Lewis e Bronsted

Green Chemistry
View Article Online

CRITICAL REVIEW View Journal | View Issue
Published on 23 September 2016. Downloaded by Federal University of Minas Gerais on 02/03/2017 19:01:26.
Zeolite and zeotype-catalysed transformations of

Cite this: Green Chem., 2016, 18,
biofuranic compounds
5701
Hu Li,a Song Yang,a Anders Riisager,b Ashok Pandey,c Rajender S. Sangwan,c
Shunmugavel Saravanamurugan*c and Rafael Luque*d
Catalytic valorisation of biomass with solid functional materials has been recognised as a promising
approach to produce value-added biochemicals and biofuels. Furanic compounds such as 5-hydroxy-
methylfurfural (HMF), 5-ethoxymethylfurfural, 2,5-dimethylfuran, 2,5-diformylfuran and 2,5-furandicar-
boxylic acid can be obtained from hexoses and pentoses via selective dehydration and subsequent
etherication, hydrogenation, oxidation reactions, which show great potential for industrial applications to
replace petroleum-based chemicals and fuels. Zeolite and zeotype micro- and mesoporous materials
with tuneable acidity, good thermal stability and shape-selectivity have recently emerged as promising
solid catalysts, exhibiting superior catalytic performance to other heterogeneous catalysts. This review
focuses on the synthesis of biomass-derived furanic compounds catalysed by zeolitic materials, rstly
Received 29th August 2016, introducing zeolite-catalysed hydrolysis of di-, oligo- and polysaccharides and isomerization reactions of
Accepted 22nd September 2016
monomeric sugars. Subsequently, the catalytic dehydration reactions of hexoses and pentoses to obtain
DOI: 10.1039/c6gc02415g HMF and furfural are reported. Particularly, a variety of reaction pathways towards upgrading of the result-
www.rsc.org/greenchem ing platform furanic molecules to valuable bioproducts over zeolitic materials are discussed.
1. Introduction cesses.3 In the case of pentose and hexose carbohydrates, a

further dehydration step can be facilitated by Brnsted acid
Bioprocessing of lignocellulosic biomass, the most abundant sites to produce furfural and 5-hydroxymethylfurfural (HMF),
organic carbon resource, has been widely explored due to its respectively.4,5 The subsequent catalytic processes integrated
significant potential to be used as renewable feedstock to with other reactions such as oxidations and hydrogenations
produce valuable chemicals and biofuels via dierent are illustrated to be capable of yielding furan-derived value-
approaches including liquefaction, pyrolysis, gasification and added chemicals and liquid fuels (Scheme 1).6,7
chemistries such as hydrolysis, dehydration, oxidation, hydro- Porous materials with easy accessibility of acidic, basic or
genation and hydrogenolysis.1 Conventional biomass upgrad- metallic sites to large lignocellulosic macromolecules have
ing strategies (e.g., gasification and pyrolysis) can yield all attracted much attention to be utilised in the valorisation of bio-
major carbon species such as cellulose, hemicellulose and polymers.8 In recent decades, various micro-, meso- and macro-
lignin, wherein syngas can be obtained via gasification, while porous catalysts including resins, metal oxides, carbons, silicas,
pyrolysis gives bio-oil along with gaseous and solid products.2 polydivinylbenzene, and zeolites have been developed for
At low temperatures (ca. <200 C), monomers of biopolymers ecient transformation of biomass-based feedstocks.9 Zeolitic
(e.g., sugars and lignin-derived aromatics) can be substantially materials exhibit a number of excellent properties to be
formed from lignocellulose with high selectivity in the pres- employed as heterogeneous catalysts in selective transformation
ence of acidic catalysts, compared to the high temperature pro- of biomass, owing to their controllable acidity, good thermal
stability, shape-selectivity, and facile introduction of mesoporos-
ity.10,11 Typically, small-, medium- and large-pore zeolites can
a be classified on the basis of pore openings [i.e., 8-, 10- and
State-Local Joint Engineering Lab for Comprehensive Utilization of Biomass,
Center for R&D of Fine Chemicals, Guizhou University, Guiyang 550025, China 12-membered rings (MR)], respectively, and some of their
b
Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, physicochemical properties are summarised in Table 1.12 The
Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark physicochemical properties of these zeolites slightly vary with
c
Centre of Innovative and Applied Bioprocessing (CIAB), Mohali, Punjab-160 071, changes in their silicon to aluminium ratios. Extensive appli-
India. E-mail: saravana@ciab.res.in
d cations of zeolites as acidic catalysts or solid supports are
Departamento de Quimica Organica, Universidad de Cordoba, Campus de
Rabanales, Edificio Marie Curie (C-3), Ctra Nnal IV, Km. 396, E-14014 Cordoba, present in the petrochemical and oil-refining industries,
Spain. E-mail: q62alsor@uco.es showing great prospects for large-scale biomass upgrading.1315
This journal is The Royal Society of Chemistry 2016 Green Chem., 2016, 18, 57015735 | 5701
View Article Online
Critical Review Green Chemistry

Scheme 1 Catalytic pathways for valuable furans derived from HMF and furfural.6,7 [H]: hydrogenation, [O]: oxygenation, HMF: 5-hydroxymethyl-
furfural, HMFCA: 5-hydroxymethyl-2-furancarboxylic acid, DFF: 2,5-diformylfuran, FFCA: 5-formyl-2-furancarboxylic acid, MA: maleic anhydride,
DMF: 2,5-dimethylfuran, DMTHF: 2,5-dimethyltetrahydrofuran, FFA: furfuryl alcohol, BHMF: 2,5-bis(hydroxymethyl)-furan, BHMTH: 2,5-bis(hydroxy-
methyl)tetrahydrofuran, THFA: tetrahydrofurfuryl alcohol, THF: tetrahydrofuran, MF: 2-methylfuran, MTHF: 2-methyltetrahydrahydrofuran, GVL:
-valerolactone, EMF: 5-ethoxymethylfurfural, CMF: 5-chloromethylfurfural, BMF: 5-bromomethylfurfural.
Table 1 Properties of some representative medium-pore, large-pore, and mesoporous zeolites12
Pore structure
Cumulative pore Micropore BET surface
Zeolite Framework type Pore shape Pore size (nm) volume (cc g1) volume (cc g1) area (m2 g1)
Medium-pore FER 8 MR 0.35 0.48 0.14 0.10 360

10 MR 0.42 0.54
MFI 10 MR 0.51 0.56 0.18 0.13 450
Large-pore MOR 8 MR 0.34 0.48 0.20 0.16 550
12 MR 0.65 0.7
MWW 10 MR 0.41 0.55 0.20 0.14 380
10 MR 0.41 0.51
Supercage 0.71 1.82 0.20 0.12 440
Side pocket 0.71 0.9
BEA 12 MR 0.56 0.67 0.26 0.16 650
FAU 12 MR 0.74 0.74 0.35 0.20 870
Mesopore PMFI 10 MR 0.51 0.56 0.34 0.12 700
Mesopore 2.8 0.31 0.16 640
PMWW 10 MR 0.41 0.51 0.36 0.13 770
Supercage 0.71 1.82
Side pocket 0.71 0.9
Mesopore 1.8
Significant eorts have consequently been made on catalytic Some excellent review articles have illustrated the opportu-
transformation of carbohydrates into furanic compounds over nities and challenges of zeolitic chemistry in the catalytic con-
zeolitic materials with enhanced stability, appropriate function- version of biomass to a wide range of bioproducts.1417 Special
alities, and controllable porosities in recent years. emphasis has been laid upon the application of zeolites
5702 | Green Chem., 2016, 18, 57015735 This journal is The Royal Society of Chemistry 2016
View Article Online
Green Chemistry Critical Review
containing dierent active sites, shape selectivity, and struc- entry 2).22 It was interesting to note that coloured byproducts
tural stability.15 Nevertheless, zeolite-catalysed production and such as HMF could be adsorbed on zeolites, thus giving col-
upgrading of furanic compounds in carbohydrates processing ourless carbohydrates. Besides sucrose, other sugars including
have been rarely reviewed. The present contribution aims to cellobiose, maltose, inulin, and starch could also be eectively
provide a comprehensive overview of recent examples centered hydrolysed to the monomeric units of glucose or fructose
on the production of furan-type chemicals and biofuels as well using commercial dealuminated H-Y faujasite (Si/Al = 15) as
as upstream and downstream reactions involving furanic com- shown in Table 2, entry 3.23 Upon dealumination, the increase
pounds directed to various products. For specific catalytic pro- in the average acidity of zeolites appears to correlate well with
cesses, the desirable characteristics of zeolitic materials and a decrease of the Brnsted acid sites, most likely to result in
possible reaction pathways and/or mechanisms have also been the improved hydrolysis observed (Table 2, entry 4) in conjunc-
discussed. tion with increased accessibility.24 The increase of the Si/Al
ratio could also lead to an identical change in the distribution
and strength of the acid sites in zeolitic materials,25 with the
2. Upstream reactions to produce catalytic performance of H-beta exhibiting the prominent
furanic compounds eect of the Si/Al ratio on maltose hydrolysis (Table 2, entry 5).24
A dispersion of H-USY (Si/Al = 15) and H-beta (Si/Al = 40)
2.1. Zeolite-catalysed hydrolysis of biopolymers zeolites into polymeric matrices such as polydimethylsiloxane
Prior to catalytic valorisation of biomass, biomass pretreat- (PDMS) and polyvinyl alcohol (PVA) could adjust the balance of
ment through chemical, physical, or biological means is gener- hydrophilic/hydrophobic environments around the composite
ally involved as the initial step to facilitate the fractionation of catalysts to achieve an almost constant catalytic activity of
lignocellulose, as well as to ease the access of substrate com- H-beta/PVA for sucrose hydrolysis in four consecutive cycles.26
ponents to the active sites of solid catalysts in subsequent reac- Depolymerisation of hemicellulose and cellulose into sugar
tions.18 In recent years, mild and high-extent hydrolysis of monomers is a crucial step for integrating biorefineries.
oligo- and polysaccharides with solid acids is becoming one of Sulphonated resins such as Amberlyst 70 and Amberlyst 35
the most preferable choices to process biopolymers, especially were demonstrated to be ecient in the hydrolysis of xylan to
in consideration of the improved selectivity towards the xylose and arabinose (ca. 80% yield) at 120 C for 4 h, compar-
cleavage of glycosidic bonds.19 Owing to controllable surfaces able to that reported for 0.036 M H2SO4 (74% yield; Table 2,
and acidities, zeolites have been extensively investigated for entry 6).27 Zeolites, especially H-ferrierite (Si/Al = 55), exhibited
the hydrolysis of di- and polysaccharides to monomeric sugars enhanced stability despite their relatively lower activity
(Tables 2 and 3). (Table 2, entry 7). By altering the reaction conditions, Sahu
To investigate the eect of the physicochemical properties and Dhepe28 demonstrated that xylose and arabinose or fur-
of zeolites on hydrolysis, disaccharides were commonly used fural were the main products in the hydrolysis of hemicellu-
as model compounds. The microporous structures of zeolites lose (Table 2, entries 810; Scheme 2). Additionally, zeolites
seem to be one of the major barriers for the diusion of di- including H-USY (Si/Al = 15), H-beta (Si/Al = 19), and
saccharide molecules such as sucrose (diameter: 0.88 nm) into H-mordenite (Si/Al = 10) could provide xylose and arabinose in
the pores (e.g., 8 supercages with a free aperture of 0.74 nm) to high total yields ca. 3641% with low amounts of furfural
react on the acidic sites. Interestingly, the anity towards di- formed when the reaction was conducted in water at 170 C
saccharides could be enhanced by dealumination of zeolites to after 1 h, (Table 2, entry 8). On the other hand, a reduction in
increase hydrophobic interactions coupled with reduced the reaction time from 3 to 1 h exclusively aorded xylose and
hydration.20 Buttersack and Laketic21 demonstrated that de- arabinose using H-USY(Si/Al = 15), with furfural being pro-
aluminated H-Y zeolite (Si/Al = 110) prepared from H-Y zeolite duced in high selectivity at longer reaction times, especially in
(Si/Al = 2.4) by replacing Al species of the original framework a biphasic H2O/p-xylene solvent system (Table 2, entry 10).
with SiCl4 could strongly accelerate sucrose hydrolysis Besides acidity, the increased hydrothermal stability and pore
(5.21 L mol1 min1), with a high conversion (90%) achieved at sizes of steamed Y zeolites (H-USY) were likely to account for
70 C without formation of side products (Table 2, entry 1). By the higher monomeric sugars yields. The mesopores/macro-
using studies on the adsorption equilibrium constants of pores of H-USY (Si/Al = 3.2) created after treatment with oxalic
sucrose (22 mL g1), glucose (0.2 mL g1), and fructose (1.0 mL acid were able to improve the accessibility of the reactants to
g1), the authors claimed that the access of sucrose molecules acid sites and facilitate the diusion of products out of pores,
could easily substitute glucose and fructose molecules gener- thus restraining the formation of byproducts and playing a
ated inside the pores of the dealuminated zeolites. However, the role in improving the yield of total reducing sugars (TRS) from
conformation of sucrose molecules required to be changed 5.8% to 55.7% (Table 2, entry 11).29
(e.g., to the elliptic form) before entering into the pores.21 Cellulose with a water-insoluble character and robust struc-
A variety of H-form dealuminated zeolites (e.g., H-MFI, ture consisting of the -1,4-glycosidic bonds of glucose units is
H-BEA, H-Y-FAU, and H-MOR) were also investigated in comparably more dicult to be hydrolysed with respect to
sucrose hydrolysis, with a high conversion (100%) to mono- hemicellulose, and harsh reaction conditions (e.g., supercriti-
mers obtained over a H-Y-FAU (Si/Al = 15) zeolite (Table 2, cal water) are often involved in a traditional deconstruction to
Table 2 Catalytic hydrolysis of sucrose, maltose, xylan, inulin, starch and hemicellulose with zeolites
Acidity Recycle,
Entry Catalyst (Si/Al) (mmol g1) Substrate (conc.) Solvent Temp. Time Product Conv. Yield/[Sel.] [Yield] Ref.
1 1 1x
1 10 wt% H-Y(2.4) 0.17 Sucrose (100 g L ) H2O 40 C Glucose + fructose 0.03 L mol min 21
Critical Review
10 wt% H-Y(110) 0.087 90% 5.21 L mol1 min1x

0.57 M HCl 0.57 2.37 L mol1
min1 a
2 6 wt% H-Y(15) Sucrose (800 g L1) H2O 75 C 150 min Glucose + fructose 100% 22
3 3 wt% H-Y(15) Sucrose (800 g L1) H2O 85 C 100 min Glucose + fructose 100% 100% [100%] 23
Cellobiose (50 g 150 C 150 min Glucose 90% 88% [98%]
L1)
Maltose (50 g L1) 150 C 150 min Glucose 90% 83% [92%]
Inulin (100 g L1) 90 C 90 min Fructose 92%
5704 | Green Chem., 2016, 18, 57015735

Starch (100 g L1) 150 C 150 min Glucose 95%
4 139 wt% H-mordenite(7) Maltose (7.2 g L1) H2O 130 C 24 h Glucose 60% 59% [93%] 24
139 wt% H-mordenite 70% 66% [94%]
(12)
5 139 wt% H-beta(25) Maltose (7.2 g L1) H2O 130 C 24 h Glucose 45% 43% [96%] 24
139 wt% H-beta(100) 85% 82% [97%]
1
6 100 wt% Amberlyst-70 2.55 Xylan (10 g L ) H2O 120 C 4h Xylose + arabinose 76% 3 cycles [11%] 27
100 wt% Amberlyst-35 5.20 80%
0.036 M H2SO4 0.036 74%
7 100 wt% H-ferrierite(55) 0.33 Xylan (10 g L1) H2O 120 C 20 h Xylose + arabinose 43% 4 cycles [35%] 27
100 wt% HY(5.5) 20%
100 wt% H-ZSM-5(50) 33%
100 wt% H-ZSM-5(80) 29%
8 50 wt% H-USY(15) 0.55 Hemicellulose H2O 170 C 3h Xylose + arabinose/ >90% 41%/12% 28
50 wt% H-beta(19) 0.91 (10 g L1) furfural 38%/6%
50 wt% H-mordenite(10) 1.18 36%/6%
9 50 wt% K10 clay 0.42 Hemicellulose H2O 170 C 3h Xylose + arabinose/ >90% 27%/12% 28
(10 g L1) furfural
10 50 wt% H-USY(15) 0.55 Hemicellulose H2O 170 C 1h Xylose + arabinose/ >90% 56%/2% 5 cycles [50%] 28
(10 g L1) 6h furfural 30%/18%
H2O/ 17%/56%
p-xylene
11 50 wt% H-USY(3.2) 1.00 Hemicellulose H2O 140 C 7h Xylose + arabinose 5.8% 29
50 wt% H-USY(16.6) 0.10 (10 g L1) 55.7% 4 cycles [47%]
a
Reaction rate. TRS: total reducing sugars, [BMIM]Cl: 1-butyl-3-methylimidazolium chloride.
View Article Online
Green Chemistry
This journal is The Royal Society of Chemistry 2016

View Article Online
valuable products. As an improved method, hydrophobic

Ref.
30
31
32
35
H-form zeolites with high Si/Al ratios [e.g., H-beta (Si/Al = 75)
and H-ZSM-5 (Si/Al = 45)] were found to show relatively high
Recycle, [Yield]
activity in the hydrolysis of cellulose to glucose (ca. 12% yield)

under hydrothermal conditions at 150 C, as compared with
blank runs in the absence of a catalyst and the use of SiO2 and
-Al2O3 (Table 3, entry 1).30 In contrast, H-form zeolites with

lower Si/Al molar ratios were more ecient in the catalytic
24.0%/22.4%
15.8%/15.1%
[18%]/[14%]
[17%]/[10%]
11.1%/1.1%
15.7%/4.2%
hydrolysis of cellulose to glucose (up to 36.9% yield in 8 min)
3.7%/0.4%
Yield/[Sel.]
[5%]/[0]
using 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) as the
35.2%
33.7%
29.6%
36.9%
26.9%
ionic liquid under microwave irradiation.31 Lanzafame et al.32
11%
12%
8%
7%
4%
4%
3%
also demonstrated that the shape-selectivity eect of micro-

porous zeolitic materials [e.g., H-mordenite(7) and H-beta(13)]
24.9%
44.6%
60.8%
44.7%
12.7%
Conv.
was capable of limiting the polymerization of in situ generated

13%
6%
6%
glucose to humins in production of glucose and HMF from
cellulose, thus exhibiting a superior performance with respect
Glucose/HMF
TRS/glucose
to mesoporous SBA-15 supported sulphated zirconia

(SO4ZrO2/SBA-15) despite the activity of SO4ZrO2 in 1,4-
Glucose
Glucose
Product
glycosidic bond cleavage33 (Table 3, entry 3). However, metal ions

present in the raw biomass were proposed to exchange with
the Brnsted acid sites of H-form zeolitic materials, which
9.5 min
9.5 min
8.5 min
3.3 min
might result in zeolite deactivation.34 To increase the acid

8 min
Time
24 h
5h
8h
6h
strength and the amount of acid sites, a sulfonated hierarchi-

cal H-USY zeolite (H-USY-meso-SO3H) was prepared through a
240 Wa
150 C
190 C
150 C
180 C
Temp.
range of cascade processes: treating H-USY (Si/Al = 3.2) with

oxalic acid to create meso/micropores (H-USY-meso), grafting
Microwave irradiation. TRS: total reducing sugars, [BMIM]Cl: 1-butyl-3-methylimidazolium chloride.
3-mercaptopropyltrimethoxysilane onto the surface of the hier-

[BMIM]Cl/H2O
archical H-USY zeolite followed by oxidation of thiols to sulfo-

nated groups (Scheme 3).35 The resulting H-USY-meso-SO3H
Solvent
exhibited a high eciency in the hydrolysis of hemicellulose

H2O
H2O
H2O
to TRS (78.0% yield) at 140 C for 9 h, especially in the hydro-

lysis of -cellulose and microcrystalline cellulose (60.8% &
Cellulose (34 g L1)
Cellulose (10 g L1)
43.7% conversion) to glucose (22.4% & 15.1% yield) at 180 C

cellulose(10 g L1)
Cellulose (9 g L )
Cellulose (5 wt%)
1
Substrate (Conc.)
Microcrystalline
after 6 h, respectively (Table 3, entry 4). These findings pointed

to a dependence of the zeolite catalytic activity on the acidity
and surface structure in polysaccharide hydrolysis. Catalytic
alcoholysis of cellulose could also be achieved using H-form
zeolites by using alcohol instead of water as reaction media,
giving alkyl glucosides as the main products (more stable
Acidity (mmol g1)
against further degradation as compared to glucose).36

Catalytic hydrolysis of cellulose with zeolites
2.2. Zeolite-catalysed sugar isomerization

2.2.1. Glucose-to-fructose isomerization. Glucose-to-fruc-
0.095
0.049
0.30
0.70
1.05
0.18
1.30
1.10
0.26
0.09
0.40
tose isomerization is being deemed as one of the vital inter-

mediate steps to produce biofuels and value-added chemicals

100 wt% H-USY-meso-SO3H
from lignocellulose, being the largest biorefinery process in

111 wt% H-mordenite(10)
10 wt% SO4-ZrO2/SBA-15
the industrial production of high-fructose corn syrup.37 Both a

10 wt% H-mordenite(7)
111 wt% H-ZSM-5(45)
100 wt% H-USY-meso
base-catalysed proton transfer and a metal center-mediated

111 wt% H-beta(12)
111 wt% H-beta(75)
10 wt% H-beta(13)
intramolecular hydride shift have been reported to be respon-

111 wt% -Al2O3
100 wt% H-USY

Catalyst (Si/Al)
sible for the isomerisation of glucose to fructose (Scheme 4).38

H-ZSM-5(140)
111 wt% SiO2
H-ZSM-5(38)
H-beta(25)
Sn-beta prepared by full incorporation of tin into the frame-

work of a pure-silica analogue of zeolite beta was demon-
NKC-9
H-Y(5)
Blank
strated to be highly ecient for the isomerization reaction,

whereas SnO2-beta synthesised using Sn sources dierent
Table 3
Entry
from SnCl4 were found to be completely inactive (Table 4,

entry 1).39 The real active site in Sn-beta was speculated to be a
1
View Article Online

Scheme 2 Product distribution in catalytic hydrolysis of hemicellulose with zeolites (glucose, mannose and galactose in small amounts are not
shown).28
Scheme 3 The route to synthesize H-USY-meso-SO3H.35
partially hydrolysed framework tin species (SiO)3SnOH To examine the nature of the active sites in Sn-beta, two
rather than isomorphously substituted Sn species molecular models (tin silsesquioxanes) with the siloxy groups
(Scheme 5).40 Subsequent studies showed the promotional adjacent to octahedrally coordinated tin centers covered by
eect of the silanol group as a base in Sn-catalysed isomeriza- either a proton or a trimethylsilyl (TMS) substituent were
tion of glucose to fructose,41 wherein the processes of hydride designed (Scheme 6a).45 The isotopic labelling experiments
transfer and proton transfer took place in a single step but the with glucose deuterated at the C2 position and enriched with
13
epimerization reaction via a 1,2-intramolecular carbon shift C at the C1 position (2-2H, 1-13C glucose) illustrated that fruc-
was inhibited.42 On the other hand, treating defect-free tose and mannose could be obtained from glucose through
Sn-beta with fluoride (Sn-betaF) led to the formation of hydro- 1,2-intramolecular hydride and 1,2-intramolecular carbon
phobic void spaces, which could exclude water from coming shifts in the presence or absence of adjacent silanol groups,
into contact with Lewis acid sites, thus confining and protect- respectively (Scheme 6b). Similarly, the reaction pathway could
ing the active sites.43 However, similar reactivity was predicted be progressively shifted from glucosefructose isomerization
for Sn tetrahedral lattice sites and the hydroxylated SnOH to glucosemannose epimerization by increasing the extent of
species of these two types of Sn-beta zeolites.44 In fact, the post synthetic Na+ exchange onto Sn-beta, which clearly indi-
hydrophobic surroundings of the Sn-beta zeolite with lattice cated the significant role of SiOH in controlling product dis-
tetrahedral Sn centers were rapidly deactivated in water, and tribution.46,47 The type of solvent was also demonstrated to
thus enabled the resulting catalyst to promote isomerization of influence the reaction pathway, wherein Sn-beta could mediate
sugars under aqueous conditions (Scheme 5).43 the intramolecular hydride shift under aqueous conditions to
View Article Online

Scheme 4 Catalytic isomerization of glucose to fructose with a base and Sn-beta via Pathway 1 ( proton transfer) and Pathway 2 (intramolecular
hydride shift), respectively.39
isomerize glucose to fructose while the Bilik reaction (i.e., mesopores from 4 to 11 nm, which was more active than the
intramolecular carbon shift) took place in methanol to epimer- conventional bulky Sn-MFI catalyst (0.63 nm pore diameter) in
ize glucose to mannose over the same zeolite.48 For both glucose-to-fructose isomerization (Table 4, entry 3).53 After
homogeneous (e.g., CrCl3 and AlCl3) and heterogeneous (e.g., investigating the activitystructure relationship of four
Sn-beta) catalysis, the intra-hydride transfer was confirmed to dierent stannosilicates (i.e., Sn-BEA, Sn-MFI, Sn-MCM-41 and
be the dominant reaction pathway in glucose-to-fructose Sn-SBA-15), Osmundsen et al.54 found that the enhanced Lewis
isomerization,49 and hydroxyl anions available in aqueous acid strength of the stannosilicates could be positively corre-
media other than neat polar aprotic solvents (e.g., DMSO and lated to their high activity in glucose isomerization (Table 4,
DMA) were reported to be crucial to accelerate the conversion entry 4). Although the narrow micropores of 10-membered
rate of glucose being selectively isomerised to fructose.50 ring zeolites (e.g., Sn-MFI and Sn-MWW) adversely aected the
Other parameters influencing the activity of zeolites in the intrachannel diusion, the observed moderate catalytic activity
isomerization of glucose to fructose were also studied. Davis of these zeolites in glucose isomerization could be ascribed to
et al.51 found that Sn-beta and Ti-beta (incorporation of Sn the lower barrier for the hydride shift under the promotion of
and Ti into the large-pore zeolite) exhibited higher glucose iso- a stronger acidic bridging silanol group close to the Lewis acidic
merization activity as compared to TS-1 (incorporation of Ti Sn site.55 Among various heteroatoms (e.g., Sn, Ti, Zr, V, Nb,
into the medium-pore zeolite). Glucose conversions over 50% Si, and Ge) confined in the beta zeolite, Sn and Zr centers were
could be obtained at 140 C in 90 min (Table 4, entry 2). The demonstrated to be the most active with apparent reaction bar-
dierence in catalytic reactivity implied that glucose molecules riers (kcal mol1) in the order of 39.0 (V) > 37.4 (Si) > 32.2 (Ge)
could diuse into the pores of the beta zeolite (ca. 0.8 nm dia- > 32.1 (Ti) > 25.7 (Nb) > 23.5 (Zr) > 23.3 (Sn).56 Either the
meter), but were unable to enter into the pores of TS-1 Brnsted basicity of the O atom associated with the Sn center
(0.50.6 nm diameter) despite the fact that the six-membered or the polarizability of the Zr site was detected to lower the
ring of glucose (0.86 nm kinetic diameter) in the pyranose reaction barrier of the rate-limiting step involving a hydride
form was capable of opening to the acyclic form in the pres- shift from C2 to C1 in the isomerization of glucose to fructose.
ence of the Lewis acid sites.52 In this context, highly crystalline In parallel to the isomerization of glucose to fructose, glucose-
3DOm-i Sn-MFI confined in 3DOm carbon (35 nm cage size) to-sorbose isomerization via an intramolecular C5C1 hydride
through a seeded growth approach was illustrated to possess shift was also observed (Scheme 7), with fructose and sorbose
tetrahedrally coordinated framework Sn centers and ordered being the predominant products in water and methanol over
Table 4 Aldoseketose isomerizations catalysed by zeolites
Substrate Recycle,
Entry Catalyst Synthetic material/method (Conc.) Solvent Temp. Time Product Conv. Yield (Yield) Ref.
a
1 2.0 mol% Sn-beta SnCl4 + silica/hydrothermal gel Glucose H2O 110 C 45 min Fructose/mannose 53% 30%/10% 39
Critical Review
2.0 mol% SnO2 + silica/hydrothermal gel (10 wt%) Fructose 5% <1%

SnO-beta
2 2.0 mol% TS-1 Ti(BuO)4 + TEOS/hydrothermal gel Glucose H2O 140 C 90 min Fructose 8% 4% 51
2.0 mol% Ti-beta Ti(i-PrO)4 + TEOS/hydrothermal gel (10 wt%) 50% 22%
2.0 mol% Sn-beta SnCl4 + silica/hydrothermal gel 81% 25%
2.0 mol% Sn-beta SnCl4 + silica/hydrothermal gel 120 C 30 min 59% 32% 4 cycles,
(30%)
1
3 4.3 mol% Sn-MFI SnCl4 + silica/hydrothermal gel Glucose MeOH 70 C Fructose 0.05 h (TOF) 53
4.3 mol% Sn-MFI + 3Dom carbon/ (1 wt%) 0.69 h1 (TOF)
5708 | Green Chem., 2016, 18, 57015735

3DOm-i Sn-MFI seeded growth
4 1.0 wt%a Sn-beta SnCl4 + TEOS/hydrothermal gel Glucose H2O or 80 C 48 h Fructose/[fructose 51%/[40%] 54
1.0 wt% Sn-MFI SnCl4 + silica/hydrothermal gel (2 wt%) [MeOH] + mannose] 0/[1%]
1.0 wt% SnCl4 + TMAS/hydrothermal gel 4%/[76%]
Sn-MCM-41
1.0 wt% Sn-SBA-15 SnCl4 + TEOS/hydrothermal gel 0/[55%]
5 3.1 wt% Ti-beta Dealuminated beta + SnCl4/ Glucose H2O or 100 C 2h Fructose + sorbose/ 18%/36% 11% + 4%/ 57
(Si/Al = 66) incorporation (1 wt%) [MeOH] [fructose + sorbose] [8% + 12%]
1.7 wt% Ti-beta 19%/21% 8% + 3%/
(Si/Al = 79) [4% + 8%]
1.8 wt% Ti-beta 20%/24% 8% + 4%/
(Si/Al = 107) [4% + 9%]
1.4 wt% Ti-beta 13%/23% 6% + 3%/
(Si/Al = 202) [4% + 6%]
6 2.0 mol% Sn-beta 200 nm beta nanocrystals Glucose H2O 90 C 2h Fructose/[sorbose] 45% 39%/[10%] 59
+ SnCl4/dealumination + (10 wt%)
Incorporation
20 wt% Sn-beta Beta zeolite + SnCl4/ 110 C Fructose/[mannose] 40.6% 32.4%/[8.2%] 3 cycles, 60
dealumination + grafting (30%)
75 wt% Sn-Al-beta Dealuminated beta + SnCl4/ 120 C Fructose 54.7% 43.2% 4 cycles, 61
post-synthesis (45.8%)
2 mol% Sn-beta Dealuminated beta + SnCl4/ 110 C 30 min Fructose/[mannose] 22.3% 16.4%/[4.4%] 62
solid-state incorporation
7 60 wt% H-Y(2.6) Commercially available Glucose (1) MeOH, 120 C (1) 1 h, (2) 1 h Fructose/[methyl (1) 44%, (2) 46% (1) 16%/[19%], 64
(3 wt%) (2) H2O fructoside] (2) 20%/[18%]
60 wt% H-USY(6) (1) 70%, (2) 72% (1) 22%/[33%], 5 cycles,
(2) 55%/[4%] (45%)
60 wt% H-USY(30) (1) 37%, (2) 37% (1) 26%/[<1%],
(2) 24%/[<1%]
60 wt% H-beta(12.5) (1) 71%, (2) 70% (1) 23%/[22%],
(2) 40%/[8%]
60 wt% H-beta(19) (1) 61%, (2) 57% (1) 21%/[16%],
(2) 29%/[8%]
60 wt% H-beta(150) (1) 10%, (2) 11% (1) 0/[0],
(2) 0/[0]
8 2 mol% Sn-beta Sn(OEt)4 + Xylose H2O 100 C 15 min Xylulose/[lyxose] 60% 27%/[11%] 3 cycles, 67
TEOS/hydrothermal gel (10 wt%) (21%)
View Article Online
Green Chemistry

View Article Online
Ref.
69
3 cycles,
Recycle,
(Yield)
(32%)

(1) 23%/[<1%],
(1) 39%/[13%],
(1) 31%/[11%],
(2) 25%/[<1%]
(1) 16%/[8%],
(2) 47%/[4%]
(2) 39%/[5%]
(2) 20%/[5%]
(1) 4%/[5%],
(2) 4%/[4%]
(1) 0/[0],
(2) 0/[0]
Yield
Sn molar weight or zeolite mass weight relative to the substrate. TEOS: tetraethyl orthosilicate, TMAS: tetramethylammonium silicate, TOF: turnover frequency.
(1) <1%, (2) <1%
(1) 34%, (2) 35%
(1) 69%, (2) 69%
(1) 54%, (2) 55%
(1) 29%, (2) 29%

(1) 8%, (2) 13%
Scheme 5 Sn sites in (a) isomorphously substituted and (b) partially

hydrolysed Sn-beta zeolites.40
Conv.
Ti-beta with varying Si/Ti contents at 100 C after 2 h, respect-

ively (Table 4, entry 5).57
Xylulose/[methyl
Sn-beta showed great potential in the industrial production

of fructose from glucose with respect to its high reactivity,
xyluloside]
Product
while the synthetic routes generally involved long crystalliza-

tion times.58 In recent years, some representative approaches
such as a renewed seeding method using 200 nm crystalline
zeolite beta nanocrystals as seeds,59 grafting Sn4+ onto the
(1) 1 h, (2) 1 h
dezincated CIT-6 in anhydrous dichloromethane at room

temperature60 and dealuminated beta zeolite in refluxing
Time
2-propanol,61 isomorphous substitution of dealuminated

zeolite with SnCl4 vapour,62 and the solid-state incorporation
100 C
Temp.
method63 have been developed to shorten the preparation

period and simplify the synthetic procedure, and similar levels
of intrinsic activity were achieved as compared to as-prepared
(1) MeOH,
Sn-beta zeolites (Table 4, entry 6). However, the Sn-beta catalyst

(2) H2O
Solvent
deactivated in water ranging from minutes to hours, wherein

the by-products formed through irreversible reactions led to
Substrate
the loss of selectivity towards fructose in the isomerization

(3 wt%)
(Conc.)
Xylose
reaction.64 To circumvent the unfavourable water inhibition in

glucosefructose isomerization, Saravanamurugan et al.65
developed a two-step reaction pathway involving initial for-
mation of methyl fructoside from sequential isomerization
and methoxylation of glucose in methanol, followed by
Synthetic material/method
addition of water to produce fructose through the hydrolysis

Commercially available
process catalysed by commercially available zeolites

(Scheme 8). The large-pore Y and BEA zeolites, especially
H-USY(6) and H-beta(12.5), gave relatively high fructose yields
of up to 55% via the two reaction steps (Table 4, entry 7).
Notably, the yield of fructose could remain constant at 4050%
over H-USY(6) during five consecutive cycles, and the structural
integrity of the regenerated catalyst after the fifth reaction also
remained unchanged as compared to its fresh counterpart.
60 wt% H-beta(12.5)
60 wt% H-beta(150)
60 wt% H-beta(19)
60 wt% H-USY(30)
2.2.2. Xylose-to-xylulose isomerization. In parallel to the

60 wt% H-USY(6)
60 wt% H-Y(2.6)
catalytic upgrading of hexoses with glucosefructose isomeri-

zation as the key step, the isomerization of xylose to xylulose
(Contd.)
mediated by Lewis acid and/or base sites could significantly

Catalyst
reduce the activation barrier towards downstream products

(i.e. furfural).66 In aqueous solution, Sn-beta was demonstrated
Table 4
Entry
to be active in xylose isomerization (60% conversion) to xylu-

lose (up to 27% yield) at 100 C, wherein the epimer lyxose
9
View Article Online

Scheme 6 Schematic of siloxy groups adjacent to octahedrally coordinated tin centers covered by a proton (a-1) or a trimethylsilyl (TMS; a-2) sub-
stituent (a), and reaction network of glucose with a-1 and a-2 deduced from isotopic labelling experiments (b).45
Scheme 7 Glucosefructose and glucosesorbose isomerization evident from isotopic tracer studies using D and 13C labels.57
Scheme 8 Reaction pathway for converting glucose to fructose in alcohol and aqueous media.64
(11% yield) could also be formed as a secondary product centres for the hydrogen and electron transfer, instead of a
(Scheme 9a; Table 4, entry 8).67 The superiority in the isomeri- hydride ion.68 Saravanamurugan et al.69 found that the in situ
zation reaction other than epimerization could be ascribed to generated xylulose from xylose isomerization would partially
the more favourable thermodynamic and kinetic characters of react with methanol to form methyl xyluloside over large-pore
xylulose than those of lyxose.68 The hydrogen transfer from the zeolites (i.e., Y and beta) when the reaction medium was
carbon C2 to C1 of xylose was exploited to be the rate-limiting altered from water to methanol. Subsequent addition of water
step for both reactions, which proceeded through a concerted could promote the hydrolysis process to yield additional xylu-
neutral hydrogen-electron transfer that involves dierent lose in the second step (Scheme 9b). In this two-step
View Article Online

Scheme 9 Reaction pathways for isomerization of xylose to xylulose in water (a) and alcohol and aqueous solution (b).67,69
reaction pathway, H-USY(6) and H-beta(12.5) showed the various transformation processes. As an isomer of glucose,
highest activity, successively giving good xylulose yields of 47% fructose could be rapidly dehydrated to HMF over H-form zeo-
and 39% from xylose at 100 C after reacting for 1 h in metha- lites, and cooperative catalysis between adjacent Brnsted acid
nol and another 1 h in a methanol/water mixture (Table 4, centers in zeolite channels can most likely contribute to reac-
entry 9). tion improvements.70 However, rehydration/hydrolysis of
in situ formed HMF occurred in the presence of acidic zeolites
to give equivalent amounts of levulinic acid and formic acid in
3. Catalytic dehydration of aqueous solution (Table 5, entry 1).71,72 In the case of fructose
carbohydrates to HMF and furfural dehydration, water removal from the catalytic system via con-
tinuous evacuation was demonstrated to be capable of sup-
Dehydration is an eective and facile approach to reduce the pressing HMF-to-levulinic acid conversion as well as the for-
oxygen content of lignocellulosic feedstocks in the presence of mation of condensation products from partially dehydrated
acidic catalysts. Brnsted acid sites are responsible for the intermediates (Table 5, entry 2).73 The addition of an organic
hydrolysis of biopolymers to monosaccharides, while Lewis solvent (e.g., MIBK: methyl isobutyl ketone) as an extracting
acid sites play a key role in the isomerization of aldoses to phase to the aqueous solution could significantly increase the
ketoses that are more prone to be dehydrated over either selectivity towards HMF from fructose by restraining humins
Brnsted or Lewis acids (Scheme 10). In this section, the cata- formation (Table 5, entry 3),7476 and the catalytic performance
lytic production of furanic compounds including potential was positively correlated with the strength of the acid sites in
HMF and furfural from hexoses and pentoses with zeolites are zeolitic materials (MOR > ZSM-5 > BEA) as well as the large
briefly discussed in Tables 5 and 6, respectively. external surface areas and mesoporous architectures (Table 5,
entry 4).77,78 Similarly, on using carbon black as an adsorbent
3.1. Zeolite-catalysed conversion of hexoses to HMF to selectively adsorb furans (HMF and furfural) rather than
Cellulose is the most abundant component (4050 wt%) of levulinic acid and fructose in the reaction mixture, the selecti-
lignocellulosic biomass, wherein glucose is an exclusive struc- vity of the furans could be improved from 27 to 44% with a
tural unit and has been widely used as a model molecule for yield of 41% at 185 C after 2 h (Table 5, entry 5).79 Zeotype
Scheme 10 Direct conversion of cellulose and hemicellulose to HMF and furfural.
Table 5 Catalytic conversion of hexose sugars to HMF using zeolites
Entry Catalysta Substrate (Conc.) Solvent Temp. Time Product Conv. Yield Recycle, (Yield) Ref.
1 100 wt% LZY zeolite (Na56 (AlO2)56(SiO2)136) Fructose (2 wt%) H2O 140 C 2 h HMF/[LA] 70.3% 1.2%/[33.5%] 71
29 wt% H-mordenites(11)b Fructose (10 wt%) H2O/MIBK (1 : 5, v/v) 165 C HMF/[Furfural] 93% 73%/[5%] 72
Critical Review
2 6.7 wt% H-beta(12.5) Fructose (3 wt%) DMSO 120 C 2 h HMF 100% 97% 73
6.7 wt% H-Y(2.4) 76%
3 20 wt% H-mordenites(12) Fructose (40 wt%) H2O 135 C HMF 10% 6% 74
50 wt% H-beta(15) Fructose (3 wt%) H2O/MIBK (1 : 5, v/v) 165 C 1 h HMF 85% 34% 75
50 wt% H-ZSM-5 90% 53%
50 wt% H-Y(10) 74% 41%
50 wt% H-mordenites(11) 76% 69%
29 wt% H-mordenites(11) Sucrose (10 wt%) 57% 56% 76
5712 | Green Chem., 2016, 18, 57015735

29 wt% H-mordenites(11) Inulin (10 wt%) 44% 39%
4 20 wt% H-mordenites(12) Fructose (6.7 wt%) H2O/MIBK (1 : 3, v/v) 165 C 2.5 h HMF 30% 26% 2 (21%) 77
8 wt% H-beta(25) nanozeolite Fructose (2.7 wt%) DMSO 120 C 2 h 72% 55% 78
8 wt% H-ZSM-5(70) nanozeolite 80% 65%
5 100 wt% BP2000/H-beta Fructose (1.2 wt%) H2O 150 C 4h HMF 80% 40% 79
6 20 wt% KCC-1 silica nanospheres Fructose (8.3 wt%) DMSO 162 C 0.5 h HMF 99.1% 67.7% 80
27.8 wt% KIT-6 mesoporous silica Fructose (3.6 wt%) 165 C 0.5 h 100% 84.1% 81
5.6 wt% TESAS-SBA-15 Fructose (30 wt%) MIBK:2-BuOH (7 : 3, 130 C 141 min 84% 60% 82
w/w)/H2O (1 : 2, w/w)
SBA-15-SO3H (packed-bed reactor) Fructose (2 wt%) THF/H2O (4 : 1, w/w) 130 C 80% 50% 83
10 wt% mesoporous SBA-15-SO3H Fructose (10 wt%) [BMIM]Cl 120 C 1h 100% 81% 4 (73%) 84
21 wt% SO4/TiO2-SiO2 Fructose (6 wt%) DMSO 110 C 1.5 h 77% 69% 4 (69%) 85
7 0.5 mol% Sn-beta + HCl (pH = 1) Glucose (10 wt%) THF/H2O (3 : 1, v/v) 180 C 70 min HMF 79% 57% 89
3.3 wt% Sn-beta + 3.3 wt% Amberlyst-70 Glucose (2 wt%) GVL 130 C 20 min HMF 92% 59% 90
15 min 90% 46%
THF 130 C 30 min 90% 63%
20 min 90% 36%
8 40 wt% H-Y(5) Glucose (10 wt%) [BMIM]Cl 140 C 0.5 h HMF 24.6% 11.8% 91
40 wt% H-mordenite(15) 27.2% 13.1%
40 wt% H-beta(25) 48.1% 23.7%
40 wt% H-ZSM-5(25) 31.3% 14.2%
40 wt% H-ZSM-5(50) 42.7% 20.5%
40 wt% H-ZSM-5(100) 35.4% 16.4%
40 wt% H-ZSM-5(300) 14.5% 8.3%
40 wt% H-beta(25) 150 C 50 min 80.6% 50.3% 6 (35.6%)
9 83 wt% dealuminated H-beta(15) Glucose (2 wt%) H2O : DMSO (9 : 1, 180 C 3 h HMF 78% 43% 5 (40%) 92
v/v)/THF (1 : 3, v/v)
20 wt% [Sn,Al]-beta Glucose (10 wt%) DMSO 160 C 4 h 60% 37% 4 (28%) 93
83 wt% dealuminated H-beta(OF) Glucose (2 wt%) H2O : DMSO (9 : 1, 180 C 3 h 91% 61% 3 (60%) 94
v/v)/THF (1 : 3, v/v)
10 30 wt% Al-MCM-41 Glucose (1 wt%) H2O/MIBK (3 : 1, v/v) 195 C 0.5 h HMF 98% 63% 2 (45%) 103
100 wt% Sn-MCM-41 Glucose (10 wt%) [EMIM]Br 110 C 4h 98% 70% 5 (65%) 104
33% wt% Zr-MCM-41 H2O/MIBK (1 : 3, v/v) 175 C 2.5 h 82% 23% 2 (17%) 105
11 1 wt% H-Y(15) Sucrose (8 wt%) H2O 100 C 0.15 mL min1 HMF 100% 106
100 wt% H-beta(38) Cellobiose (1 wt%) 175 C 1h Glucose/[HMF] 82% 75%/[0] 107
67 wt% Al-TUD-1(21) Cellobiose (10 wt%) 170 C 6h HMF/[Glucose]/ 98% 12%/[50%]/(10%) 108
Sucrose (10 wt%) (fructose) 100% 17%/[20%]/(12%)
Inulin (10 wt%) 20%/[5%]/(8%)
100 wt% H-Y(2.5) + 12.5 wt% CrCl2 Cellulose (6.7 wt%) [BMIM]Cl 120 C 6 h + 6 h HMF 47.5% 110
67 wt% H-ZSM-5(25) Microalgae (1 wt%) THF/H2O (2 : 3, v/v) 200 C 2 h 80% 48% 6 (37%) 111
View Article Online
Green Chemistry

View Article Online
catalysts were also demonstrated to be ecient in fructose con-
Zeolite mass weight relative to the substrate. b Si/Al molar ratio shown in the bracket. HMF: 5-hydroxymethylfurfural, LA: levulinic acid, MIBK: methyl isobutyl ketone, DMSO: dimethyl-
Recycle, (Yield) Ref.
sulfoxide, BP2000: a type of carbon black, TESAS: 3-((3-(trimethoxysilyl)-propyl)thio)propane-1-sulfonic acid, THF: tetrahydrofuran, GVL: -valerolactone, [BMIM]Cl: 1-butyl-3-methyl-
112
113
114
version to HMF (Table 5, entry 6).8085 Catalysts with lower
surface hydrophobicity and lower acid density with medium to
5 (40%) strong acid strength favoured the selectivity towards HMF.86,87
The cooperative eect of Lewis and Brnsted acid sites was
more prominent in the synthesis of HMF when glucose was

utilised as a substrate, wherein Lewis acid promoted glucose

isomerization to fructose followed by subsequent fructose de-

hydration on Brnsted sites.88 As direct evidence, the combi-
nation of a solid Lewis acid (e.g., Sn-beta) with a homogeneous
or heterogeneous Brnsted acid (e.g., HCl and Amberlyst 70)
70.3%
Yield
46%
42%
was highly ecient for glucose-to-HMF conversion (Table 5,

entry 7).89,90 In a single zeolite-mediated catalytic system
Conv.
100%
(Scheme 11), Hu et al.91 illustrated that the H-beta(25) zeolite

67%

with a Brnsted/Lewis acidity ratio of 1.03 exhibited superior

activity in comparison with other zeolites including H-Y(5),
H-mordenite(15), H-beta(25), H-ZSM-5(25), H-ZSM-5(50),
H-ZSM-5(100) and H-ZSM-5(300) in glucose dehydration,
Product
HMF
giving HMF in a high yield of 50.3% with 80.6% glucose con-

version in [BMIM]Cl at 150 C after 50 min (Table 5, entry 8).
Several key factors were speculated to result in the enhanced
activity of the system: (1) Cl with moderate nucleophilicity
and basicity could positively influence Lewis acid-mediated
isomerization reactions; (2) the release of H+ from the chan-
Time
160 C 0.5 h
190 C 4 h
200 C 5 h
nels of the H-beta zeolite was possibly promoted by the ion-

exchange with [BMIM]+, so as to facilitate the contact of
Temp.
Brnsted acid sites with fructose; (3) the ionic liquid [BMIM]Cl
was helpful for the complete dissolution of glucose, thus
being more accessible by the H-beta zeolite; (4) [BMIM]+ in
v/v)/THF (1 : 3, v/v)
H2O : DMSO (9 : 1,
the ionic liquid could stabilize HMF without further

decomposition.
[EMIM]Cl
A range of synthetic methods such as dealumination of zeo-

Solvent
lites through calcination at high temperature (>700 C) or

H2O
treating with steam (50 kPa in N2, >500 C), partial dealumina-
tion coupled with isomorphous substitution of Al with Sn, and
Cellulose (2.5 wt%)
Cellulose (2.4 wt%)
imidazolium chloride, [EMIM]Cl: 1-ethyl-3-methylimidazolium chloride.

Cellulose (10 wt%)
an organic structure-directing agent (OSDA)-free process have

Substrate (Conc.)
been developed to design tailored zeolites containing more

Lewis acid sites, and the resulting bifunctional solid acids gen-
erally exhibited improved catalytic performance in the pro-
duction of HMF from glucose (Table 5, entry 9).9294 In the
absence of Lewis acid sites, 3-deoxyglucosone was found to be
the main intermediate to form HMF from glucose over proto-
nic acids (Scheme 12a),95 with a relative content of 3-deoxy-
glucosone being employed to distinguish dierent reaction
200 wt% desilicated H-ZSM-5(30)
83 wt% dealuminated H-beta(15)
pathways.96
20 wt% H-Y(2.5) + 6 mol% LiCl
In parallel, levoglucosan could also be generated from de-

hydration of glucose catalysed by a strong acid such as
Amberlyst 15 (Scheme 12b).97 A high temperature of 200 C
was required to promote the stable intermediate being further
transformed into HMF, furfural or 5-methylfuran using
H-MCM-22 or H-MCM-44 as catalysts bearing both Brnsted
(Contd.)
Entry Catalysta
and Lewis acid sites.98100 Byproducts including organic acids

and polymers in aqueous solution seemed to be concomitantly
produced with HMF,101 which might be attributed to the pre-
Table 5
ferential adsorption of HMF in zeolites.102 Interestingly, side

12
reactions could be significantly suppressed when an ionic

a
Table 6 Catalytic conversion of hexose and pentose sugars to furfural using zeolites
Entry Catalysta Substrate (Conc.) Solvent Temp. Time Product Conv. Yield Recycle, (Yield) Ref.
b
1 56 wt% H-beta(12) Xylose (3.6 wt%) H2O 170 C 4 h HMF 100% 77% 118
2 27 wt% H-Y(15) Xylose (7.5 wt%) H2O/toluene 170 C 50 min HMF 51% 42% 119
Critical Review
27 wt% H-mordenite(12) (1 : 3, v/v) 41% 34%

83 wt% H-ZSM-5(12) Xylose (3 wt%) H2O/toluene 140 C 4 h 89.7% 42.8% 120
83 wt% H-beta(12.5) (3 : 7, v/v) 89.5% 39.8%
83 wt% H-Y(2.5) 97.4% 41.1%
83 wt% H-mordenite(10) 81.1% 35.2%
80 wt% H-mordenite(10) Xylose (5 wt%) H2O (distillation) 175 C 0.75 mL min1 75% 121
3 4 wt% H-beta(12.5) Xylose (2 wt%) H2O/GVL 160 C 0.24 h1 HMF 71% 122
(1 : 9, w/w)
5714 | Green Chem., 2016, 18, 57015735

GaUSY(15) + Amberlyst-36 (1 : 2, w/w) Xylose (5 wt%) H2O/(1, v/v) 140 C 3.4 min 98% 72% 123
GaUSY(15) + Amberlyst-36 (1 : 2, w/w) Xylan (2.5 wt%) H2O/MIBK 130 C 13.6 min 69%
(1 : 9, v/v)
4 83 wt% SAPO-11 Xylose (10 wt%) H2O/toluene 180 C 4 h HMF 96% 51% 124
67 wt% H-MCM-22(38) Xylose (3 wt%) (3 : 7, v/v) 170 C 32 h 97% 68% 3 (40%) 125
67 wt% H-MCM-22(24) 16 h 92% 70% 4 (58%)
67 wt% ITQ-2(24) 99% 66% 4 (45%)
67 wt% H-ZSM-5(46) 6h 88% 60%
67 wt% del-Nu-6(1)(32) Xylose (10 wt%) 90% 47% 3 (45%) 126
67 wt% H-mordenite(6) 90% 34%
5 33 wt% dealuminated H-ZSM-5(12) Xylose (3 wt%) H2O 170 C 6 h Furfural 84% 42% 127
33 wt% desilicated H-ZSM-5(12) 92% 40%
6 67 wt% micro/mesoporous Xylose (10 wt%) H2O/toluene 170 C 6 h Furfural 98% 74% 4 (69%) 129
beta(12.5)/TUD-1 (3 : 7, v/v)
67 wt% H-beta(12.5) 98% 54% 4 (59%)
7 67 wt% MCM-41 Xylose (3 wt%) H2O/BuOH (1 : 1, v/v) 170 C 3 h Furfural 97% 44% 131
50 wt% SO3H-MCM-41 Xylose (4 wt%) H2O/toluene 155 C 2 h 94.9% 92.8% 2 (42%) 132
(1 : 1, v/v)
13 wt% AAO/SBA-15-SO3H Xylose (10 wt%) H2O/toluene 160 C 4 h 90% 67% 133
(3 : 7, v/v)
60 wt% SBA-15-SO3H Xylose (2 wt%) H2O/toluene 170 C 20 h 96% 82% 134
(1 : 1, v/v)
8 200 wt% H-mordenite(10) 2 wt% Wood chips (poplar) H2O/GVL 170 C 1.5 h Furfural 98% 75% 135
(1 : 9, w/w)
50 wt% HUSY(15) Hemicellulose (3 wt%) H2O 2h 54% 5 (46%) 136
222 wt% H-ZSM-5(12.5) H2O/toluene 190 C 3 h 96.8% 82.4% 5 (67.1%) 137
(1 : 2, v/v)
3.75 wt% H-beta(12.5) Corn fiber (3.75 wt%) H2O/GVL 160 C 2 h 62% 138
(1 : 9, w/w)
50 wt% CuSO4/HZSM-5(150) Bagasse (60 mL min1)) H2O 500 C 3 min 28% 139
25 wt% SAPO-44 Hemicellulose (3 wt%) H2O/toluene 170 C 8 h 93% 8 (90%) 140
(1 : 1, v/v)
9 10 wt% H-beta(25) Fructose (5 wt%) H2O/GBL 150 C 1h Furfural 99.9% 63.5% 141
(1 : 19, v/v) 160 C 2h 57.7%
Maltose (5 wt%) 150 C Furfural/[HMF] 45.2%/[11.9%]
Sucrose (5 wt%) 150 C 53.7%/[11.4%]
Inulin (5 wt%) 150 C 62.8%/[10.2%]
20 wt% H-beta(25) Starch (5 wt%) 170 C 3h 48.1%/[13.5%]
60 wt% H-beta(25) Cellulose (5 wt%) 180 C 6h 38.5%/[25.6%]
a
Zeolite mass weight relative to the substrate. b Si/Al molar ratio shown in the bracket. HMF: 5-hydroxymethylfurfural, LA: levulinic acid, MIBK: methyl isobutyl ketone, DMSO: dimethyl-
sulfoxide, THF: tetrahydrofuran, GVL: -valerolactone, SAPOs: silicoaluminophosphates, AAO: anodic aluminum oxide, GBL: -butyrolactone.
View Article Online
Green Chemistry

View Article Online

Scheme 11 Possible reaction mechanism for converting glucose to HMF with H-beta in [BMIM]Cl.91
Scheme 12 Cascade reaction routes for converting glucose to HMF.95,97
liquid or a biphasic solvent was introduced as the reaction in the process of fructose being dehydrated to HMF at 130 C
medium, thus giving enhanced HMF yields (up to 70%) from for 5 h, leading to a solution containing 1.226.2 mg L1 Al
glucose over metal-containing MCM-41 such as Al-MCM-41, and 226 mg L1 Si.115 Regrettably, the leaching composition
Sn-MCM-41 and Zr-MCM-41 (Table 5, entry 10).103105 primarily composed of AlOSi and SiOSi connectivity was
Catalytic conversion of glucose-containing di- and polysac- unable to catalyze the isomerization of hexoses but generated
charides including sucrose, cellobiose, inulin, starch, cell- side or sequential reactions of fructose and HMF. The hydro-
ulose, and microalgae to HMF could also be performed using lysis of SiOAl bridges to release Al3+ species was found to be
zeolites (Table 5, entry 11).106111 Recent studies have focused significantly enhanced in the presence of NaCl (even with a
on improving the catalytic performance of zeolites in direct low concentration of 0.070.18 wt%).116 Salts naturally present
conversion of cellulose to HMF either by incorporation of extra in biomass seem to have the potential to negatively impact the
metal species to increase acidity or by desilication or dealumi- hydrothermal stability of zeolites, which should be taken into
nation to control Brnsted and Lewis acid sites distribution account for more eective design of inert zeolitic materials.
(Table 5, entry 12).112114 However, the stability of zeolites in
aqueous solution was ignored in most cases. Although high- 3.2. Zeolite-catalysed conversion of pentoses to furfural
silica zeolites are more stable and the framework of MOR was Around 2535% of lignocellulosic biomass is hemicellulose
more stable with respect to that of BEA and FAU-Y, around mainly consisting of xylose units, which can be converted to
12 wt% aluminosilicate species of the zeolites was dissolved furfural through cascade acid-catalysed hydrolysis and de-
View Article Online
hydration.117 H-beta(12) was demonstrated to be active in the structural modifications, the resulting high ratio of Brnsted
sequential aqueous phase xylose-to-xylulose isomerization and to Lewis acid sites was also said to be responsible for the
pentose dehydration, giving furfural in a good yield of 77% enhanced activity in aqueous-phase dehydration.130 With an
with 100% xylose conversion at 170 C in 4 h (Table 6, entry improved pore architecture and increased Brnsted acidity,
1).118 Nevertheless, water-soluble and insoluble byproducts zeotype catalysts such as MCM-41, sulfonic MCM-41, SBA-15-
such as substituted furanyl/phenyl compounds from decompo- SO3H and propylsulfonic SBA-15 were demonstrated to be
sition reactions of furfural, and aliphatic/aromatic intermedi- highly ecient in producing furfural from xylose (up to 93%
ates from pentoses were detected ( possibly arising via sequen- yield, Table 6, entry 7)131134
tial fragmentation, recombination, ring-closure and aromatisa- Both commercially available and functionalised zeolites
tion reactions). To avoid the adverse reactions associated with have also been utilised in the direct transformation of hemi-
furfural, the biphasic system and distillation process were thus cellulose and even raw biomass into furfural with attractive yields
explored to in situ separate active intermediates out of the reac- through multi-step reactions involving hydrolysis, isomeriza-
tion zone catalysed by zeolites (Table 6, entry 2).119121 On the tion and dehydration reactions (Table 6, entry 8).135140 Most
other hand, a combined catalytic system containing both recently, Cui et al.141 reported a synergy between an organic
Lewis and Brnsted acid catalysts was able to increase the solvent (-butyrolactone) and a H-beta zeolite for the pro-
selectivity towards furfural from xylose (Table 6, entry 3), duction of furfural from hexoses successively through selective
wherein isomerization of xylose (other pentoses like arabinose) cleavage of the CC bond to in situ form pentoses and sub-
and subsequent dehydration were catalyzed by Lewis and sequent dehydration (Scheme 13). In the catalytic process, the
Brnsted acids, respectively.122,123 Particularly, individual zeo- formation of acyclic hexoses was highly required for CC bond
litic materials functionalised with the paired acidic sites cleavage, where H-beta displayed superiority to other zeolites.
exhibited advantages of high catalytic activity and good recycl- In contrast, cyclic hexoses were more prone to be dehydrated
ability (Table 6, entry 4).124126 to HMF. The solvent -butyrolactone, on the other hand,
Shape selectivity was also pointed out to influence the aected the interaction between the CvO bonds of hexoses
eciency of zeolites on dehydrating xylose to furfural. and the acid sites of H-beta, as well as suppressed furfural
H-ZSM-5(12) with a channel size analogous to the molecular degradation. In this way, moderate to good yields of furfural
size of furfural was found to exhibit a higher catalytic perform- (38.568.5%) could be achieved from fructose, glucose,
ance as compared to zeolites including H-mordenite(10), H-Y maltose, sucrose, inulin, starch, and cellulose, respectively,
(2.5), H-beta(13) and H-ferrierite(10).127,128 Interestingly, desili- using H-beta as the catalyst at a reaction temperature of
cation of H-ZSM-5(12) with NaOH could create additional 150180 C in a -butyrolactone/water mixture (Table 6, entry
mesopores while dealumination of H-ZSM-5(12) with HCl 9).141 This reaction strategy opens a viable pathway for the inte-
increased the relative content of Brnsted acid sites, both of grated conversion of pentoses and hexoses to an identical
which exhibited comparable xylose conversion and higher fur- molecule, and greatly simplifies the processes of ligno-
fural yield with respect to the parent H-ZSM-5(12), respectively cellulosic biomass pretreatment and product separation.
(Table 6, entry 5).127 Embedding H-beta(12) with a Lewis/
Brnsted acid ratio of 1.31 into a purely siliceous
TUD-1 mesoporous matrix (7.0 nm pore diameter) led to a 4. Catalytic upgrading of furanic
composite material (BEATUD; Si/Al = 34) possessing an
compounds
increased average pore size of 4.5 nm as well as dual Lewis and
Brnsted acid sites with a molar ratio of 1.19. Furfural yields HMF and furfural can be produced via dehydration from
obtained from xylose with BEATUD were higher as compared hexoses and pentoses, respectively. A series of value-added
to those observed using H-beta(12) (Table 6, entry 6).129 chemicals (e.g., 2,5-diformylfuran and 2,5-furandicarboxylic
Besides enlarging the pore dimension of zeolites achieved by acid) and furan-type biofuels (e.g., 2,5-dimethylfuran and
Scheme 13 Plausible pathways of converting fructose with H-beta and other acids.141
View Article Online
the recent progress in catalytic upgrading of furanic com-

pounds with zeolites, with particular emphasis on the strat-
egies to improve product selectivities.
4.1. Zeolite-catalysed alkoxylation

The dehydrated product HMF derived from hexoses can be
further converted to 5-alkoxymethylfurfurals (e.g. 5-ethoxy-

methylfurfural, EMF; Scheme 15), promising fuel additives,
when the reaction medium is changed from an aqueous solu-
tion to alcoholic solvents.144,145 The energy density of EMF is
8.7 kWh L1, which is comparable to that of diesel (9.7
kWh L1) and gasoline (8.8 kWh L1), and much higher with
respect to that of ethanol (6.1 kWh L1).146 Heteropolyacid-
and sulfonic acid-functionalised materials have been recently
demonstrated to be ecient in the conversion of HMF and
sugars containing fructose units to EMF in good yields (up to
91.5%).147151 However, this type of Brnsted acid catalysts was
poorly active for the synthesis of EMF from glucose; in turn,
ethyl glucopyranoside was formed as the main product in high
yields (91.7%) at 90120 C.152,153 The increase of the reaction
temperature to 140 C might lead to the formation of ethyl
Scheme 14 Schematic representation of furanic products derived from levulinate derived from the subsequent alcoholysis
HMF and furfural.142,143 reaction.154156 Although acetalisation of HMF preceding ether-
ification in ethanol was detected,157 the reaction equilibrium
could be further shifted from the acetalised products (diethyl-
5-ethoxymethylfurfural) can be synthesized from these plat- acetal of HMF and EMF) to EMF catalysed by a strong protonic
form molecules using zeolites (Scheme 14) when subjected to acid such as H4SiW12O40/MCM-41 nanospheres,158 Ar-
downstream reactions including alkoxylation, oxidation and SO3H-SBA-15159 and H3PW12O40/MCM-41.160
hydrogenation.142,143 In recent decades, much attention has The presence of strong Lewis acid sites was shown to
been placed on the use of zeolitic materials to generate valu- enable the increase of selectivity towards EMF by restricting
able substances from biomass derivatives. This section depicts side reactions.161163 More importantly, the introduction of
Scheme 15 Reaction routes for synthesis of EMF from hexoses.146
View Article Online
Scheme 16 One-pot, two-step synthesis of EMF from glucose with Sn-beta and Amberlyst 131.164
Lewis acid sites integrated with Brnsted acid sites into the (12.5) provided an increasingly active system to the parent
reaction system was likely to catalyse the one-pot synthesis of H-beta(12.5) in the etherification of HMF with tert-butanol at
EMF from glucose through sequential isomerization, dehydra- 120 C.167 The increase in Lewis acidity after the ionic liquid
tion and etherification reactions. Lew et al.164 found that the immobilization enhanced the overall reactivity with a 76%
combination of a Lewis acid zeolite Sn-beta with Amberlyst selectivity obtained towards BMF at 46% HMF conversion. Two
131 could directly convert glucose to EMF with a moderate moles of HMF could be etherified to a prepolymer 5,5-(oxy-bis
yield of 31% in absolute ethanol at 90 C. The catalytic system (methylene))bis-2-furfural (OBMF) with high conversion
was composed of a two-step reaction process comprising (3599%) and selectivity (ca. 99%) over zeolites (e.g., Sn-beta,
sequential glucose isomerization catalysed by Sn-beta (5 h) fol- Zr-beta, Nb-beta, and Ta-beta) with Lewis acid sites and meso-
lowed by dehydrationetherification using Amberlyst 131 for porous materials (e.g., Sn-MCM-41 and Al-MCM-41) bearing
another 24 h (Scheme 16). A commercially available zeolite Brnsted and Lewis acid sites (Scheme 17) using nonprotic sol-
H-USY(6) integrated with Amberlyst-15 was demonstrated to be vents (e.g. trifluorotoluene).169 In contrast, a long-chain alco-
more ecient for the one-pot, two-step transformation of holic solvent containing carbon atoms of 612 would enable
glucose to EMF (up to 46% yield) in ethanol at 96 C after the dimethyl acetal of HMF (i.e., OBMF) to further undergo
reacting for 5 h with H-USY(6) and another 6 h with further transacetalization with the alcohol to give a bis(dialkyl) acetal
addition of Amberlyst-15.165 As an improved approach, de- in 8798% yields and ca. 96% selectivity as catalysed by a
aluminated beta zeolite [DeAl-H-beta(12.5)] prepared via calcina- zeolite (1.5Nabeta) prepared by partially exchanged H+ of
tion of H-beta(12.5) at 700 C in air for 6 h could fulfill the H-beta(12) with a 1.5 wt% Na+ content (Scheme 17).170 The
same goal via a single step catalytic process, and a moderate 1.5Nabeta zeolite could be reused four times with an identical
EMF yield of 37% was achieved at 125 C in 10 h.165 The de- conversion and selectivity. In addition, the catalytic etherifica-
aluminated zeolite could be recycled for at least five consecutive tion of furfuryl alcohol derived from pentoses with a meso-
runs with EMF yields remaining 2838% and intermediate porous aluminosilicate could also be performed showing a
HMF yields of 1012%, indicating good reusability of the cata- great potential of using zeolites for the production of biofuel
lytic system. furanic ethers from both hexoses and pentoses.171
Secondary and tertiary alcohols were also demonstrated to
be capable of producing the corresponding 5-alkoxymethyl- 4.2. Zeolite-catalysed oxidation reactions
furfurals such as 5-iso-propoxymethylfurfural (PMF) and 5-tert- Organic acids including levulinic acid (LA) and lactic acid
butoxymethylfurfural (BMF) from alkoxylation with HMF in (LAC) can be directly obtained from C6 carbohydrates over
the presence of an acidic catalyst.166,167 In recent years, only a acidic catalysts in the absence of H2 and O2 as shown in
few studies on the use of zeolitic materials to transform HMF Scheme 18.172 Unlike the anaerobic conversion process,
into BMF, a biodiesel additive, have been conducted.168 The aerobic conditions are amenable for the transformation of
immobilization of an ionic liquid, [BMIM][CrCl4], on H-beta biomass-derived platform molecules into another class of car-
Scheme 17 Plausible pathways for synthesis of 5,5-(oxy-bis(methylene))bis-2-furfural (OBMF) and bis(dialkyl) acetal.170
View Article Online
range of organic acids from renewables in the presence/

absence of oxygen is described.
4.2.1. Anaerobic transformations of carbohydrates to
organic acids. Levulinic acid (LA) is a platform chemical
widely employed to synthesize biofuels, oxygenated fuel addi-
tives and several biomass-derived chemicals (e.g. succinic
acid), resins, pharmaceuticals, herbicides, polymers, flavour-
ing agents, plasticisers, antifreeze agents, and solvents

(Scheme 19).176178 In general, LA was produced from hexose
sugars involving HMF as a key intermediate via cascade de-
hydrationhydrolysis steps in the absence of oxygen, wherein
formic acid was also formed in equivalent moles to LA.179
Strong Brnsted acids such as Amberlite IR-120 and HCl were
demonstrated to be active in the conversion of fructose or
sugars with fructose units to LA in water at moderate reaction
temperatures (ca. 100 C).180 Comparatively, high temperatures
(ca. 200 C) or long reaction durations (ca. 1224 h) were
required when glucose or glucose-containing sugars were
employed as substrates.180 The combination of Brnsted and
Lewis acid sites in appropriate concentrations was likely to
facilitate glucose-to-LA transformation by promoting the
Scheme 18 Synthesis of organic acids from cellulose via glucose.
process of glucose-to-fructose isomerization.181 In view of the
controllable acidity, zeolites were thus recently developed as
heterogeneous catalysts for the synthesis of LA from glucose.
In particular, the introduction of metal chlorides (e.g., CrCl3
boxylic acids including gluconic, glycolic and acetic acids as and FeCl3) to H-Y zeolites through a wetness impregnation
well as furoates.173 Interestingly, formic acid can be produced method was illustrated to greatly increase Lewis acidity, which
from sugars via either aerobic or anaerobic oxidation.174,175 In could significantly enhance their catalytic activities in produ-
this section, the zeolite-mediated catalytic production of a cing LA from glucose (up to 62% yield) at 160180 C.182185
Scheme 19 Upgrading of levulinic acid (LA) to value-added chemicals and fuels.176
View Article Online
To investigate the eect of acidity and porosity of zeolites, a side to alkyl levulinate.194 Zhou et al.195 demonstrated that a
series of MFI-type zeolites (ZRP) with dierent Si/Al ratios were low concentration of nitric acid (0.2 mol L1) could remove
prepared and their activity was studied in the conversion of extraframework aluminum species from H-USY (Si/Al = 3.2)
glucose to LA.186 ZRP-15 (Si/Al = 15) with moderate acidity without influencing those in the framework, accordingly,
(2.33 mmol g1) and pore size (3.67 nm) was found to aord resulting in an increase of mesoporosity (2.8 to 2.9 nm) but a
the highest yield of LA (35.8%), while a relatively lower LA slight decrease of acidity (2.36 to 1.75 mmol g1). The syn-
yield of 29.5% at a similar glucose conversion (ca. 96%) was thesized H-USY-0.2 zeolite exhibited a superior catalytic
obtained over ZRP-12.5 (Si/Al = 12.5) with a higher acidity activity with respect to the parent counterpart in full conver-
(3.03 mmol g1) and larger pore size (5.82 nm) under identical sion of glucose to ML (32% vs. 22% yield) at 160 C in 5 h,
reaction conditions (180 C, 8 h). It was deduced that a high and an optimum ML yield of 54% could be achieved at 180 C
content of strong acid sites rather than that of total acid sites after 20 h reaction. Importantly, the structure of H-USY-0.2
was helpful for obtaining high yields of LA from glucose, while remained unchanged, with ML yield slightly decreasing by 8%
a large pore channel of mesoporous zeolites seemed to after five consecutive cycles.
increase the local protonic acidity that might result in side 4.2.2. Aerobic transformation of carbohydrates to organic
reactions including CC bond cleavage to give lactic acid. acids. An aqueous phase partial oxidation (APPO) process was
However, leaching of the surface Si, Al and O contents in demonstrated to be capable of directly transforming cellulose
aqueous solution led to a decrease in the relative crystallinity into useful products in moderate to good yields over zeolites
of zeolites (e.g., ZSM-5), and the increase of the carbon content (1014%) and especially ZrO2 (ca. 50%) at 240 C and 2.4 MPa
by adsorption of organic matter on the zeolite surface directly 2.8% O2 with 97.2% N2 for 20 min.196 The glycosidic bonds of
caused a gradual decrease in catalytic activity.187 cellulose were proposed to be cleaved via partial oxidation by
To circumvent the hydrothermal and thermal instability of in situ superoxide radical anions, giving equivalent amounts of
zeolites, alcohols replacing water have been adopted as an gluconic acid and glucose that would be further converted into
alternative reaction medium, with alkyl levulinates derived LA undergoing a chain of reactions involving the HoferMoest-
from further LA esterification obtained as main type decarboxylation (in the case of gluconic acid) and sub-
products.188190 In parallel, 5-alkoxymethylfurfural (e.g., EMF) sequent dehydration/rehydration for both cases (Scheme 20).
seemed to be the key intermediate leading to the formation of Gluconic acid has been identified as a versatile platform mole-
an alkyl levulinate (e.g., ethyl levulinate: EL) when sugar was cule to synthesise food additives, nylons, and plastics.197 For
utilised as the substrate.191 After checking dierent zeolites the synthesis of gluconic acid from sugars, oxidase enzymes
(e.g., Y, BEA and ZSM), Saravanamurugan and Riisager found and noble metals generally exhibited superior activities under
that the H-USY (Si/Al = 6) zeolite containing more Lewis acid aerobic conditions.198201 Among various solid supports, zeo-
sites was illustrated to exhibit the best performance in the syn- lites having a high porosity, and acidic sites were helpful to
thesis of methyl (ML: 49% yield) and ethyl (EL: 41% yield) immobilize active centers and hydrolyze polysaccharides,
levulinates from glucose at 160 C for 20 h in methanol and which also played roles in accelerating the catalytic perform-
ethanol, respectively.192 The H-USY zeolite could also be ance of both enzyme- and metal-mediated oxidation
reused for at least five cycles with almost unchanged ML and processes.202,203
EL yields (ca. 4550% and 4045%, respectively). The use of Instead of being employed as a support, Lewis acidic zeo-
H-USY (Si/Al = 6) could not only largely restrain the formation lites i.e. Sn-beta were demonstrated to be highly ecient in
of dialkyl ethers in the alcoholysis procedure,193 but also facili- the selective oxidation of levoglucosenone (LGO) using H2O2
tate a further conversion of in situ generated alkyl glucopyrano- as an oxidant to produce optically pure (S)--hydroxymethyl-
Scheme 20 Reaction routes for producing levulinic acid (LA) from cellulose.196
View Article Online

Scheme 21 Reaction pathway for the oxidation of levoglucosenone to (S)--hydroxymethyl-,-butenolide.204
,-butenolide (HBO), wherein a key intermediate, formate (Scheme 22).205207 Large-pore zeolite (e.g., H-beta and H-Y)
lactone, was formed through the BaeyerVilliger oxidation at supported gold particles and V2O5 were demonstrated to be
room temperature, followed by hydrolysis to give the product active for oxidation of HMF into 2,5-furandicarboxylic acid
at 45 C (Scheme 21).204 In the one-pot cascade reaction, the (ca. 99% yield) and 2,5-diformylfuran (ca. 84% yield) under a
combined utilization of Sn-beta with an acid resin (e.g., low H2 pressure of 0.10.3 MPa.208,209 A further integration of
Amberlyst 15) could allow a much higher HBO yield of 90% via the oxidative step with additional reactions i.e. etherification
a two-step process after reacting for ca. three days. Lewis acid and acetalisation catalysed by H-beta and gold particles could
sites introduced by isolated tin species in the framework of also be conducted to produce biodegradable surfactant ether
Sn-beta were found to be mainly responsible for the Baeyer molecules.210 Interestingly, immobilization of vanadyl ions
Villiger oxidation as well as FBO hydrolysis to HBO. (VO2+) on amino modified SBA-15 (SBA-NH2) could greatly
Nevertheless, the hydrolysis step was comparatively slower enhance the stability and reusability of the as-prepared catalyst
than that catalysed by Brnsted acids (e.g., Al-beta(F) and SBA-NH2-VO2+, giving 2,5-furandicarboxylic acid and 2,5-
Amberlyst 15). Interestingly, undesired competitive degra- diformylfuran in a total yield of 92% at 110 C and O2 with a
dation reactions promoted by Brnsted acid sites were almost flow rate of 20 mL min1 in 4-chlorotoluene.211 The selectivity
suppressed using Sn-beta, which indicated the synergistic towards 2,5-diformylfuran could be further improved when
eect of Brnsted and Lewis acid sites in oxidation of LGO to SBA-15 immobilised 2,2,6,6-tetramethylpiperidine-1-oxyl
HBO.204 (TEMPO) was used as the catalyst, and a moderate yield of 73%
A series of oxygenated furanic compounds such as 2,5-di- was obtained at 40 C with an O2-filled balloon (1 atm) after
formylfuran, 5-formyl-2-furancarboxylic acid, 2,5-furandicar- 1 h.212 More importantly, TEMPO-SBA-15 could be easily recov-
boxylic acid, 5-hydroxymethyl-2-furancarboxylic acid, 2-furoic ered and recycled for at least five runs with negligible loss in
acid, and maleic anhydride could be synthesised through catalytic performance. Starting from fructose, Yang et al.213
selective oxidation reactions from HMF and furfural reported that the use of a solid acid Fe3O4-SBA-SO3H combined
Scheme 22 Selective oxidation of 5-hydroxymethylfurfural (HMF) and furfural to other furanic compounds.205
View Article Online
with an oxidant K-OMS-2 could sequentially catalyse dehydra- and oxidative cleavage reactions in a continuous flow and
tion and subsequent oxidation to give 2,5-diformylfuran in packed bed reactor at 200 C with a contact time of 3.9 min
good yields (80%) via a one-pot, two-step process at 110 C in (Scheme 23, Path 3), oering a competitive advantage over the
an O2 flow rate of 10 mL min1. The two mixed catalysts could aerobic oxidation process that involves butane as maleic anhy-
be conveniently separated by an external magnet and succes- dride feedstock.217
sively reused in multiple runs.
Using titanium silicate (TS-1) as a catalyst and H2O2 as an 4.3. Zeolite-catalysed hydrogenation reactions
oxidizing agent, furfural could be fully oxidised to maleic 4.3.1. Partial hydrogenations to oxygenated products
anhydride in 78% yield at 50 C after 24 h (Scheme 23, Path 4.3.1.1. Catalytic hydrogenations. Zeolites have been gener-
1).214 The sequential addition of TS-1 and Amberlyst 70 ally used as solid supports to adjust the catalytic surroundings
through a two-step process could further increase the yield of (e.g., acidity and dispersity) of metal particles in catalytic
maleic anhydride to 92%, and highly decrease the addition of hydrogenation processes using molecular hydrogen. HMF is
H2O2 from 12.3 to 6.6 wt%. Notably, TS-1 was able to be an important dehydration product of hexose sugars which can
recycled for at least six runs with no visible deactivation, not- be upgraded to 2,5-dimethylfuran (DMF) featuring good pro-
withstanding the slight leaching of Ti species. Li and Zhang215 spects as biofuel due to its high octane number (RON = 119)
showed that vanadium oxide catalysts V2O5 and V2O5/SiO2 and appropriate energy density (ca. 31 MJ L1).218,219 In the
were both active in the heterogeneous oxidation of HMF, selec- catalytic process, 2,5-bis-(hydroxymethyl)furan (BHMF),
tively giving maleic anhydride in a moderate yield of 79% at 5-methylfurfuryl alcohol (MFA), and 2,5-dimethyl-
100 C and 0.5 MPa O2 after 4 h (Scheme 23, Path 2). A one- tetrahydrofuran (DMTHF) could be observed as dominant
pot, two-step reaction process involving HCl-catalysed fructose intermediates and by-products (Scheme 24), dierent from
dehydration to HMF in 2-propanol at 100 C for 3 h, and V2O5 DMF. The distribution of products was demonstrated to be
or V2O5/SiO2-mediated HMF oxidation to maleic anhydride aected by the reaction parameters, in particular, relatively
under the above optimised reaction conditions was further lower temperatures (100 C) were helpful to produce BHMF,
explored, and an overall maleic anhydride yield of 50% could and DMF with certain amounts of MFA and DMTHF formed at
be obtained.215 The cleavage of the CC bond took place due high temperatures 220 C.220,221 Various bi- and monometal-
to the OH group rather than CHO of HMF at a higher O2 lic catalysts including CuRu/C, RuSn/C, Pd/C and Ru/C have
pressure of 1.0 MPa, and a lower O2 pressure of 0.1 MPa would been recently explored for HMF to DMF hydrodeoxygenation
be more helpful to oxidise HMF to 2,5-diformylfuran.216 in moderate to good yields at 220260 C.222225 Using a facile
Maleic anhydride could also be produced from levulinic acid ion exchange method, Nagpure et al.226 synthesized a series of
in good yields (71%) using VOx supported on SiO2 via aerobic transition metal (i.e., Pt, Pd, Rh, Ru, Au, Ni, and Cu)
Scheme 23 Synthesis of maleic acid or maleic anhydride from furfural, HMF and levulinic acid.214216
View Article Online

Scheme 24 Reaction pathways for hydrodeoxygenation of HMF and furfural to 2,5-dimethylfuran (DMF) and 2-methylfuran, respectively.220,221
exchanged NaY catalysts, with interesting catalytic perform- yields) under identical conditions, wherein a reaction pathway
ance in the selective hydrogenolysis of HMF to DMF with involving acidic HMFI-assisted ring-opening, followed by Pt-
respect to HMF conversion. The reactivity was found to be in catalysed hydrogenation was proposed. Instead of using noble-
the order of Cu < Ni < Au < Rh < Pd = Pt = Ru ranging from metal catalysts (e.g., Pt and Ru), a base-metal bifunctional cata-
30.1 to 100% at 220 C within 1 h. The well-dispersed Ru nano- lyst (Co@HZSM-5) was developed to be ecient to hydrogenate
particles possibly contributed to the superior activity (78% LA in a batch reactor at 240 C or a fixed-bed reactor at 280 C,
selectivity at 100% conversion) and good recyclability of 2 wt% giving VA in yields of 97% and 93%, respectively.234 In
Ru/NaY in six consecutive cycles with a constant DMF yield of addition, GVL could be selectively converted to related valuable
80%. In parallel, furfural derived from xylose dehydration compounds including butenes, 2-methyltetrahydrofuran,
over an H-form zeolite (e.g., H-mordenite) could be hydrogen- 4-methoxypentanoate and aromatic hydrocarbons via corres-
ated with a Cu/Fe catalyst to produce 2-methylfuran with a ponding decarboxylation, hydrogenation/dehydration, alcoho-
high yield of up to 98% at 252 C through a one-pot, two step lysis and pyrolysis reactions.235238
catalytic process.227 A bifunctional catalyst 5% Pd/Al-SBA-15 4.3.1.2. Transfer hydrogenations. Organic molecules such as
was demonstrated to be active for the one-pot hydrogenation short chain alcohols and formic acid can also donate hydrogen
esterification of furfural with acetic acid, and a synergistic to upgrade biomass and its derivatives through catalytic trans-
eect between the metallic and acidic sites was disclosed, fer hydrogenation.239 In liquid phase catalytic hydrogenation
wherein the good accessibility of large molecules to the metal of LA and its esters to GVL, the turnover controlling transition
and acid sites in mesoporous Al-SBA-15 was more helpful for state was illustrated to involve an intramolecular hydride trans-
cascade catalytic processes.228 fer via a six-membered transition state.240 Zr-containing cata-
Zeolite supported metal particles (e.g., Ru/ZSM-5) were also lysts were most frequently employed to promote transfer
reported to be ecient in the conversion of sugar-derived LA hydrogenation for producing GVL from lignocellulosic
and its esters to -valerolactone (GVL) through cascade hydro- biomass.241,242 Wang et al.243 demonstrated that a Zr-beta
genation and cyclization,229 and increasing attention has been zeolite was highly active for the MeerweinPonndorfVerley
placed on catalytic upgradation of GVL with supported metals (MPV) reduction of LA, producing GVL with a high yield of
(Scheme 25).230,231 At 200 C and 40 MPa H2, 1 wt% Ru/TiO2 >99% and a steady space-time-yield of 0.46 molGVL gZr1 h1
could catalyse LA being hydrogenated to give high selectivity within 87 h at 250 C in a continuous flow reactor. The pres-
towards GVL (97.5%) at 100% conversion, while 1 wt% Ru/ ence of medium to strong Lewis acid sites integrated with rela-
H-ZSM-5 directly aorded a moderate valeric acid (VA) yield of tively few basic sites probably contributed to the high activity
45.8% in dioxane.232 The ring-opening of GVL requiring acid and good reusability/durability. Likewise, ZrO2 on SBA-15 pre-
sites was inferred to be the rate-determining step on the pared by wet impregnation was shown to be ecient for the
pathway to VA. A much higher yield of VA (99%) was obtained aforementioned transfer hydrogenation, producing GVL with a
from solvent-free hydrogenation of LA over a HMFI zeolite-sup- high selectivity of 93% at 100% LA conversion.244 The well-dis-
ported Pt metal cluster (Pt/HMFI) at 200 C and 40 MPa H2 persed acidic sites derived from ZrO2 and ease of accessibility
after 24 h.233 Pt/HMFI was also eective for the selective syn- for the substrate and active sites were most likely responsible
thesis of VA esters from LA in methanol or ethanol (8184% for the excellent catalytic performance. Catalytic production of
View Article Online

Scheme 25 Reaction network for converting sugar-derived LA to -valerolactone (GVL) to other useful chemicals and fuels.231
GVL with high performance (ca. 80% yield) could also be activities in downstream transfer hydrogenation of furfural to
achieved at 120 C by using 2-butanol as the solvent and GVL.247 The one-pot integration of Au/ZrO2 with H-ZSM-5
H-donor over zeolites simultaneously bearing Brnsted and could thus eciently catalyse the in situ formed furfural from
enhanced Lewis acid sites through cascade reactions involving hemicellulose, undergoing tandem reactions to produce GVL
the MPV reduction twice and ring-opening and closing with a 61.5% overall yield at 120 C for 24 h. Importantly, the
processes using furfural as the starting material mixed catalysts were quite robust in four continuous reaction
(Scheme 26).245,246 A significant amount of medium-strength cycles without detecting leached species.
acid centers oered by zeolites (e.g., H-ZSM-5) was highly Furfural, a co-product of LA derived from sugars containing
required for the initial hydrolysis and dehydration steps to give both hexose and pentose units, could be transformed into LA
furfural, while the strong interface interaction between ZrO2 through transfer hydrogenation to furfuryl alcohol and sub-
and Au species provided an optimum medium for excellent sequent alcoholysis to yield an alkyl levulinate.248 The
Scheme 26 Synthesis of -valerolactone (GVL) from furfural though cascade reactions involving the MeerweinPonndorfVerley (MPV) reduction
twice, and ring-opening and closing processes.245,246
View Article Online
Scheme 27 Direct conversion of xylose to levulinic acid (LA) with H-Y zeolite using in situ generated HCOOH as the H-donor.255
H-ZSM-5 zeolite with a Si/Al molar ratio of 25 was able to groups could further undergo etherification with the alcohol
produce LA from furfuryl alcohol with a high yield (>70%) in to produce 2,5-bis(alkoxymethyl)furan (BAMF) considered as a
either pure water or a monophasic solvent consisting of tetra- potential biodiesel additive, as shown in Scheme 28.256,257 Sn-
hydrofuran (THF) and water (1/2, w/w).249,250 Nonetheless, beta exhibited a superior activity as compared to Zr-beta (87%
acidic zeolites (e.g., H-ZSM-5) exhibited lower activity in the vs. 79% yield) in transfer hydrogenation coupled with etherifi-
ethanolysis of furfuryl alcohol to EL as compared to sulphated cation of HMF to 2,5-bis[(1-methylethoxy)methyl]furan at
catalysts, and a large amount of diethyl ether was co- 180 C, 2-propanol, 2.04 MPa N2 for 6 h.258 In contrast, the
formed.251253 A controllable increase of the density and acces- catalytic performance of metal-modified zeolites to generate
sibility of acid sites in zeolites showed promising potential to 2,5-bis(ethoxymethyl)furan yield was in the order of Hf-beta
improve EL selectivity while restraining the formation of unde- (67%) > Zr-beta (54%) > Sn-beta (41%) > Al-beta (7%) > Nb-beta
sirable products (e.g. diethyl ether).254 Interestingly, one-pot (3%) > Ta-beta (2%) > Ti-beta (0) Si-beta (0) after reacting at
conversion of xylose to LA with a moderate yield of 30% 120 C for 24 h in ethanol.259 The rate-limiting hydride shift
could be carried out over a H-Y(Si/Al = 15) zeolite treated with transition state involved in the cascade reactions was hypoth-
0.25 M NaOH solution in hot-compressed water in the absence esized to be optimally stabilised by hard Lewis acidic centers
of external hydrogen, wherein in situ generated formic acid (e.g., Hf, Zr and Sn) rather than weaker Lewis acid sites (e.g.,
during the reaction acted as a H-donor in the hydrogenation of Nb, Ta and Ti) of the zeolites, especially when a primary
furfural to furfuryl alcohol, thus facilitating the formation of alcohol was used as a H-donor.
LA (Scheme 27).255 The amount of new strong acid sites was 4.3.2. Full hydrogenation to hydrocarbons
increased while no significant change in the Si/Al ratio was 4.3.2.1. Light hydrocarbons. C3C6 hydrocarbons are vital
observed because the realumination of aluminium species feedstocks used in petrochemistry, in which C3 and C4 olefins
occurred on the external surface of the zeolite with an increase can be used as precursors for the production of polymer
of NaOH concentration, which was correlated to improvements materials, while C5 and C6 alkanes can be directly utilised as
in LA yields produced from xylose. additives to fossil gasoline.260262 These light hydrocarbons
As illustrated in Section 4.1, the alkoxylation of HMF with could be directly produced from lignocellulosic biomass via
alcohols over H-form zeolites could give rise to the formation cracking reactions (Scheme 29) or hydrolytic hydrogenations
of 5-alkoxymethylfurfural (e.g., EMF). The presence of Lewis (Scheme 30). Kato and Sekine263 found that cellulose could be
acid sites in a secondary alcohol (e.g., 2-propanol and transformed into C3 and C4 hydrocarbons with moderate
2-butanol) enabled the transfer hydrogenation of the aldehyde selectivity (up to ca. 50%) in the presence of 1 wt% Pt sup-
group in HMF to be carried out to give 2,5-bis(hydroxymethyl) ported on a large-pore zeolite such as H-beta(Si/Al = 12.5) and
furan (BHMF), and the resulting BHMF with two hydroxyl H-USY(Si/Al = 7) at 170 C under an inert atmosphere.
Scheme 28 Lewis acid-catalysed conversion of HMF to 2,5-bis(alkoxymethyl)furan (BAMF) in 2-propanol.256
Scheme 29 Possible reaction network of synthesizing hydrocarbons from cellulose over Pt/H-USY.263
View Article Online

Scheme 30 Reaction routes for catalytic production of C5 and C6 alkanes from hemicellulose and cellulose.264
Supports such as -Al2O3 showed a comparably poor selectivity from sugar polyols. No evident CC dissociation was detected
(<15%) towards C3 and C4 components. In particular, the Pt/ over an identical catalytic system consisting of Ir-ReOx/SiO2
H-beta zeolite synthesised via ion exchange exhibited a and H-ZSM-5 in a biphasic solvent (n-dodecane and H2O) even
superior selectivity for C3 and C4 hydrocarbons to that when cellulose was used as the substrate, with 83% yield of
obtained by impregnation, pointing to the need of a large pore n-hexane achieved at 190 C and 6 MPa H2 after 12 h.268 The
system and eective acidity. C5 and C6 sugars were the most whole catalytic process starting from cellulose to n-hexane was
likely intermediates in the production of C3 and C4 hydrocar- proposed to successively involve hydrolysis, hydrogenation,
bons from cellulose at 170 C over 1 wt% Pt/H-USY catalysts, and hydrogenolysis (Scheme 30), wherein H-ZSM-5 enhanced
respectively.264 cellulose hydrolysis in hot water as well as the CO bond
Interestingly, CC cleavage was largely inhibited when Ni hydrogenolysis activity of Ir-ReOx/SiO2. Notably, the yield of
particles were employed as active metal sites supported on zeo- n-hexane remained almost constant, slightly decreasing from
lites [e.g., 2 wt% Ni/H-ZSM-5 and 1.0 wt% Ni2P/H-USY(Si/Al = 83 to 66% after four consecutive cycles.
40)]. In this way, pentane could be obtained from hemicellu- 4.3.2.2. Long-chain hydrocarbons. The high volatility of light
lose-derived C5 compounds such as xylitol and 2-methyl- hydrocarbons makes them of low value as a fuel additive,
tetrahydrofuran in high yields (ca. 91%) at a high reaction despite the fact that C2C9 alkanes were able to be directly pro-
temperature of 240 C and 0.54 MPa H2.265,266 As a more duced from hydrocracking of biomass-derived com-
active catalytic system, the combination of Ir-ReOx/SiO2 with pounds.269,270 In recent decades, significant eorts have been
H-ZSM-5 by using n-dodecane as the cosolvent could catalyse made for the production of diesel (C9C22) and jet fuel (C8
the hydrogenolysis of aqueous sorbitol, xylitol, erythritol and C16) range alkanes from lignocellulose-derived platform chemi-
glycerol to n-hexane, n-pentane, n-butane and propane with cals by CC coupling reactions.271,272 Catalytic aldol conden-
high yields (95%) at 140 C and 8 MPa H2 after 24144 h, sation between HMF or furfural and acetone with a base or
respectively.267 CC cracking reactions were significantly sup- acid was frequently used to increase the carbon-chain length
pressed on Ir-ReOx/SiO2, while other metals including Ru, Ni, of furanic compounds (Scheme 31). Shen et al.273 found that a
and Pt previously reported to be active in CO bond hydro- nitrogen-substituted NaY zeolite with increased base strength
genolysis exhibited much lower selectivity towards n-alkanes exhibited a higher performance as compared to untreated NaY
Scheme 31 Aldol condensation of HMF or furfural with acetone catalysed by a base or acid.273
View Article Online

Scheme 32 Reaction network for hydrodeoxygenation of furfuralacetone condensation products.277
in aldol condensation of furfural/HMF with acetone (conver- Bohre et al.278 demonstrated that the aldol condensation
sion: 55.5%/40.1% vs. 6.7%/14.1% with comparable selectivity) product obtained from HMF and acetone could be selectively
at 120 C after 16 h in water/methanol (1 : 1, v/v). The hydrodeoxygenated to n-nonane and 1-ethoxynonane with a
monomer and dimer aldol product distribution was found to total yield of 96% over a bifunctional 5 wt% Pd/beta catalyst in
be almost equal despite an increased conversion to ca. 100% ethanol at 230 C and 5 MPa H2 for 8 h. The attractive results
(by prolonging reaction duration to 24 h or changing reaction indicate that isolated aldol products have a significant poten-
medium to either water/methanol or pure water). H-form zeo- tial to be selectively upgraded to diesel and gasoline range
lites such as H-beta(Si/Al = 12.5), H-USY(Si/Al = 40) and fuels.
H-ZSM-5(Si/Al = 11.5) could largely enhance the selectivity Alternative approaches such as ketonization, oligomeriza-
towards the monomer aldol product (ca. 80%), but furfural tion and alkylation have also been developed to increase the
conversion was lower than 40% after reacting at 100 C for carbon-chain length of biomass derivatives.279 Particularly,
2 h.274 Kikhtyanin et al.275 also verified that the acidic, other SO3H-functionalised catalysts have been recently demonstrated
than basic, centers took part in the aldol condensation and to be highly ecient for hydroxyalkylation/alkylation of
the Brnsted acid sites in situ generated from the metal 2-methylfuran with various biomass-derived carbonyl com-
cations interacting with water exhibited an enhanced perform- pounds to produce C11 oxygenated intermediate molecules
ance in the reaction. Layered two-dimensional zeolites with a (Scheme 33).280282 Strong Brnsted acids (e.g., H2SO4 and
MWW framework topology showed superior accessibility of the Amberlyst 15) allowed trimerization of 2-methylfuran to form a
acidic sites with respect to classical three-dimensional zeolites, C15 alkane (i.e., 5,5-bisylvyl-2-pentanone) via acid-catalysed
thus achieving high furfural conversions with all MWW family hydrolysis of 2-methylfuran to 4-oxopentanal, followed by
catalysts.276 hydroxyalkylation and alkylation of the intermediary aldehyde
For hydrodeoxygenation of furfuralacetone condensation with two molecules of 2-methylfuran.283,284 Zeolitic materials
products (Scheme 32), most supported Pt catalysts (e.g., Pt/ with an adequate 3D structure, medium to large micropores,
Al2O3, Pt/TiO2, Pt/hydrotalcite, Pt/beta, Pt/Al-SBA-15 and Pt/ and more medium to strong Brnsted acid sites could also cata-
WO3-ZrO2) were most likely to completely hydrogenate the ali- lyse the hydrolysis/condensation of 2-methylfuran to 5,5-bisylvyl-
phatic CvC bonds of condensed substrates at 200 C after
480 min, thus showing high conversions.277 However, the cata-
lytic hydrogenation of furanic CvC and ketonic CvO bonds
was restricted, especially using hydrotalcite and Al2O3 as sup-
ports. Pt/TiO2 could further promote the hydrogenation reac-
tions in spite of the low selectivity towards linear alcohols
caused by slow rate-dehydration and ring-opening steps. Non-
saturated rings preferentially facilitated ring-opening reac-
tions, implying that total hydrodeoxygenation could be
achieved by selective hydrogenation to ketonic CvO and ali- Scheme 33 Hydroxyalkylation/alkylation of sylvan (2-methylfuran) with
phatic CvC bonds before the ring-opening step. Recently, aldehydes.
View Article Online

Scheme 34 Possible reaction pathways for conversion of furoins to hydrocarbon liquid fuel (alkane).286
2-pentanone.285 H-beta with a Si/Al ratio of 20 gave a higher Computational studies indicated that the DielsAlder cyclo-
2-methylfuran conversion of 43.3% with a moderate yield of addition was the rate-limiting step mediated by Lewis acids,
31.4% in ethanol/water (85 : 15, v/v) at 100 C for 3 h, while while Brnsted acids were extremely active in promoting the
H-beta zeolites possessing Si/Al ratios 50 aorded lower obtained oxa-norbornene derivative being dehydrated to aro-
2-methylfuran conversions (ca. 20%) with product yields lower matics.297,298 On the other hand, a kinetic model revealed the
than 15% despite a constant selectivity regardless of the Si/Al tandem reactions involving the first step uncatalysed Diels
molar ratios. Interestingly, H-beta with a Si/Al molar ratio of Alder cycloaddition and the second step heterogeneous acid-
180 was highly selective for complete hydrodeoxygenation of catalysed dehydration.299 To balance the selectivity and stabi-
the N-heterocyclic carbene (NHC)-catalysed benzoin conden- lity of zeolites, some improved methods such as metal modifi-
sation product 5,5-dimethylfuroin to dodecanes with high cation, hydrophobicity adjustment, and surface and structure
yields (up to 76%) and selectivity to n-dodecane (94%) at optimization have been recently explored.300303
230 C and 6 MPa H2 for 8 h (Scheme 34).286 In addition to the aforementioned applications, zeolites
have been increasingly involved in other catalytic processes.
Catalytic production of biodiesel from plant oils in high yields
4.4. Zeolite-catalysed miscellaneous reactions
could be achieved through either transesterification or esterifi-
Zeolite-catalysed DielsAlder cycloadditions of furanic com- cation reactions by using modified zeolites directly as acidic
pounds (e.g., furan, furfural, HMF, 2,5-dimethylfuran, catalysts or as solid supports to immobilize acid or base
2-methylfuran, and furfuryl alcohol) with olefins (e.g., ethylene species.304307 Both fatty acids and waste oils could be deoxyge-
and propylene), followed by dehydration could aord aromatic nated to jet fuel range alkanes and aromatic hydrocarbons
compounds in high selectivities (up to 100%; Scheme 35) as a when metal particles were introduced onto the zeolites.308,309
promising and alternative catalytic route to the current fossil- Meanwhile, glycerol as a by-product could be further upgraded
based approach.287291 H-form zeolites and mixed metal via various reactions such as dehydration, oxidehydration,
oxides (WOxZrO2) containing both Brnsted and Lewis acid (trans)etherification and oxidation over zeolitic
sites were demonstrated to be comparably more active than materials.310314 Catalytic acetalisation with zeolites at room
those primarily having Lewis acid sites irrespective of micro- temperature to protect carbonyl functionalities in biomass-
porosity, indicating the importance of Brnsted acidity in the derivatives (e.g., furfural) has also been investigated, and a
production of aromatics.292,293 Brnsted acid sites in H-beta good acetyl yield of 79% could be obtained employing H-USY(6)
exhibited superior activity with respect to Lewis acid sites in as the catalyst.315 In combination with biological catalysis,
Sn-beta and Zr-beta for the oligomerization of DMF and 2,5- microporous zeolites were capable of confining enzymes with
hexanedione, which caused the rapid deactivation of H-beta observed robust activity and enhanced stability.316,317 The
despite its high selectivity in DielsAlder cycloaddition. Sn- rapid advances in biomass valorisation make additional devel-
beta and Zr-beta were both comparably more stable.294296 opments of zeolitic materials crucial to advance in the design
of new increasingly active and stable zeolites and zeotype
materials in future biorefineries.
5. Conclusions and outlooks

Zeolitic materials have been demonstrated to be highly active
and selective for a range of catalytic transformations of
biomass concerning furanic compounds as either a target
Scheme 35 Reaction network for conversion of furanic compounds to product or a starting material. The controllable Brnsted/Lewis
phenyl compounds.287291 acid sites by varying the Si/Al ratio, multifunctionality by intro-
View Article Online
ducing extra metal species or modifying agents and universal Acknowledgements

shape-selectivity oered by the microporous structures can
play a significant role in advancing the design and tuneability HL and SY wish to acknowledge the financial support from the
of zeolites in view of their catalytic performance for biomass/ National Natural Science Foundation of China (21576059), and
waste valorisation in future biorefineries. To speed up the the Key Technologies R&D Program of China (2014BAD23B01).
industrialization process of biomass valorisation catalysed by AP, RSS and SS thank the Department of Biotechnology
zeolites, some possible issues can be taken into consideration (Government of India), New Delhi, India.
for further optimization of zeolitic materials to be more appli-

cable to typical biomass valorisation processes and/or reaction
conditions: References
(1) medium-pore zeolites (5.25.9 ) were found to show the
highest aromatic yields in the production of aromatics from 1 C. H. Zhou, X. Xia, C. X. Lin, D. S. Tong and J. Beltramini,
biomass; in contrast, small-pore zeolites gave CO, CO2 and Chem. Soc. Rev., 2011, 40, 55885617.
coke as the main products without any aromatics and oxyge- 2 E. Taarning, C. M. Osmundsen, X. Yang, B. Voss,
nates, and large-pore zeolites caused the formation of more S. I. Andersen and C. H. Christensen, Energy Environ. Sci.,
coke and less aromatic and oxygenate compounds.318 Shape- 2011, 4, 793804.
selectivity constraints call for additional rational design of 3 S. Caratzoulas, M. E. Davis, R. J. Gorte, R. Gounder,
novel zeolite materials based on the fundamental understand- R. F. Lobo, V. Nikolakis, S. I. Sandler, M. A. Snyder,
ing of pore size and structure which can be fulfilled by using M. Tsapatsis and D. G. Vlachos, J. Phys. Chem. C, 2014,
template/steam-assisted and base/acid-treated synthetic 118, 2281522833.
processes.319323 4 Y. Romn-Leshkov and M. E. Davis, ACS Catal., 2011, 1,
(2) The introduction of exogenous metal species into the 15661580.
framework of the zeolites can result in the generation of strong 5 O. Muraza and A. Galadima, Ind. Eng. Chem. Res., 2014,
Lewis acidity as well as metal sites, but the synthetic process is 53, 1786917877.
generally time-consuming. The development of more facile 6 X. Tong, Y. Ma and Y. Li, Appl. Catal., A, 2010, 385, 113.
and eective methods for metal incorporation (e.g. mechano- 7 O. O. James, S. Maity, L. A. Usman, K. O. Ajanaku,
chemistry324) can further facilitate the catalytic processing of O. O. Ajani, T. O. Siyanbola, S. Sahu and R. Chaubey,
biomass using zeolites. Energy Environ. Sci., 2010, 3, 18331850.
(3) Product distribution in zeolite-catalysed biomass conver- 8 M. Stocker, Angew. Chem., Int. Ed., 2008, 47, 92009211.
sion, particularly derived from polysaccharides and raw ligno- 9 L. Wang and F. S. Xiao, Green Chem., 2015, 17, 2439.
cellulosic biomass, is rather complex. An extensive examin- 10 J. S. Kruger, V. Nikolakis and D. G. Vlachos, Curr. Opin.
ation and quantification of both target products and by-pro- Chem. Eng., 2012, 1, 312320.
ducts will facilitate understanding the carbon balance and 11 N. M. Xavier, S. D. Lucas and A. P. Rauter, J. Mol. Catal. A:
possible reaction pathways of zeolite-mediated catalytic Chem., 2009, 305, 8489.
systems in view of future optimisation in the synthesis and 12 Y. He, T. C. Ho, L. Emdadi, Y. Wu, J. Bouraima and
design of zeolites as well as catalytic processes (e.g. continuous D. Liu, Catal. Sci. Technol., 2014, 4, 30643073.
flow).325 13 C. Perego and A. Bosetti, Microporous Mesoporous Mater.,
(4) Zeolites can be used as either acidic catalysts or solid 2011, 144, 2839.
supports for biomass valorisation. Active sites predominantly 14 D. Kubicka and O. Kikhtyanin, Catal. Today, 2015, 243,
responsible for specific reactions including unexpected path- 1022.
ways still lack comprehensive studies and require additional 15 C. Martnez and A. Corma, Coord. Chem. Rev., 2011, 255,
eorts to fully understand the role of active sites (e.g. bifunc- 15581580.
tional metalzeolite systems) in biomass conversion. 16 T. Ennaert, J. V. Aelst, J. Dijkmans, R. D. Clercq,
Systematic investigations on the catalytic mechanisms of W. Schutyser, M. Dusselier, D. Verboekend and B. F. Sels,
zeolite-catalysed processes may oer constructive directions on Chem. Soc. Rev., 2016, 45, 584611.
the structural optimization of zeolites in view of future poten- 17 M. Moliner, Dalton Trans., 2014, 43, 41974208.
tial implementation in biorefinery concepts at large-scale. 18 F. Guo, Z. Fang, C. C. Xu and R. L. Smith Jr., Prog. Energy
In summary, zeolitic materials exhibit an outstanding Combust. Sci, 2012, 38, 672690.
potential for future industrial production of furanic/levulinic 19 L. Hu, L. Lin, Z. Wu, S. Zhou and S. Liu, Appl. Catal., B,
compounds from biomass despite the fact that their stability 2015, 174175, 225243.
and product selectivity still needs to be further improved by 20 C. Buttersack, W. Wach and K. Buchholz, J. Phys. Chem.,
emerging technologies. We hope that the cascade reactions 1993, 97, 1186111864.
with corresponding products showcased in this review can 21 C. Buttersack and D. Laketic, J. Mol. Catal., 1994, 94,
serve as a starting point for further developments in this field L283L290.
and for more practical multi-catalytic processes with zeolitic 22 C. Moreau, R. Durand, F. Alis, M. Cotillon, T. Frutz and
materials. M. A. Tholeyre, Ind. Crops Prod., 2000, 11, 237242.
View Article Online
23 C. Moreau, R. Durand, J. Duhamet and P. Rivalier, 50 A. A. Marianou, C. M. Michailof, A. Pineda,

J. Carbohydr. Chem., 1997, 16, 709714. E. F. Iliopoulou, K. S. Triantafyllidis and A. A. Lappas,
24 A. Abbadi, K. F. Gotlieb and H. van Bekkum, Starch/Strke, ChemCatChem, 2016, 8, 11001110.
1998, 50, 2328. 51 M. Moliner, Y. Romn-Leshkov and M. E. Davis, Proc.
25 L. Vilcocq, P. C. Castilho, F. Carvalheiro and L. C. Duarte, Natl. Acad. Sci. U. S. A., 2010, 107, 61646168.
ChemSusChem, 2014, 7, 10101019. 52 R. Bermejo-Deval, R. S. Assary, E. Nikolla, M. Moliner,
26 D. S. Pito, I. M. Fonseca, A. M. Ramos, J. Vital and Y. Romn-Leshkov, S. J. Hwang, A. Palsdottir,
J. E. Castanheiro, Chem. Eng. J., 2012, 184, 347351. D. Silverman, R. F. Lobo, L. A. Curtiss and M. E. Davis,
27 P. D. Car, M. Pagliaro, A. Elmekawy, D. R. Brown, Proc. Natl. Acad. Sci. U. S. A., 2012, 109, 97279732.
P. Verschuren, N. R. Shiju and G. Rothenberg, Catal. Sci. 53 H. J. Cho, P. Dornath and W. Fan, ACS Catal., 2014, 4,
Technol., 2013, 3, 20572061. 20292037.
28 R. Sahu and P. L. Dhepe, ChemSusChem, 2012, 5, 751761. 54 C. M. Osmundsen, M. S. Holm, S. Dahl and E. Taarning,
29 L. Zhou, M. Shi, Q. Cai, L. Wu, X. Hu, X. Yang, C. Chen Proc. R. Soc. London, Ser. A, 2012, 468, 20002016.
and J. Xu, Microporous Mesoporous Mater., 2013, 169, 54 55 G. Li, E. A. Pidko and E. J. M. Hensen, Catal. Sci. Technol.,
59. 2014, 4, 22412250.
30 A. Onda, T. Ochi and K. Yanagisawa, Green Chem., 2008, 56 Y. P. Li, M. Head-Gordon and A. T. Bell, ACS Catal., 2014,
10, 10331037. 4, 15371545.
31 Z. Zhang and Z. K. Zhao, Carbohydr. Res., 2009, 344, 2069 57 R. Gounder and M. E. Davis, ACS Catal., 2013, 3, 14691476.
2072. 58 A. Corma, L. T. Nemeth, M. Renz and S. Valencia, Nature,
32 P. Lanzafame, D. M. Temi, S. Perathoner, A. N. Spadaro 2001, 412, 423425.
and G. Centi, Catal. Today, 2012, 179, 178184. 59 C. C. Chang, Z. Wang, P. Dornath, H. J. Cho and W. Fan,
33 V. Degirmenci, D. Uner, B. Cinlar, B. H. Shanks, RSC Adv., 2012, 2, 1047510477.
A. Yilmaz, R. A. van Santen and E. J. M. Hensen, Catal. 60 M. Moliner-Marin, Y. Romn-Leshkov, M. E. Davis and
Lett., 2011, 141, 3342. E. Nikolla, Isomerisation of Sugars, US 20110207923A1,
34 P. Bhaumik, A. K. Deepa, T. Kane and P. L. Dhepe, 2011.
J. Chem. Sci., 2014, 126, 373385. 61 J. Dijkmans, D. Gabrils, M. Dusselier, F. de Clippel,
35 L. Zhou, Z. Liu, M. Shi, S. Du, Y. Su, X. Yang and J. Xu, P. Vanelderen, K. Houthoofd, A. Malfliet, Y. Pontikes and
Carbohydr. Polym., 2013, 98, 146151. B. F. Sels, Green Chem., 2013, 15, 27772785.
36 L. Xue, K. Cheng, H. Zhang, W. Deng, Q. Zhang and 62 M. Liu, S. Jia, C. Li, A. Zhang, C. Song and X. Guo,
Y. Wang, Catal. Today, 2016, 274, 6066. Chin. J. Catal., 2014, 35, 723732.
37 J. N. Chheda, G. W. Huber and J. A. Dumesic, Angew. 63 C. Hammond, D. Padovan, A. Al-Nayili, P. P. Wells,
Chem., Int. Ed., 2007, 46, 71647183. E. K. Gibson and N. Dimitratos, ChemCatChem, 2015, 7,
38 R. W. Nagorski and J. P. Richard, J. Am. Chem. Soc., 2001, 33223331.
123, 794802. 64 N. Rajabbeigi, A. I. Torres, C. M. Lew, B. Elyassi, L. Ren,
39 Y. Romn-Leshkov, M. Moliner, J. A. Labinger and Z. Wang, H. J. Cho, W. Fan, P. Daoutidis and
M. E. Davis, Angew. Chem., Int. Ed., 2010, 49, 89548957. M. Tsapatsis, Chem. Eng. Sci., 2014, 116, 235242.
40 M. Boronat, P. Concepcin, A. Corma, M. Renz and 65 S. Saravanamurugan, M. Paniagua, J. A. Melero and
S. Valencia, J. Catal., 2005, 234, 111118. A. Riisager, J. Am. Chem. Soc., 2013, 135, 52465249.
41 M. Boronat, P. Concepcin, A. Corma and M. Renz, Catal. 66 J. B. Binder, J. J. Blank, A. V. Cefali and R. T. Raines,
Today, 2007, 121, 3944. ChemSusChem, 2010, 3, 12681272.
42 N. Rai, S. Caratzoulas and D. G. Vlachos, ACS Catal., 2013, 67 V. Choudhary, A. B. Pinar, S. I. Sandler, D. G. Vlachos and
3, 22942298. R. F. Lobo, ACS Catal., 2011, 1, 17241728.
43 R. Gounder and M. E. Davis, AIChE J., 2013, 59, 3349 68 V. Choudhary, S. Caratzoulas and D. G. Vlachos,
3358. Carbohydr. Res., 2013, 368, 8995.
44 G. Yang, E. A. Pidko and E. J. M. Hensen, ChemSusChem, 69 M. Paniagua, S. Saravanamurugan, M. Melian-Rodriguez,
2013, 6, 16881696. J. A. Melero and A. Riisager, ChemSusChem, 2015, 8, 1088
45 S. K. Brand, J. A. Labinger and M. E. Davis, ChemCatChem, 1094.
2016, 8, 121124. 70 M. Wang, Y. Xia, L. Zhao, C. Song, L. Peng, X. Guo, N. Xue
46 J. R. Christianson, S. Caratzoulas and D. G. Vlachos, ACS and W. Ding, J. Catal., 2014, 319, 150154.
Catal., 2015, 5, 52565263. 71 J. Jow, G. L. Rorrer, M. C. Hawley and D. T. A. Lamport,
47 R. Bermejo-Deval, M. Orazov, R. Gounder, S. J. Hwang and Biomass, 1987, 14, 185194.
M. E. Davis, ACS Catal., 2014, 4, 22882297. 72 C. Moreau, R. Durand, S. Razigade, J. Duhamet,
48 R. Bermejo-Deval, R. Gounder and M. E. Davis, ACS Catal., P. Faugeras, P. Rivalier, P. Ros and G. Avignon, Appl.
2012, 2, 27052713. Catal., A, 1996, 145, 211224.
49 V. Choudhary, A. B. Pinar, R. F. Lobo, D. G. Vlachos and 73 K. Shimizu, R. Uozumi and A. Satsuma, Catal. Commun.,
S. I. Sandler, ChemSusChem, 2013, 6, 23692376. 2009, 10, 18491853.
View Article Online
74 V. V. Ordomsky, J. van der Schaaf, J. C. Schouten and 102 J. S. Kruger, V. Choudhary, V. Nikolakis and D. G. Vlachos,
T. A. Nijhuis, ChemSusChem, 2012, 5, 18121819. ACS Catal., 2013, 3, 12791291.
75 P. Rivalier, J. Duhamet, C. Moreau and R. Durand, Catal. 103 I. Jimnez-Morales, M. Moreno-Recio, J. Santamara-
Today, 1995, 24, 165171. Gonzlez, P. Maireles-Torres and A. Jimnez-Lpez, Appl.
76 C. Moreau, R. Durand, C. Pourcheron and S. Razigade, Catal., B, 2015, 164, 7076.
Ind. Crops Prod., 1994, 3, 8590. 104 Q. Xu, Z. Zhu, Y. Tian, J. Deng, J. Shi and Y. Fu,
77 V. V. Ordomsky, J. van der Schaaf, J. C. Schouten and BioResources, 2013, 9, 303315.
T. A. Nijhuis, J. Catal., 2012, 287, 6875. 105 I. Jimnez-Morales, J. Santamara-Gonzlez, A. Jimnez-

78 Y. Shi, X. Li, J. Hu, J. Lu, Y. Ma, Y. Zhang and Y. Tang, Lpez and P. Maireles-Torres, Fuel, 2014, 118, 265271.
J. Mater. Chem., 2011, 21, 1622316230. 106 C. Moreau, R. Durand, F. Alis, M. Cotillon, T. Frutz and
79 P. Dornath and W. Fan, Microporous Mesoporous Mater., M. A. Tholeyre, Ind. Crops Prod., 2000, 11, 237242.
2014, 191, 1017. 107 L. Zhou, Z. Liu, Y. Bai, T. Lu, X. Yang and J. Xu, J. Energy
80 A. N. Chermahini, F. Shahangi, H. A. Dabbagh and Chem., 2016, 25, 141145.
M. Saraji, RSC Adv., 2016, 6, 3380433810. 108 S. Lima, M. M. Antunes, A. Fernandes, M. Pillinger,
81 H. Hafizi, A. N. Chermahini, M. Saraji and M. F. Ribeiro and A. A. Valente, Molecules, 2010, 15, 3863
G. Mohammadnezhad, Chem. Eng. J., 2016, 294, 380388. 3877.
82 A. J. Crisci, M. H. Tucker, M. Y. Lee, S. G. Jang, 109 Y. Yang, X. Xiang, D. Tong, C. Hu and M. M. Abu-Omar,
J. A. Dumesic and S. L. Scott, ACS Catal., 2011, 1, 719728. Bioresour. Technol., 2012, 116, 302306.
83 M. H. Tucker, A. J. Crisci, B. N. Wigington, N. Phadke, 110 M. Tan, L. Zhao and Y. Zhang, Biomass Bioenergy, 2011,
R. Alamillo, J. Zhang, S. L. Scott and J. A. Dumesic, ACS 35, 13671370.
Catal., 2012, 2, 18651876. 111 J. J. Wang, Z. C. Tan, C. C. Zhu, G. Miao, L. Z. Kong and
84 X. Guo, Q. Cao, Y. Jiang, J. Guan, X. Wang and X. Mu, Y. H. Sun, Green Chem., 2016, 18, 452460.
Carbohydr. Res., 2012, 351, 3541. 112 H. Abou-Yousef and E. B. Hassan, J. Ind. Eng. Chem., 2014,
85 E. Kl and S. Ylmaz, Ind. Eng. Chem. Res., 2015, 54, 20, 19521957.
52205225. 113 K. Y. Nandiwale, N. D. Galande, P. Thakur, S. D. Sawant,
86 B. Karimi and H. M. Mirzaei, RSC Adv., 2013, 3, 2065520661. V. P. Zambre and V. V. Bokade, ACS Sustainable Chem.
87 N. Lucas, G. Kokate, A. Nagpure and S. Chilukuri, Eng., 2014, 2, 19281932.
Microporous Mesoporous Mater., 2013, 181, 3846. 114 R. Otomo, T. Tatsumi and T. Yokoi, Catal. Sci. Technol.,
88 T. D. Swift, H. Nguyen, Z. Erdman, J. S. Kruger, V. Nikolakis 2015, 5, 40014007.
and D. G. Vlachos, J. Catal., 2016, 333, 149161. 115 J. S. Kruger, V. Nikolakis and D. G. Vlachos, Appl. Catal.,
89 E. Nikolla, Y. Romn-Leshkov, M. Moliner and A, 2014, 469, 116123.
M. E. Davis, ACS Catal., 2011, 1, 408410. 116 D. W. Gardner, J. Huo, T. C. Ho, R. L. Johnson,
90 J. M. R. Gallo, D. M. Alonso, M. A. Mellmer and B. H. Shanks and J. P. Tessonnier, ACS Catal., 2015, 5,
J. A. Dumesic, Green Chem., 2013, 15, 8590. 44184422.
91 L. Hu, Z. Wu, J. Xu, Y. Sun, L. Lin and S. Liu, Chem. Eng. 117 H. Li, J. Ren, L. Zhong, R. Sun and L. Liang, Bioresour.
J., 2014, 244, 137144. Technol., 2015, 176, 242248.
92 R. Otomo, T. Yokoi, J. N. Kondo and T. Tatsumi, Appl. 118 L. R. Ferreira, S. Lima, P. Neves, M. M. Antunes,
Catal., A, 2014, 470, 318326. S. M. Rocha, M. Pillinger, I. Portugal and A. A. Valente,
93 L. Li, J. Ding, J. G. Jiang, Z. Zhu and P. Wu, Chin. J. Catal., Chem. Eng. J., 2013, 215216, 772783.
2015, 36, 820828. 119 C. Moreau, R. Durand, D. Peyron, J. Duhamet and
94 R. Otomo, T. Yokoi and T. Tatsumi, ChemCatChem, 2015, P. Rivalier, Ind. Crops Prod., 1998, 7, 9599.
7, 41804187. 120 S. B. Kim, S. J. You, Y. T. Kim, S. M. Lee, H. Lee, K. Park
95 H. Jadhav, C. M. Pedersen, T. Slling and M. Bols, and E. D. Park, Korean J. Chem. Eng., 2011, 28, 710716.
ChemSusChem, 2011, 4, 10491051. 121 P. S. Metkar, E. J. Till, D. R. Corbin, C. J. Pereira,
96 H. Jadhav, E. Taarning, C. M. Pedersen and M. Bols, K. W. Hutchenson and S. K. Sengupta, Green Chem., 2015,
Tetrahedron Lett., 2012, 53, 983985. 17, 14531466.
97 M. Ohara, A. Takagaki, S. Nishimura and K. Ebitani, Appl. 122 J. M. R. Gallo, D. M. Alonso, M. A. Mellmer, J. H. Yeap,
Catal., A, 2010, 383, 149155. H. C. Wong and J. A. Dumesic, Top. Catal., 2013, 56,
98 M. Kaldstrom, N. Kumar, T. Heikkila, M. Tiitta, T. Salmi 17751781.
and D. Y. Murzin, ChemCatChem, 2010, 2, 539546. 123 C. Aellig, D. Scholz, P. Y. Dapsens, C. Mondelli and
99 M. Kaldstrom, N. Kumar, T. Heikkila, M. Tiitta, T. Salmi J. Prez-Ramrez, Catal. Sci. Technol., 2015, 5, 142149.
and D. Y. Murzin, Biomass Bioenergy, 2011, 35, 19671976. 124 S. Lima, A. Fernandes, M. M. Antunes, M. Pillinger,
100 M. Kaldstrom, N. Kumar, T. Heikkila and D. Y. Murzin, F. Ribeiro and A. A. Valente, Catal. Lett., 2010, 135, 4147.
Appl. Catal., A, 2011, 397, 1321. 125 M. M. Antunes, S. Lima, A. Fernandes, M. Pillinger,
101 K. Lourvanij and G. L. Rorrer, Ind. Eng. Chem. Res., 1993, M. F. Ribeiro and A. A. Valente, Appl. Catal., A, 2012,
32, 1119. 417418, 243252.
View Article Online
126 S. Lima, M. Pillinger and A. A. Valente, Catal. Commun., 152 B. Liu and Z. Zhang, RSC Adv., 2013, 3, 1231312319.
2008, 9, 21442148. 153 H. Li, K. S. Govind, R. Kotni, S. Saravanamurugan,
127 S. J. You and E. D. Park, Microporous Mesoporous Mater., A. Riisager and S. Yang, Energy Convers. Manage., 2014,
2014, 186, 121129. 88, 12451251.
128 R. ONeill, M. N. Ahmad, L. Vanoye and F. Aiouache, Ind. 154 H. Wang, T. Deng, Y. Wang, Y. Qi, X. Hou and Y. Zhu,
Eng. Chem. Res., 2009, 48, 43004306. Bioresour. Technol., 2013, 136, 394400.
129 S. Lima, M. M. Antunes, A. Fernandes, M. Pillinger, 155 Y. Yang, M. M. Abu-Omar and C. Hu, Appl. Energy, 2012,
M. F. Ribeiro and A. A. Valente, Appl. Catal., A, 2010, 388, 99, 8084.

141148. 156 T. Flannelly, S. Dooley and J. J. Leahy, Energy Fuels, 2015,
130 R. Weingarten, G. A. Tompsett, W. C. Conner Jr. and 29, 75547565.
G. W. Huber, J. Catal., 2011, 279, 174182. 157 E. R. Sacia, M. Balakrishnan and A. T. Bell, J. Catal., 2014,
131 J. Zhang, J. Zhuang, L. Lin, S. Liu and Z. Zhang, Biomass 313, 7079.
Bioenergy, 2012, 39, 7377. 158 P. Che, F. Lu, J. Zhang, Y. Huang, X. Nie, J. Gao and J. Xu,
132 S. Kaiprommarat, S. Kongparakul, P. Reubroycharoen, Bioresour. Technol., 2012, 119, 433436.
G. Guan and C. Samart, Fuel, 2016, 174, 189196. 159 J. Yu, S. Zhu, P. J. Dauenhauer, H. J. Cho, W. Fan and
133 D. Hua, P. Li, Y. Wu, Y. Chen, M. Yang, J. Dang, Q. Xie, R. J. Gorte, Catal. Sci. Technol., 2016, 6, 57295736.
J. Liu and X. Sun, J. Ind. Eng. Chem., 2013, 19, 13951399. 160 A. Liu, Z. Zhang, Z. Fang, B. Liu and K. Huang, J. Ind. Eng.
134 I. Agirrezabal-Telleria, J. Requies, M. B. Gemez and Chem., 2014, 20, 19771984.
P. L. Arias, Appl. Catal., B, 2012, 115116, 169178. 161 P. Lanzafame, D. M. Temi, S. Perathoner, G. Centi,
135 E. I. Grbz, J. M. R. Gallo, D. M. Alonso, S. G. Wettstein, A. Macario, A. Aloise and G. Giordano, Catal. Today, 2011,
W. Y. Lim and J. A. Dumesic, Angew. Chem., Int. Ed., 2013, 175, 435441.
52, 12701274. 162 B. Liu, Z. Zhang, K. Huang and Z. Fang, Fuel, 2013, 113,
136 P. L. Dhepe and R. Sahu, Green Chem., 2010, 12, 2153 625631.
2156. 163 K. Barbera, P. Lanzafame, A. Pistone, S. Millesi,
137 H. Gao, H. Liu, B. Pang, G. Yu, J. Du, Y. Zhang, H. Wang G. Malandrino, A. Gulino, S. Perathoner and G. Centi,
and X. Mu, Bioresour. Technol., 2014, 172, 453456. J. Catal., 2015, 323, 1932.
138 J. M. R. Gallo, D. M. Alonso, M. A. Mellmer, J. H. Yeap, 164 C. M. Lew, N. Rajabbeigi and M. Tsapatsis, Ind. Eng.
H. C. Wong and J. A. Dumesic, Top. Catal., 2013, 56, Chem. Res., 2012, 51, 53645366.
17751781. 165 H. Li, S. Saravanamurugan, S. Yang and A. Riisager, Green
139 H. Zhang, X. Liu, M. Lu, X. Hu, L. Lu, X. Tian and J. Ji, Chem., 2016, 18, 726734.
Bioresour. Technol., 2014, 169, 800803. 166 J. Liu, Y. Tang, K. Wu, C. Bi and Q. Cui, Carbohydr. Res.,
140 P. Bhaumik and P. L. Dhepe, RSC Adv., 2014, 4, 26215 2012, 350, 2024.
26221. 167 E. Salminen, N. Kumar, P. Virtanen, M. Tenho, P. Maki-
141 J. Cui, J. Tan, T. Deng, X. Cui, Y. Zhu and Y. Li, Green Arvela and J. P. Mikkola, Top. Catal., 2013, 56, 765769.
Chem., 2016, 18, 16191624. 168 F. Yang, S. Zhang, Z. C. Zhang, J. Mao, S. Li, J. Yin and
142 H. Li, P. S. Bhadury, A. Riisager and S. Yang, Catal. Sci. J. Zhou, Catal. Sci. Technol., 2015, 5, 46024612.
Technol., 2014, 4, 41384168. 169 O. Casanova, S. Iborra and A. Corma, J. Catal., 2010, 275,
143 G. Y. Jeong, A. K. Singh, S. Sharma, K. W. Gyak, 236242.
R. A. Maurya and D. P. Kim, NPG Asia Mater., 2015, 7, e173. 170 K. S. Arias, S. I. Al-Resayes, M. J. Climent, A. Corma and
144 H. Wang, T. Deng, Y. Wang, X. Cui, Y. Qi, X. Mu, X. Hou S. Iborra, ChemSusChem, 2013, 6, 123131.
and Y. Zhu, Green Chem., 2013, 15, 23792383. 171 P. Neves, M. M. Antunes, P. A. Russo, J. P. Abrantes, S. Lima,
145 G. A. Kraus and T. Guney, Green Chem., 2012, 14, 1593 A. Fernandes, M. Pillinger, S. M. Rocha, M. F. Ribeiro and
1596. A. A. Valente, Green Chem., 2013, 15, 33673376.
146 M. M. Antunes, P. A. Russo, P. V. Wiper, J. M. Veiga, 172 W. Deng, Q. Zhang and Y. Wang, Catal. Today, 2014, 234,
M. Pillinger, L. Mafra, D. V. Evtuguin, N. Pinna and 3141.
A. A. Valente, ChemSusChem, 2014, 7, 804812. 173 H. Li, Z. Fang, R. L. Smith Jr. and S. Yang, Prog. Energy
147 B. Liu, Z. Zhang and K. Deng, Ind. Eng. Chem. Res., 2012, Combust. Sci, 2016, 55, 98194.
51, 1533115336. 174 J. Reichert, B. Brunner, A. Jess, P. Wasserscheid and
148 B. Liu, Z. Zhang and K. Huang, Cellulose, 2013, 20, 2081 J. Albert, Energy Environ. Sci., 2015, 8, 29852990.
2089. 175 R. Weingarten, Y. T. Kim, G. A. Tompsett, A. Fernndez,
149 S. Wang, Z. Zhang, B. Liu and J. Li, Catal. Sci. Technol., K. S. Han, E. W. Hagaman, W. C. Conner Jr., J. A. Dumesic
2013, 3, 21042112. and G. W. Huber, J. Catal., 2013, 304, 123134.
150 Z. Zhang, Y. Wang, Z. Fang and B. Liu, ChemPlusChem, 176 D. W. Rackemann and W. O. S. Doherty, Biofuels, Bioprod.
2014, 79, 233240. Biorefin., 2011, 5, 198214.
151 A. Liu, B. Liu, Y. Wang, R. Ren and Z. Zhang, Fuel, 2014, 177 F. D. Pileidis and M. M. Titirici, ChemSusChem, 2016, 9,
117, 6873. 562582.
View Article Online
178 W. Luo, P. C. A. Bruijnincx and B. M. Weckhuysen, 203 D. An, A. Ye, W. Deng, Q. Zhang and Y. Wang, Chem.
J. Catal., 2014, 320, 3341. Eur. J., 2012, 18, 29382947.
179 A. Mukherjee, M. J. Dumont and V. Raghavan, Biomass 204 C. Paris, M. Moliner and A. Corma, Green Chem., 2013, 15,
Bioenergy, 2015, 72, 143183. 21012109.
180 K. Yan, C. Jarvis, J. Gu and Y. Yan, Renewable Sustainable 205 Z. Zhang and K. Deng, ACS Catal., 2015, 5, 65296544.
Energy Rev., 2015, 51, 986997. 206 H. Li, Q. Zhang, P. S. Bhadury and S. Yang, Curr. Org.
181 V. Choudhary, S. H. Mushrif, C. Ho, A. Anderko, Chem., 2014, 18, 547597.
V. Nikolakis, N. S. Marinkovic, A. I. Frenkel, S. I. Sandler 207 J. Zhang, J. Li, Y. Tang, L. Lin and M. Long, Carbohydr.
and D. G. Vlachos, J. Am. Chem. Soc., 2013, 135, 39974006. Polym., 2015, 130, 420428.
182 N. Yaaini, N. A. S. Amin and S. Endud, Microporous 208 J. Cai, H. Ma, J. Zhang, Q. Song, Z. Du, Y. Huang and
Mesoporous Mater., 2013, 171, 1423. J. Xu, Chem. Eur. J., 2013, 19, 1421514223.
183 N. Yaaini, N. A. S. Amin and M. Asmadi, Bioresour. 209 I. Sdaba, Y. Y. Gorbanev, S. Kegns, S. S. R. Putluru,
Technol., 2012, 116, 5865. R. W. Berg and A. Riisager, ChemCatChem, 2013, 5, 284293.
184 N. A. S. Ramli and N. A. S. Amin, Appl. Catal., B, 2015, 210 K. S. Arias, M. J. Climent, A. Corma and S. Iborra,
163, 487498. ChemSusChem, 2014, 7, 210220.
185 N. A. S. Ramli and N. A. S. Amin, Energy Convers. Manage., 211 X. Liu, J. Xiao, H. Ding, W. Zhong, Q. Xu, S. Su and
2015, 95, 1019. D. Yin, Chem. Eng. J., 2016, 283, 13151321.
186 W. Zeng, D. Cheng, H. Zhang, F. Chen and X. Zhan, Reac. 212 N. Mittal, G. M. Nisola, J. G. Seo, S. P. Lee and
Kinet., Mech. Catal., 2010, 100, 377384. W. J. Chung, J. Mol. Catal. A: Chem., 2015, 404405, 106
187 Y. Liu, L. Lin, X. Sui, J. Zhuang and C. Pang, Appl. Mech. 114.
Mater., 2013, 260261, 12061209. 213 Z. Z. Yang, J. Deng, T. Pan, Q. X. Guo and Y. Fu, Green
188 K. Y. Nandiwale and V. V. Bokade, Environ. Prog. Chem., 2012, 14, 29862989.
Sustainable Energy, 2015, 34, 795801. 214 N. Alonso-Fagndez, I. Agirrezabal-Telleria, P. L. Arias,
189 K. Y. Nandiwale, S. K. Sonar, P. S. Niphadkar, P. N. Joshi, J. L. G. Fierro, R. Mariscal and M. L. Granados, RSC Adv.,
S. S. Deshpande, V. S. Patil and V. V. Bokade, Appl. Catal., 2014, 4, 5496054972.
A, 2013, 460461, 9098. 215 X. Li and Y. Zhang, Green Chem., 2016, 18, 643647.
190 D. R. Fernandes, A. S. Rocha, E. F. Mai, C. J. A. Mota and 216 Z. Du, J. Ma, F. Wang, J. Liu and J. Xu, Green Chem., 2011,
V. Teixeira da Silva, Appl. Catal., A, 2012, 425426, 199 13, 554557.
204. 217 A. Chatzidimitriou and J. Q. Bond, Green Chem., 2015, 17,
191 G. Z. Xu, C. Chang, W. N. Zhu, B. Li, X. J. Ma and 43674376.
F. G. Du, Chem. Pap., 2013, 67, 13551363. 218 B. Saha and M. M. Abu-Omar, ChemSusChem, 2015, 8,
192 S. Saravanamurugan and A. Riisager, ChemCatChem, 11331142.
2013, 5, 17541757. 219 L. Hu, L. Lin and S. Liu, Ind. Eng. Chem. Res., 2014, 53,
193 R. Le Van Mao, Q. Zhao, G. Dima and D. Petraccone, 99699978.
Catal. Lett., 2011, 141, 271276. 220 Y. Zhu, X. Kong, H. Zheng, G. Ding, Y. Zhu and Y. W. Li,
194 S. Saravanamurugan and A. Riisager, Catal. Commun., Catal. Sci. Technol., 2015, 5, 42084217.
2012, 17, 7175. 221 M. Chatterjee, T. Ishizaka and H. Kawanami, Green Chem.,
195 L. Zhou, H. Zhao, L. Cui, Y. Bai, J. Bian, T. Lu, Y. Su and 2014, 16, 47344739.
X. Yang, Catal. Commun., 2015, 71, 7478. 222 Y. Romn-Leshkov, C. J. Barrett, Z. Y. Liu and
196 H. Lin, J. Strull, Y. Liu, Z. Karmiol, K. Plank, G. Miller, J. A. Dumesic, Nature, 2007, 447, 982985.
Z. Guo and L. Yang, Energy Environ. Sci., 2012, 5, 9773 223 M. Chidambaram and A. T. Bell, Green Chem., 2010, 12,
9777. 12531262.
197 X. Jin, M. Zhao, J. Shen, W. Yan, L. He, P. S. Thapa, 224 J. Zhang, L. Lin and S. Liu, Energy Fuels, 2012, 26, 4560
S. Ren, B. Subramaniam and R. V. Chaudhari, J. Catal., 4567.
2015, 330, 323329. 225 J. M. R. Gallo, D. M. Alonso, M. A. Mellmer and
198 S. Alonso, M. Rendueles and M. Daz, Bioresour. Technol., J. A. Dumesic, Green Chem., 2013, 15, 8590.
2015, 196, 314323. 226 A. S. Nagpure, N. Lucas and S. V. Chilukuri, ACS
199 F. Zhao, H. Li, Y. Jiang, X. Wang and X. Mu, Green Chem., Sustainable Chem. Eng., 2015, 3, 29092916.
2014, 16, 25582565. 227 J. Lessard, J. F. Morin, J. F. Wehrung, D. Magnin and
200 C. Ma, W. Xue, J. Li, W. Xing and Z. Hao, Green Chem., E. Chornet, Top. Catal., 2010, 53, 12311234.
2013, 15, 10351041. 228 W. Yu, Y. Tang, L. Mo, P. Chen, H. Lou and X. Zheng,
201 P. Qi, S. Chen, J. Chen, J. Zheng, X. Zheng and Y. Yuan, Catal. Commun., 2011, 13, 3539.
ACS Catal., 2015, 5, 26592670. 229 J. M. Nadgeri, N. Hiyoshi, A. Yamaguchi, O. Sato and
202 P. N. R. Vennestrm, E. Taarning, C. H. Christensen, M. Shirai, Appl. Catal., A, 2014, 470, 215220.
S. Pedersen, J. D. Grunwaldt and J. M. Woodley, 230 D. M. Alonso, S. G. Wettstein and J. A. Dumesic, Green
ChemCatChem, 2010, 2, 943945. Chem., 2013, 15, 584595.
View Article Online
231 K. Yan, Y. Yang, J. Chai and Y. Lu, Appl. Catal., B, 2015, 256 J. Luo, J. Yu, R. J. Gorte, E. Mahmoud, D. G. Vlachos and
179, 292304. M. A. Smith, Catal. Sci. Technol., 2014, 4, 30743081.
232 W. Luo, U. Deka, A. M. Beale, E. R. H. van Eck, 257 Q. Cao, W. Liang, J. Guan, L. Wang, Q. Qu, X. Zhang,
P. C. A. Bruijnincx and B. M. Weckhuysen, J. Catal., 2013, X. Wang and X. Mu, Appl. Catal., A, 2014, 481, 4953.
301, 175186. 258 J. Jae, E. Mahmoud, R. F. Lobo and D. G. Vlachos,
233 K. Kon, W. Onodera and K. Shimizu, Catal. Sci. Technol., ChemCatChem, 2014, 6, 508513.
2014, 4, 32273234. 259 J. D. Lewis, S. V. de Vyver, A. J. Crisci, W. R. Gunther,
234 P. Sun, G. Gao, Z. Zhao, C. Xia and F. Li, ACS Catal., 2014, V. K. Michaelis, R. G. Grin and Y. Romn-Leshkov,
4, 41364142. ChemSusChem, 2014, 7, 22552265.
235 A. B. Kellicutt, R. Salary, O. A. Abdelrahman and 260 P. S. Chum and K. W. Swogger, Prog. Polym. Sci., 2008, 33,
J. Q. Bond, Catal. Sci. Technol., 2014, 4, 22672279. 797819.
236 T. Mizugaki, K. Togo, Z. Maeno, T. Mitsudome, 261 D. M. Alonso, J. Q. Bond and J. A. Dumesic, Green Chem.,
K. Jitsukawa and K. Kaneda, ACS Sustainable Chem. Eng., 2010, 12, 14931513.
2016, 4, 682685. 262 G. W. Huber, S. Iborra and A. Corma, Chem. Rev., 2006,
237 Z. Li, Y. Jiang, X. Tang, M. Zuo, X. Zeng, Y. Sun and L. Lin, 106, 40444098.
RSC Adv., 2015, 5, 82978300. 263 Y. Kato and Y. Sekine, Catal. Lett., 2013, 143, 418423.
238 Y. Zhao, Y. Fu and Q. X. Guo, Bioresour. Technol., 2012, 264 S. Ogo, T. Nishio, H. Sekine, A. Onda and Y. Sekine, Fuel
114, 740744. Process. Technol., 2016, 141, 123129.
239 M. J. Gilkey and B. Xu, ACS Catal., 2016, 6, 14201436. 265 T. Jiang, Q. Zhang, T. J. Wang, Q. Zhang and L. L. Ma,
240 R. S. Assary, L. A. Curtiss and J. A. Dumesic, ACS Catal., Energy Convers. Manage., 2012, 59, 5865.
2013, 3, 26942704. 266 A. Cho, A. Takagaki, R. Kikuchi and S. T. Oyama, Top.
241 X. Tang, X. Zeng, Z. Li, L. Hu, Y. Sun, S. Liu, T. Lei and Catal., 2015, 58, 219231.
L. Lin, Renewable Sustainable Energy Rev., 2014, 40, 608 267 K. Chen, M. Tamura, Z. Yuan, Y. Nakagawa and
620. K. Tomishige, ChemSusChem, 2013, 6, 613621.
242 F. Liguori, C. Moreno-Marrodan and P. Barbaro, ACS 268 S. Liu, M. Tamura, Y. Nakagawa and K. Tomishige, ACS
Catal., 2015, 5, 18821894. Sustainable Chem. Eng., 2014, 2, 18191827.
243 J. Wang, S. Jaenicke and G. K. Chuah, RSC Adv., 2014, 4, 269 G. W. Huber, J. N. Chheda, C. J. Barrett and J. A. Dumesic,
1348113489. Science, 2005, 308, 14461450.
244 S. S. Enumula, V. R. B. Gurram, M. Kondeboina, 270 K. Murata, Y. Liu, M. Inaba and I. Takahara, Catal. Lett.,
D. R. Burri and S. R. R. Kamaraju, RSC Adv., 2016, 6, 2010, 140, 813.
2023020239. 271 S. Li, N. Li, G. Li, L. Li, A. Wang, Y. Cong, X. Wang and
245 L. Bui, H. Luo, W. R. Gunther and Y. Romn-Leshkov, T. Zhang, Green Chem., 2015, 17, 36443652.
Angew. Chem., 2013, 125, 81808183. 272 A. D. Sutton, F. D. Waldie, R. Wu, M. Schlaf, L. A. Pete
246 M. M. Antunes, S. Lima, P. Neves, A. L. Magalhes, Silks III and J. C. Gordon, Nat. Chem., 2013, 5, 428432.
E. Fazio, F. Neri, M. T. Pereira, A. F. Silva, C. M. Silva, 273 W. Shen, G. A. Tompsett, K. D. Hammond, R. Xing,
S. M. Rocha, M. Pillinger, A. Urakawa and A. A. Valente, F. Dogan, C. P. Grey, W. C. Conner Jr., S. M. Auerbach and
Appl. Catal., B, 2016, 182, 485503. G. W. Huber, Appl. Catal., A, 2011, 392, 5768.
247 S. Zhu, Y. Xue, J. Guo, Y. Cen, J. Wang and W. Fan, ACS 274 O. Kikhtyanin, V. Kelbichov, D. Vitvarov, M. Kubu and
Catal., 2016, 6, 20352042. D. Kubicka, Catal. Today, 2014, 227, 154162.
248 R. Mariscal, P. Maireles-Torres, M. Ojeda, I. Sdaba and 275 O. Kikhtyanin, D. Kubicka and J. Cejka, Catal. Today,
M. L. Granados, Energy Environ. Sci., 2016, 9, 11441189. 2015, 243, 158162.
249 I. Guzmn, A. Heras, M. B. Gemez, A. Iriondo, 276 O. Kikhtyanin, P. Chlubn, T. Jindrov and D. Kubika,
J. F. Cambra and J. Requies, Ind. Eng. Chem. Res., 2016, Dalton Trans., 2014, 43, 1062810641.
55, 51395144. 277 R. Ramos, Z. Tiler, O. Kikhtyanin and D. Kubika, Catal.
250 M. A. Mellmer, J. M. R. Gallo, D. M. Alonso and Sci. Technol., 2016, 6, 18291841.
J. A. Dumesic, ACS Catal., 2015, 5, 33543359. 278 A. Bohre, B. Saha and M. M. Abu-Omar, ChemSusChem,
251 J. P. Lange, W. D. van de Graaf and R. J. Haan, 2015, 8, 40224029.
ChemSusChem, 2009, 2, 437441. 279 J. C. Serrano-Ruiz, A. Pineda, A. M. Balu, R. Luque,
252 G. Zhao, L. Hu, Y. Sun, X. Zeng and L. Lin, BioResources, J. M. Campelo, A. A. Romero and J. M. Ramos-Fernndez,
2014, 9, 26342644. Catal. Today, 2012, 195, 162168.
253 G. Wang, Z. Zhang and L. Song, Green Chem., 2014, 16, 280 A. Corma, O. de la Torre and M. Renz, Energy Environ. Sci.,
14361443. 2012, 5, 63286344.
254 P. Neves, S. Lima, M. Pillinger, S. M. Rocha, J. Rocha and 281 M. Balakrishnan, E. R. Sacia and A. T. Bell, ChemSusChem,
A. A. Valente, Catal. Today, 2013, 218219, 7684. 2014, 7, 10781085.
255 B. Chamnankid, C. Ratanatawanate and K. Faungnawakij, 282 H. Li, S. Saravanamurugan, S. Yang and A. Riisager, ACS
Chem. Eng. J., 2014, 258, 341347. Sustainable Chem. Eng., 2015, 3, 32743280.
View Article Online
283 A. Corma, O. de la Torre and M. Renz, ChemSusChem, 305 L. D. Borges, N. N. Moura, A. A. Costa, P. R. S. Braga,
2011, 4, 15741577. J. A. Dias, S. C. L. Dias, J. L. de Macedo and G. F. Ghesti,
284 A. Corma, O. de la Torre, M. Renz and N. Villandier, Appl. Catal., A, 2013, 450, 114119.
Angew. Chem., 2011, 123, 24232426. 306 H. Wu, J. Zhang, Q. Wei, J. Zheng and J. Zhang, Fuel
285 M. H. Chvez-Sifontes, M. E. Domine and S. Valencia, Process. Technol., 2013, 109, 1318.
Catal. Today, 2015, 257, 305317. 307 S. S. Vieira, Z. M. Magriotis, N. A. V. Santos, A. A. Saczk,
286 B. L. Wegenhart, L. Yang, S. C. Kwan, R. Harris, C. E. Hori and P. A. Arroyo, Bioresour. Technol., 2013, 133,
H. I. Kenttamaa and M. M. Abu-Omar, ChemSusChem, 248255.

2014, 7, 27422747. 308 D. Wang, B. Ma, B. Wang, C. Zhao and P. Wu, Chem.
287 Y. T. Cheng and G. W. Huber, Green Chem., 2012, 14, Commun., 2015, 51, 1510215105.
31143125. 309 T. Li, J. Cheng, R. Huang, J. Zhou and K. Cen, Bioresour.
288 P. T. M. Do, J. R. McAtee, D. A. Watson and R. F. Lobo, Technol., 2015, 197, 289294.
ACS Catal., 2013, 3, 4146. 310 L. G. Possato, R. N. Diniz, T. Garetto, S. H. Pulcinelli,
289 C. L. Williams, C. C. Chang, P. Do, N. Nikbin, C. V. Santilli and L. Martins, J. Catal., 2013, 300, 102112.
S. Caratzoulas, D. G. Vlachos, R. F. Lobo, W. Fan and 311 M. M. Diallo, J. Mijoin, S. Laforge and Y. Pouilloux, Catal.
P. J. Dauenhauer, ACS Catal., 2012, 2, 935939. Commun., 2016, 79, 5862.
290 Z. Lin, M. Ierapetritou and V. Nikolakis, AIChE J., 2013, 312 M. D. Gonzlez, Y. Cesteros and P. Salagre, Appl. Catal., A,
59, 20792087. 2013, 450, 178188.
291 J. J. Pacheco and M. E. Davis, Proc. Natl. Acad. Sci. U. S. A., 313 Y. T. Algoufi and B. H. Hameed, Fuel Process. Technol.,
2014, 111, 83638367. 2014, 126, 511.
292 D. Wang, C. M. Osmundsen, E. Taarning and 314 H. Li, R. Kotni, Q. Zhang, S. Saravanamurugan and
J. A. Dumesic, ChemCatChem, 2013, 5, 20442050. S. Yang, Mini-Rev. Org. Chem., 2015, 12, 162177.
293 S. K. Green, R. E. Patet, N. Nikbin, C. L. Williams, 315 J. M. Rubio-Caballero, S. Saravanamurugan, P. Maireles-
C. C. Chang, J. Yu, R. J. Gorte, S. Caratzoulas, W. Fan, Torres and A. Riisager, Catal. Today, 2014, 234, 233236.
D. G. Vlachos and P. J. Dauenhauer, Appl. Catal., B, 2016, 316 A. P. Djukic-Vukovic, L. V. Mojovic, B. M. Jokic,
180, 487496. S. B. Nikolic and J. D. Pejin, Bioresour. Technol., 2013, 135,
294 J. Yu, S. Zhu, P. J. Dauenhauer, H. J. Cho, W. Fan and 454458.
R. J. Gorte, Catal. Sci. Technol., 2016, DOI: 10.1039/ 317 A. Y. Kovalevsky, L. Hanson, S. Z. Fisher, M. Mustyakimov,
C6CY00501B. S. A. Mason, V. T. Forsyth, M. P. Blakeley, D. A. Keen,
295 C. C. Chang, H. J. Cho, J. Yu, R. J. Gorte, J. Gulbinski, T. Wagner, H. L. Carrell, A. K. Katz, J. P. Glusker and
P. Dauenhauer and W. Fan, Green Chem., 2016, 18, 1368 P. Langan, Structure, 2010, 18, 688699.
1376. 318 J. Jae, G. A. Tompsett, A. J. Foster, K. D. Hammond,
296 C. C. Chang, S. K. Green, C. L. Williams, P. J. Dauenhauer S. M. Auerbach, R. F. Lobo and G. W. Huber, J. Catal.,
and W. Fan, Green Chem., 2014, 16, 585588. 2011, 279, 257268.
297 Y. P. Li, M. Head-Gordon and A. T. Bell, J. Phys. Chem. C, 319 R. J. White, A. Fischer, C. Goebel and A. Thomas, J. Am.
2014, 118, 2209022095. Chem. Soc., 2014, 136, 27152718.
298 N. Nikbin, P. T. Do, S. Caratzoulas, R. F. Lobo, 320 A. G. Machoke, A. M. Beltrn, A. Inayat, B. Winter,
P. J. Dauenhauer and D. G. Vlachos, J. Catal., 2013, 297, T. Weissenberger, N. Kruse, R. Gttel, E. Spiecker and
3543. W. Schwieger, Adv. Mater., 2015, 27, 10661070.
299 R. E. Patet, N. Nikbin, C. L. Williams, S. K. Green, 321 J. V. Aelst, D. Verboekend, A. Philippaerts, N. Nuttens,
C. C. Chang, W. Fan, S. Caratzoulas, P. J. Dauenhauer and M. Kurttepeli, E. Gobechiya, M. Haouas, S. P. Sree,
D. G. Vlachos, ACS Catal., 2015, 5, 23672375. J. F. M. Denayer, J. A. Martens, C. E. A. Kirschhock,
300 E. Mahmoud, J. Yu, R. J. Gorte and R. F. Lobo, ACS Catal., F. Taulelle, S. Bals, G. V. Baron, P. A. Jacobs and B. F. Sels,
2015, 5, 69466955. Adv. Funct. Mater., 2015, 25, 71307144.
301 J. J. Pacheco, J. A. Labinger, A. L. Sessions and 322 R. Martnez-Franco, C. Paris, M. E. Martnez-Armero,
M. E. Davis, ACS Catal., 2015, 5, 59045913. C. Martnez, M. Moliner and A. Corma, Chem. Sci., 2016,
302 R. Xiong, S. I. Sandler, D. G. Vlachos and 7, 102108.
P. J. Dauenhauer, Green Chem., 2014, 16, 40864091. 323 M. Ojeda, A. Grau-Atienza, R. Campos, A. A. Romero,
303 T. W. Kim, S. Y. Kim, J. C. Kim, Y. Kim, R. Ryoo and E. Serrano, J. M. Marinas, J. G. Martinez and R. Luque,
C. U. Kim, Appl. Catal., B, 2016, 185, 100109. ChemSusChem, 2015, 8, 13281333.
304 S. S. Vieira, Z. M. Magriotis, M. Filipa Ribeiro, I. Graa, 324 A. Grau-Atienza, R. Campos, E. Serrano, M. Ojeda,
A. Fernandes, J. M. F. M. Lopes, S. M. Coelho, A. A. Romero, J. Garcia-Martinez and R. Luque,
N. A. V. Santos and A. A. Saczk, Microporous Mesoporous ChemCatChem, 2014, 6, 35303539.
Mater., 2015, 201, 160168. 325 R. Luque, Curr. Green Chem., 2015, 2, 9095.

Lewis e Bronsted

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Lewis e Bronsted

Hochgeladen von

Copyright:

Verfügbare Formate

Green Chemistry

View Article Online

Zeolite and zeotype-catalysed transformations of

1. Introduction cesses.3 In the case of pentose and hexose carbohydrates, a

Critical Review Green Chemistry

Table 1 Properties of some representative medium-pore, large-pore, and mesoporous zeolites12

Medium-pore FER 8 MR 0.35 0.48 0.14 0.10 360

Green Chemistry Critical Review

10 wt% H-Y(110) 0.087 90% 5.21 L mol1 min1x

5704 | Green Chem., 2016, 18, 57015735

This journal is The Royal Society of Chemistry 2016

Green Chemistry Critical Review

valuable products. As an improved method, hydrophobic

activity in the hydrolysis of cellulose to glucose (ca. 12% yield)

lower Si/Al molar ratios were more ecient in the catalytic

also demonstrated that the shape-selectivity eect of micro-

was capable of limiting the polymerization of in situ generated

to mesoporous SBA-15 supported sulphated zirconia

glycosidic bond cleavage33 (Table 3, entry 3). However, metal ions

might result in zeolite deactivation.34 To increase the acid

strength and the amount of acid sites, a sulfonated hierarchi-

range of cascade processes: treating H-USY (Si/Al = 3.2) with

3-mercaptopropyltrimethoxysilane onto the surface of the hier-

archical H-USY zeolite followed by oxidation of thiols to sulfo-

exhibited a high eciency in the hydrolysis of hemicellulose

to TRS (78.0% yield) at 140 C for 9 h, especially in the hydro-

Cellulose (10 g L1)

43.7% conversion) to glucose (22.4% & 15.1% yield) at 180 C

after 6 h, respectively (Table 3, entry 4). These findings pointed

against further degradation as compared to glucose).36

2.2. Zeolite-catalysed sugar isomerization

tose isomerization is being deemed as one of the vital inter-

mediate steps to produce biofuels and value-added chemicals

from lignocellulose, being the largest biorefinery process in

the industrial production of high-fructose corn syrup.37 Both a

100 wt% H-USY-meso

base-catalysed proton transfer and a metal center-mediated

111 wt% H-beta(75)

intramolecular hydride shift have been reported to be respon-

100 wt% H-USY

sible for the isomerisation of glucose to fructose (Scheme 4).38

Sn-beta prepared by full incorporation of tin into the frame-

strated to be highly ecient for the isomerization reaction,

from SnCl4 were found to be completely inactive (Table 4,

Critical Review Green Chemistry

Scheme 3 The route to synthesize H-USY-meso-SO3H.35

Green Chemistry Critical Review

Table 4 Aldoseketose isomerizations catalysed by zeolites

2.0 mol% SnO2 + silica/hydrothermal gel (10 wt%) Fructose 5% <1%

5708 | Green Chem., 2016, 18, 57015735

This journal is The Royal Society of Chemistry 2016

Green Chemistry Critical Review

(1) 69%, (2) 69%

(1) 54%, (2) 55%

(1) 29%, (2) 29%

Scheme 5 Sn sites in (a) isomorphously substituted and (b) partially

Ti-beta with varying Si/Ti contents at 100 C after 2 h, respect-

Sn-beta showed great potential in the industrial production

while the synthetic routes generally involved long crystalliza-

dezincated CIT-6 in anhydrous dichloromethane at room

2-propanol,61 isomorphous substitution of dealuminated

method63 have been developed to shorten the preparation

Sn-beta zeolites (Table 4, entry 6). However, the Sn-beta catalyst

deactivated in water ranging from minutes to hours, wherein