 6.1

and 6.2. Figure 6.1 illustrates the post-synthesis grafting method that
often leads to functional groups on the exterior surface and near the pore
openings of the mesoporous silica particle. In contrast, co-condensation
drives the majority of functional groups inside the pores with some of them
with the undesirable possible location inside the pore walls. When applying
co-condensation, the Lin group obtained materials functionalized with a
variety of functional groups, including thiols, sulfonic acids, amines and
ureas.34
In addition, they discovered that by performing the post-synthesis grafting
on materials prior to removing the surfactant templates, certain functional
Figure 6.1
Schematic representation of post-synthesis grafting of organo-silanes

onto mesoporous silica surface in respect to the silanol groups existent
on the pores surface.
Figure 6.2
Schematic representation of silica functionalization via co-condensation

of an organosilane in the presence of a silica source (showed silicic acid).
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Figure 6.3
Chapter 6
TEM image of a mesoporous silica nanosphere showing the hexagonal,

parallel array of pores.
groups could be selectively grafted to the outside of the nanoparticles. Another

interesting discovery was that multiple functional groups could be simultaneously added, thus moving toward forming multifunctional materials.
Novel catalysts could be created by combining grafting and co-condensation to generate selective functionalization of MSNs, leading to a synergy
of catalytic properties.
These durable materials were shown to catalyze several common organic
reactions. In addition to organic functional groups, the Lin group also reported
the incorporation of inorganic materials into the channels. The general structure of the mesoporous nanomaterial catalyst is shown in Figure 6.3 below.
The Lin group used these catalysts for multistep organic reactions.35 One
of the most significant applications of the catalysts fabricated in Lins group
was biodiesel preparation, for which the group focused on mesoporous
sulfonic acids.36
Biodiesel fabrication presents a series of challenges, as shown in
Scheme 6.2. To bypass the potential saponification reaction, a solid acid
catalyst is needed to transform free fatty acids, typically present in oil
feedstocks in various percentages.
6.2.3.1
Acid Catalyst
To address the first stage of biodiesel fabrication, the Lin group created
periodically ordered, sulfonic acid-functionalized mesoporous silicas with
pores sizes ranging from 20 to 60 and high acid-exchange capacities
(12 mequiv. of H1 (g of SiO2) 1). To do this the Lin group utilized a recently
developed synthetic method which allows the facile incorporation of various
acidic sulfonic groups to the mesoporous structures with the ability to finetune the loading of these groups.
As depicted in Scheme 6.3 the sulfonic acids are contained in the channels. The soybean oil and the solvent methanol enter the channel and
transesterification occurs in the channel. Free fatty acids also enter the
channel and are esterified with methanol.
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Scheme 6.2
Challenges in biodiesel fabrication: presence of free fatty acids.
Scheme 6.3
Synthesis of benzene-sulfonic mesoporous silica catalyst.
123
In addition to the intrinsic catalytic ability and the quantity of acid

groups in these catalytic systems, two important factors that can also
influence the overall performance of the proposed heterogeneous solid
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Chapter 6
acid catalysts are the sizes of the mesopores and the pore surface
properties. These characteristics can have large eects on pore mass transfer
of reactant, product, and intermediate species. In particular, the functionalization of these derivatized mesoporous silica materials with various
surface-bound groups allows the modulation of the catalytic systems to enhance substrate selectivity by tuning substrate accessibility and pore
hydrophobicity.
Thus, to address the above toward increasing selectivity of the transesterification reactions, various functional groups have been employed in
addition to the sulfonic acid groups. The materials design involved making
the pore surface hydrophobic. The reasoning behind this step was matching
the channel hydrophobicity with the long alkyl chains in the triglycerides,
and thus, promoting their fast diusion into the channels; increasing reaction kinetics.
In preliminary investigations, the Lin group tested the catalytic activity of
the aforementioned mesoporous solid acid catalyst in comparison with
two commercially available homogeneous catalysts (sulfuric acid, H2SO4,
and p-toluene sulfonic acid, p-TSA) and an SBA-type mesoporous silica
catalyst with a propylsulfonic acid functionality (SBA-15-SO3H-P123)
also developed in the Lin group. Compared with its homogeneous counterpart, p-TSA, it showed similar reaction kinetics, indicating a fast masstransfer process for the reactants and the products to diuse in and out of
the large pores (Figure 6.4).
6.2.3.2
AcidBase Catalyst
In parallel with fatty acids transformation, transesterification reactions

convert triglycerides in oil feedstocks in biodiesel. To avoid introducing a
second base catalyst, acid and base groups were introduced simultaneously
and site-separated on the dierent surfaces of mesoporous silica nanoparticle through co-condensation to functionalize the internal surface and
post-synthesis grafting to functionalize the external surface. As a result of
this ideal site-isolation, reaction cascades requiring two or more catalysts,
which are incompatible in one solution system, could be done by this new
internal and external surface-bifunctionalized particle.
Furthermore, following the same strategy used for sulfonic acid catalysts,
the unoccupied pore surface of the superbase and the acid-derivatized
mesoporous silicas were functionalized with propyl, phenyl, or pentafluorophenyl groups via post-synthesis grafting procedures using propyl,
phenyl, and pentafluorophenyl trialkoxysilanes, respectively, to yield a series
of multi-functionalized mesoporous silica supported microreactors for the
transesterification and esterification of various FFA-containing oil feedstocks. These mixed-functional materials allowed control of the surface reactivity of these materials. There were three organosulfonic acid functional
groups used in the study. The catalytic activities of the functionalized
mesoporous silicas were compared with several commercial catalysts,
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Figure 6.4
125
Schematic representation of the proposed catalytic system for the synthesis of methyl soyate and glycerol formation.
including homogeneous catalysts (sulfuric acid and p-TSA) and heterogeneous catalysts such as Nafions.
Following the success of acid catalyst for esterification, the Lin group also
conducted a preliminary transesterification of purified soybean oil to methyl
ester using a functionalized mesoporous solid catalyst. The resulting
nanomaterials were inexpensive to produce, were reproducible, and could be
reactivated simply by heating. A 100% conversion of the soybean oil to
methyl ester was accomplished in 20 min at 25 1C with a 5-fold excess of
methanol. The above studies suggested that a mesoporous sulfonic acid with
superbase and hydrophobic-group functionality could be employed for the
transformation of crude oil feedstocks in biodiesel from soybean oil eciently. Based on these preliminary results, there is an opportunity to design
a series of new solid catalysts with (i) higher amounts of catalytic groups,
and (ii) more reactive catalytic functionalities for both the proposed esterification and transesterification of various feedstocks.
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6.3 Industrial Partnership

We sought an industrial partner to explore the large-scale applications of
the Lin catalysts. West Central Cooperative is a full-service, farmer-owned
cooperative located in west-central Iowa, less than a one-hour drive from
Iowa State University. The corporate headquarters at Ralston, Iowa acts as
the hub for the companys trade territory that spans ten counties and extends 55 miles in each direction. West Centrals operating divisions include grain, agronomy, feed, soy processing, and administration. West
Central Soy is the manufacturing division of West Central Cooperative.
West Central Soy products are processed in a $30 million manufacturing
complex in Ralston, Iowa. More than six million bushels of soybeans are
processed annually at this facility. The product line of West Central Soy
includes: biodiesel, grati remover, penetrant and lubricant, methyl
esters, diesel fuel additive, asphalt release concentrate, fifth wheel grease,
and soy-based lubricants.
West Centrals $6 million biodiesel plant is adjacent to its Soy Center. The
biodiesel plant processes 8 million pounds of the co-ops soybean oil into
methyl esters each year. West Centrals current methyl ester process involves
heating the soybean oil and introducing alcohol and a catalyst. The resulting
reaction separates glycerol from the soybean oil. The catalyst is then removed
from the methyl ester through water washing and a neutralization process.
The end products are biodiesel, glycerol, and fatty acid. The excess water and
catalyst is left with the glycerol byproduct, which is sold at an 80% purity level
to companies that further process it into hundreds of industrial products.
In 2000, methyl-ester-production practices at the West Central Cooperative biodiesel plant include the use of a non-recyclable catalyst
(sodium methoxide, 1%). During processing, the catalyst concentrates in
the glycerol phase and must be neutralized with aqueous hydrochloric
acid. This adds downstream shipping weight in the form of water,
methanol, and sodium chloride (transportation energy costs) and energy
required to distill the glycerol. They also need to dispose of the nonrecyclable catalyst in landfills (at the rate of 10 pounds per 1000 pounds of
methyl ester produced).
They perceive several environmental benefits of a heterogeneous catalyst:
less energy expended to produce the (currently) non-renewable catalyst;
less transportation (and its associated emissions) to move the
(currently) non-renewable catalyst from its point of production to the
end user;
less potential of contamination from a spill of (currently) non-renewable catalyst during transport, handling, and storage;
minimal water usage due to the elimination of the wash step; and
lower disposal costs associated with the removed catalyst residue since
it will be recyclable and regeneratable.
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127
Utilizing a heterogeneous solid acid catalyst for the synthesis of biodiesel

could also circumvent the catalyst separation problem and at the same time
eliminate the free fatty acids (FFA) in the crude FFA-containing feedstocks.
To prevent ionic base-induced saponification during the transesterification
reaction, the West Central process uses sodium methoxide. Therefore, a
highly ecient solid acid catalyst can serve not only as a pretreatment
catalyst to remove FFAs from the triglycerides, but also as a catalyst for the
conversion of the oil to biodiesel.
The synthesis of over 700 g of the acid-functionalized mesoporous solid
catalyst was completed using a pilot-scale test stand configured at the West
Central facilities. Analysis by the Lin lab confirmed success in both reactivity
and structural integrity of the synthesized materials. These catalysts also
perform as expected with respect to recyclability during multiple bench-scale
conversion reactions. Figure 6.5 shows a representation of the catalyst produced to date.
The economic modeling used to gauge the viability of these catalyst materials was modified with data from the pilot-scale synthesis activities.
Knowing the usage rates and costs of the raw materials used in the synthesis,
the economic model could be refined with more realistic inputs. The results
of this ongoing feasibility test still show promise in use of these catalysts as
an economically viable alternative to todays homogeneous catalyst
technology.
Upon completion of the acid-catalyst synthesis reactions, the pilot-scale
test stand was re-configured to utilize the catalyst in larger scale conversion
reactions (1 gallon h 1). Much of the same resources from previous tests
were able to be reused in the new configuration, with the exception of the
1-gallon reaction vessel that was incorporated into the flow scheme
(Scheme 6.4).
Figure 6.5
Acid-functionalized mesoporous solid catalyst, synthesized at West Central.
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128
Chapter 6
Scheme 6.4
6.4 Conclusions
Multifunctional mesoporous silica nanosphere catalysts have been synthesized by Lins group through simultaneous derivatization with acidcontaining aryl radicals and superbase on the surface of mesoporous silica.
The derivatization was designed to reach a complete separation of the acid
and base groups, which enables the catalyst to perform this otherwise antagonistic acidbase function. The benefit of such catalyst is the capability of
converting both free fatty acids and triglycerides in a one-pot reaction with
high yield and excellent separation which allows biodiesel fabrication in one
step. This implies a tremendous processing-costs reduction due to eliminating expensive intermediate steps. Compared with other solid acid and
solid base catalysts, the MSN catalyst materials show stable and highly efficient catalytic performance in biodiesel production with conversions
reaching 100%. The catalysts are highly ecient, environmentally friendly,
inexpensive, and easy to prepare.
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08:24:10.
Subject Index
A (LTA zeolite A), 80, 81, 82
acidbase bi-functionalized catalyst
biodiesel production, 1245
large-pore mesoporous silica
nanoparticles, 1923
acid catalyst in biodiesel production,
1224, 127
activity of enzymes (catalytic activity)
immobilized on porous silica
supports, characterization, 11215
adsorption
enzyme immobilization by,
103, 104, 107, 108, 10910
by zeolites, 889
AEL (zeolite SAPO-11), 82, 90
Alcaligenes lipase immobilization,
111
aldol reaction, 37, 120
alkylation, aromatics, 90, 93, 94
allyl acetate epoxidation, 50
aluminosilicate minerals, zeolites
as, 77, 78, 81
amino groups of amino acids and
covalent enzyme immobilization,
110
aminopropyl (AP) groups, 37, 38
3-aminopropyltrimethoxysilane
(APTMS), 8, 10, 13, 19, 20, 34, 37
APTMS (3-aminopropyltrimethoxysilane), 8, 10, 13, 19, 20, 34, 37
arenesulfonic acids in biodiesel
production, 119
arginine e-amino group and
110
aromatics alkylation, 90, 93, 94

aspartic acid carboxyl groups and
110
Aspergillus oryzae b-galactosidase
immobilization, 111
Bacillus circulans b-galactosidase
immobilization, 111
base group-functionalized large-pore
mesoporous silica nanoparticles,
1923, see also acidbase
bi-functionalized catalyst
BEA* (beta zeolite), 78, 80, 82, 89, 90,
92, 94
benzene, alkylation, 90, 93, 94
benzene-sulfonic mesoporous silica,
123
beta zeolite (BEA*), 78, 80, 82, 89, 90,
92, 94
bi-functionalized mesoporous silica,
35, 36, 37, 120
nanomaterials, 1324, 35,
36, 37
bimodal mesoporous structure
(BMS), 106
biocatalysis see enzymes
biofuels, 1
biodiesel, 1, 11730
supported metal catalysts,
623
bioindustry
fuels see biofuels
supported metal catalysis,
626
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132
biomass conversion (cellulosic/

lignocellulosic), 127, 628
background of, 12
to chemicals, 623
enzyme-assisted, 34, 613, 64
to fuels see biofuels
in ionic liquid systems, 23
multi-functionalized
mesoporous nanoparticles
for, 127
supported metal catalysts,
628
bisphenols A and Z, 402, 44, 120
bis-silane, 423
bis(trimethylsilyl)acetamide (BSA), 71
block copolymers, mesoporous silica
synthesis, 30, 31, 32
BSA (N,O-bis(trimethylsilyl)acetamide),
71
CaA (5A zeolite), 88
Candida antarctica B lipase
immobilization, 111
carbamate and xanthate
co-condensation, 39, 40, 41
carbene insertion, 56
carbon, mesoporous (CMK-3), 667
carbon monoxide
hydrogen and (syngas), 68
preferential oxidation under
excess hydrogen, 6870
carboxyl groups of amino acids and
110
cations, inorganic, zeolite synthesis,
856
cellobiose conversion to HMF, 19,
22, 23
cellulase, 34, 613, 24, 64
immobilization, 1011
cellulosic biomass see biomass
cetyltrimethylammonium bromide
(CTAB), 5, 31, 34
CHA (SAPO-34), 82, 90, 94
charge, surface, mesoporous silica
nanoparticles, 11
Subject Index
chemical(s), supported metal

catalysts in biomass conversion
to, 623
chemical (covalent) binding, enzyme
immobilization by, 103, 107, 108,
11012
clustered surface distribution of
functionalized immobilized
species, 545
CMKJ-3 (mesoporous carbon), 667
co-catalysis see cooperative
catalysis
co-condensation (in situ addition of
organosilane), 323, 36, 52, 71,
1201
colorimetric assays of enzyme
concentration in porous silica, 113
connectivity, zeolites, 79, 85, 86
cooperative catalysis (co-catalysis),
401
cellulose-to-HMF conversion,
1923
copolymers, mesoporous silica
copper (Cu), 49, 504
cost (economic) modeling in
covalent binding, enzyme
immobilization by, 103, 107, 108,
11012
critical micelle concentration, 30
cross-linked enzyme aggregates
(CLEAs), 108, 109
CTAB (cetyltrimethylammonium
bromide), 5, 31, 34
cumene production, 93, 94
2-cyclohexen-1-one epoxidation, 50
cysteine thiol group and covalent
enzyme immobilization, 110
deacetalization, one-pot, 35, 120
density functional theory (DFT),
71, 72
dewaxing, catalytic, 923
dimensionality of zeolites, 78, 7980,
81, 82, 84, 868
View Online
Subject Index
08:24:10.
dimethylsulfoxide (DMSO), fructoseto-HMF conversion, 5

DMSO (dimethylsulfoxide), fructoseto-HMF conversion, 5
economic modeling in biodiesel
production, 127
electron microscopy of mesoporous
materials
enzymes, 11314
nanomaterials, 8, 15
Ellmans reagent, 39
EMIMCl (1-ethyl-3methylimidazolium chloride),
23, 16, 19, 21
encapsulation, enzyme, 2, 108, 109
cellulase, 3
in hexagonally ordered porous
silica materials, 103
in hierarchically ordered
porous silica materials,
1067
environmental benefits of
heterogeneous catalysts, 126
enzymes (in biocatalysis), 10016
cellulose conversion, 34,
613, 64
immobilization on porous
silica supports see
immobilization
epoxidation, 48, 50, 52, 56
erionite (ERI), 90
ethylbenzene production, 93, 94
ethylene glycol, cellulose conversion
to, 656
1-ethyl-3-methylimidazolium
(EMIM) chloride, 23, 16, 19, 21
excimer fluorescence, 534, 55
fatty acid(s), free (FFAs), biodiesel
production and, 118, 119, 122,
123, 124, 127, 128
fatty acid methyl esters (biodiesel),
1, 11730
FAU (zeolite Y), 78, 80, 81, 82, 89,
90, 91
133
FDU-12 (mesoporous silica), 4, 6, 32

Fe(II), 48
ferrierite (FER), 80, 82, 90
FischerTropsch synthesis, 94
5A zeolites (CaA), 88
fluid catalytic cracking with zeolites,
8990
fluorescence, excimer, 534, 55
fluorescence spectroscopy of
enzymes immobilized in porous
silica, 114
4-connected networks, zeolites, 77,
78, 79
free fatty acids (FFAs) and biodiesel
production, 118, 119, 122, 123,
124, 127, 128
fructose
glucose conversion to, 4, 22
to HMF conversion, 45, 1318,
19, 212, 223
FSM silica, 69, 103
FSM-16, 69, 104, 105
fuel production from biomass see
biofuels
functionalized mesoporous silica
nanoparticles see nanoparticles
techniques of
functionalization, 323, 702
b-galactosidase immobilization,
107, 111
gases, permanent, zeolites in
separation of, 889
germanium (Ge)-based zeolites, 86
glucose
cellulose conversion to, 613
supported metal
catalysts, 634, 667
to fructose conversion, 4, 22
to HMF conversion, 2, 19,
223
glutamic acid carboxyl groups and
110
glycerol formation, 125
gottardite, 78
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134
grafting
post-synthesis, 32, 34, 3640,
42, 45, 467
biodiesel production,
1202, 124
random ligand, 49
hemicellulose, hydrolytic
hydrogenation, 65
Henry reaction, 35, 37, 38
hexagonally ordered porous silica
materials, enzyme
immobilization/encapsulation in,
1036
hierarchically ordered porous silica
materials, enzyme
immobilization/encapsulation in,
1067
highly ultrastable zeolite Y (VUSY), 92
histidine imidazole group and covalent
horseradish peroxidase, 105
hydrocarbons
zeolite USY in hydrocracking
of, 91
zeolites in separation of, 889
hydrogen
from biomass, 68
preferential oxidation of
carbon monoxide under
excess of, 6870
hydrogenation, hydrolytic
cellulose, 645
hemicellulose, 65
hydrophilic/hydrophobic volume
ratios, mesoporous silica
synthesis, 30
hydroxides, zeolite synthesis, 85
hydroxyl (OH) groups
of mesoporous silica
nanoparticles, 9, 20, 21
of serine and threonine acids
and covalent enzyme
immobilization, 110
5-hydroxymethylfurfural (HMF), 23,
46, 1324
Subject Index
IBN-X, 104
IMF (zeolite), 85
imidazole group of histidine and
110
immobilization (on porous/
mesoporous silica supports)
enzyme, 10016
cellulose conversion, 34,
613
characterization of
catalytic activity,
11215
strategies of enzyme
immobilization,
10712
types of support used in
enzyme
immobilization, 1017
in single-site catalysis, 37, 49, 53
surface distribution of
functionalized
immobilized species,
546
indole group of tryptophan and
110
industry, zeolites applications, 80,
904, see also bioindustry
adsorption, 88
infrared spectroscopy, enzyme
concentration in porous silica, 113
inorganic species, zeolites, 856
International Zeolite Association
(IZA) Structural Commissions
3-letter (framework type) code, 79,
82, 89, 90
ion-exchange adsorption, zeolites
in, 88
ionic liquid systems, cellulose
conversion in, 23
iron(II)/Fe(II), 48
ITQ-2 (zeolite), 87
IZA Structural Commissions 3-letter
(framework type) code, 79, 82,
89, 90
View Online
Subject Index
08:24:10.
kinetics, fructose-to-HMF
conversion, 1318, 1618
L (LTL zeolite), 82, 90, 92, 93
large-pore mesoporous silica
nanoparticles (LPMSNs), 813
acidbase bi-functionalized,
1923
large-pore zeolites, 7980
light paran isomerization, 92, 93
lignin valorization, 678
lignocellulosic biomass see biomass
Lin group, 5, 120
biodiesel production, 29,
1202, 128
lipase immobilization, 111
Lobry de BruynAlberda van
Ekenstein transformation, 4
LTA (zeolite A), 80, 81, 82
LTL (zeolite L), 82, 90, 92, 93
lysine e-amino group and covalent
manganese (Mn), 50, 51, 52, 56
MCM family of mesoporous
materials, 29, 30, 31, 37, 6970,
71, 81, 102, 104, 105
MCM-22 (MMW), 80, 81, 82, 83,
84, 86, 87, 89, 90, 94
MCM-41, 29, 31, 37, 6970, 71,
102, 104, 105
MCM-48, 29, 30, 104
MCM-56, 87
medium-pore zeolites, 7980, 845
mercaptopropyl groups, 40, 44
3-(mercaptopropyl)trimethoxysilane
(MPTMS), 14, 15, 19, 20, 34, 45
MeSi(OEt)3 (methyltriethoxysilane),
71
mesoporous carbon (CMK-3), 667
mesoporous materials in biodiesel
production, 11925, 127, 128
mesoporous silica, 160
functionalized see
functionalized mesoporous
silica
135
immobilization on see
immobilization
single-site catalysis, 2860
examples, 3454
structural aspects, 2933
pore sizes see pore sizes
synthesis, 2933
metal catalysts, supported, 6176, see
also organometallic complexes;
rare earth metal zeolites
in bioindustry, 626
metal templating, 48, 49, 51
methanol conversion, zeolites, 94
methyl ester formation, 11112, 118,
125, 126
methyltriethoxysilane (MeSi(OEt)3),
71
MFI (ZSM-5), 78, 80, 81, 82, 83, 84,
85, 89, 90, 91, 92, 934
micelles, mesoporous silica
synthesis, 29, 30, 31, 32, 103
Michaelis constant, enzymes
immobilized in porous silica,
114
microporous structure of zeolites,
77
mordenite (MOR), 80, 82, 89, 90, 92,
93, 95
MPTMS (3-(mercaptopropyl)trimethoxysilane), 14, 15, 19, 20, 34, 45
MSE (zeolite), 81
MSU-X, 104
MTT (ZSM-23), 82, 92
MTW (ZSM-12), 82, 90
Mucor niehei lipase immobilization,
111
multi-functionalized mesoporous
silica nanoparticles see
nanoparticles
multi-point vs. single-point enzyme
anchoring, 110, 111
multi-site heterogeneous catalysis
(MSHC), 33, 34
mutinaite, 78
MWW (MCM-22) zeolites, 80, 81, 82,
83, 84, 86, 87, 89, 90, 94
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136
nanoparticles/nanomaterials,
mesoporous silica (mesoporous
silica nanoparticles), 349, 48,
54, 120
bi-functional, 1324, 35, 36, 37
biodiesel production, 1201,
124, 125
for cellulosic biomass
conversion, 127
characterization, 8, 15, 201
Pt catalysts on, 69
surface area, 8, 9, 10, 15, 21,
29, 42
nitrogen adsorptiondesorption
isotherms, mesoporous silica
nitrogen porosity for PdSBA15
materials, 47
NMR, mesoporous silica
nuclear magnetic resonance (NMR),
mesoporous silica nanomaterials,
810, 15
1-octene epoxidation, 50, 52, 56
olefins, 51, 52
epoxidation, 48, 50
one-dimensionality (1D), zeolites,
79, 82
one-pot reactions
cellulose-to-HMF conversion,
1924
deacetalization, 35, 120
organic reactions in biodiesel
production, 11920
organic structure-directing agents
see structure-directing agents
organoamines, 378
organometallic complexes, 45, 46, 51
organosilanes, 10, 14, 15, 19, 20, 32
in situ addition of ( cocondensation), 323, 36, 52,
71, 1201
oxidation of carbon monoxide under
excess hydrogen, preferential, 6870
Subject Index
palladium (Pd), 458

parans, light, isomerization,
92, 93
penicillin acylase cross-linked
enzyme aggregates, 109
peracetic acid, 501
permanent gases, zeolites in
separation of, 889
phenol ring of tyrosine and covalent
phosphotungstic acid (HPW) groups,
36, 37
platinum (Pt)
as supported metal catalyst,
645, 66, 67, 68, 6970
zeolites, 92, 93
PMOs, 104
pore openings
mesoporous silica, 32, 42
zeolites, 82, 87, 92
pore sizes/dimensions
mesoporous silica, 30, 32, see
also large-pore mesoporous
silica nanoparticles; smallpore mesoporous silica
nanoparticles
enzyme immobilization
and, 102, 104, 105,
107
nanoparticles, and
cellulosic biomass
conversion, 56, 8, 11,
12, 21, 24
supported metal catalysts
and, 6972
zeolites and, 7980, 82, 88
porous silica see silica
propylene glycol, cellulose
conversion to, 656
proton forms of zeolites, 856
pyrene, 53, 55, 56
random ligand grafting, 49
random surface distribution of
species, 545
rare earth metal zeolites, 91
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Subject Index
08:24:10.
rigidization in enzyme anchoring, 110

ruthenium (Ru) as supported metal
catalyst, 645, 667
SAPO-11 (AEL), 82, 90
SAPO-34 (CHA), 82, 90, 94
SBA-1, 104
SBA-15 (mesoporous silica), 34, 31,
32, 36, 42, 45, 467, 49, 52, 534,
56, 104, 105, 106, 111, 120
SBA-16, 32, 104
SBA-A, 43, 44
SBA-AT-p, 43, 44
SBA-AT-r, 43, 44
SBA-g3, 42, 43
SBA-T, 43, 44
scanning electron microscopy (SEM)
of mesoporous silica
scanning transmission electron
microscopy (STEM) of enzymes
immobilized in porous silica
enzymes, 11314
self-immobilization, enzyme, 107, 109
serine hydroxyl groups and covalent
silica
mesoporous see mesoporous
silica
porous, biocatalysis and, 1001
enzyme immobilization
see immobilization
zeolite synthesis from mixture
of alumina and, 812
silylation, 712
single-site catalysis, mesoporous
silica-supported see mesoporous
silica
single-point vs. multipoint enzyme
anchoring, 110, 111
small-pore mesoporous silica
nanoparticles (SPMSNs), 813
sodium cations, zeolite synthesis,
856
solvents for lignocellulosic biomass
degradation, 2
fructose-to-HMF conversion, 5
137
soybean oil, biodiesel production,

118, 119, 122, 125, 126
spectrometric/spectroscopic
determinations with enzymes
activity, 114
concentration, 11213, 113
structure-directing agents (SDA) in
zeolite synthesis
inorganic, 856
organic, 80, 834
sulfonic acids in biodiesel
production, 11920, 122, 123, 124
sulfonic groups, fructose-to-5-HMF
conversion using, 1318
surface area, mesoporous silica
nanoparticles, 8, 9, 10, 15, 21,
29, 42
surface charge of mesoporous silica
nanoparticles, 11
surface distribution of
species, 546
surface functionality of mesoporous
silica materials, 33, 701, 702
nanoparticles, 21
surfactant in mesoporous silica
mesoporous silica
nanoparticles, 6
syngas from biomass, 68
TESP-SA (3-triethoxysilylpropyl
succinic acid anhydride), 913
thermolytic molecular precursor
(TMP) method, 44, 45
theta-1 (ZSM-22; TON), 82, 90
thiolamine pairs, 3940
thiols/thiol groups, 14, 39, 44
as cocatalysts, 42
covalent enzyme
immobilization and, 110
three-dimensionality (3D), zeolites,
78, 80, 82, 85, 868
threonine hydroxyl groups and
110
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138
titanium silicalite (TS-1; ZSM-5;

MFI), 78, 80, 81, 82, 83, 84, 85, 89,
90, 91, 92, 934
TMCS (trimethylchlorosilane), 71
TMSOTf (trimethylsilyl
trifluoromethanesulfonate),
71, 72
toluene disproportionation and
alkylation, 94
p-toluenesulfonic acid (TsOH), 5
TON (theta-1; ZSM-22), 82, 90
transesterification, 124, 125
triglycerides, 118
trialkoxysilanes, 43, 49, 124
3-triethoxysilylpropyl succinic acid
anhydride (TESP-SA), 913
triglycerides, transesterification,
118
trimethylchlorosilane (TMCS), 71
trimethylsilyl
trifluoromethanesulfonate
(TMSOTf), 71, 72
tryptophan indole group and
110
TS-1 (ZSM-5; MFI), 78, 80, 81, 82, 83,
84, 85, 89, 90, 91, 92, 934
tschernikite, 78
TUN (zeolite), 85
tungsten (W) as supported metal
catalyst, 66
two-dimensionality (2D), zeolites, 80,
82, 85, 868
tyrosine phenol ring and covalent
ultrastable zeolite Y (USY), 8990,
91, 92
ultravioletvisible spectroscopy see
UV-VIS spectrometric/
spectroscopic determinations
Subject Index
uniform surface distribution of

species, 545
USY (ultrastable Y zeolite), 90, 91, 92
UV-VIS spectrometric/spectroscopic
determinations of enzymes
activity, 114
concentration, 11213
valorization of lignin, 678
vinylcyclohexane epoxidation, 50
VUSY (highly ultrastable zeolite YY),
92
West Central Cooperative, 126, 127
X (zeolite X), 88, 89
xanthate and carbamate
co-condensation, 39, 40, 41
Y (FAU; zeolite Y), 78, 80, 81, 82, 89,
90, 91
zeolites, 7799
adsorption, 889
catalysis, 8994
conventional, 7886
structures, 7981
synthesis, 816
dimensionality, 78, 7980, 81,
82, 84, 868
history, 78
novel classes, 778
organic structure-directing
agents, 80, 834
ZSM-5 (MFI; TS-1), 78, 80, 81, 82, 83,
84, 85, 89, 90, 91, 92, 934
ZSM-12 (MTW), 82, 90
ZSM-22 (Theta-1; TON), 82, 90
ZSM-23 (MTT), 82, 92

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Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-FP001

Heterogeneous Catalysis for Todays Challenges

Synthesis, Characterization and Applications

RSC Green Chemistry

Professor James Clark, Department of Chemistry, University of York, UK

Titles in the Series:

The Future of Glycerol: New Uses of a Versatile Raw Material

30: Polyhydroxyalkanoates (PHAs) Based Blends, Composites and

How to obtain future titles on publication:

For further information please contact:

Heterogeneous Catalysis for

RSC Green Chemistry No. 33

This book is dedicated to Dr Victor S.-Y.

RSC Green Chemistry No. 33

Conversion and Kinetics Study of Fructose-to-5Hydroxymethylfurfural (HMF) using Sulfonic and

Recent Developments in Supported Metal Catalysts

Chapter 4 Zeolites in the 21st Century

4.4 From 2D to 3D Zeolites and Vice Versa

Chapter 5 Enzyme Immobilization on Mesoporous Silica Supports

Introduction Biocatalysis and Porous Silica

6.3 Industrial Partnership

Background of Cellulosic Biomass Conversion

and lignin oers a broad spectrum of conversion (thermal cracking, fast

Cellulosic Conversion in Ionic Liquid Systems

Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles

co-workers also discovered SnCl4 in [EMIM]BF4 can convert glucose to HMF

Enzyme-assisted Cellulose Conversion

However, the structure of SBA-15 is 2D hexagonal with length of several mm,

Production of 5-Hydroxymethylfurfural from Cellulosic

5-Hydroxymethylfurfural (HMF), converted from lignocellulosic biomass, is

Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles

Mesoporous Catalysts from Cellulosic Conversion

1.2 Cellulase-immobilized Mesoporous Silica

Optimization of Reaction Conditions

Optimal reaction conditions with respect to temperature, the amount of

An illustration showing the production of 5-HMF converted from

Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles

cellulosic hydrolysis when using cellulase as a catalyst. Therefore, we first

of cellulase while keeping the maximum yield of glucose. Various amounts

Characterization of Mesoporous Silica Nanomaterials

Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles

Characterization of LPMSNs and SPMSNs. SEM, nitrogen adsorption

Summary of structural properties and functionalities of SPMSNs, LPMSNs

N.D. not done.

Cellulase was immobilized into SPMSN and LPMSN by physical adsorption

Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles

Summary of cellulase loading amount and yields of glucose for free

Cellulose Hydrolysis by using Cellulase-immobilized

As we have previously examined, 4.5 mg of free cellulase was enough to

Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles

domains) of the cellulase, thereby retaining the activity of cellulase. In fact,

Synthetic Process for Bi-functionalized MSN

The synthetic process of the bi-functionalized MSN is shown in Scheme 1.2

Synthetic process for preparing the bi-functionalized MSN.

Synthesis of Multi-functionalized Mesoporous Silica Nanoparticles

absorbed on the surface of (HSO3 IL)-MSN. The final product

Characterization of Mesoporous Silica Nanomaterials

Fructose-to-HMF Conversion using Bi-functionalized

Summary of characterization of bi-functionalized MSNs.

16.0 27.6 2.3

the reaction with the presence of the bi-functionalized MSN surprisingly

(a) Results of fructose-to-HMF conversion in dierent systems.