Catalysis Today 189 (2012) 227

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

The past, present and future of heterogeneous catalysis

Ioana Fechete a , Ye Wang b , Jacques C. Vdrine c,
a
Laboratoire des Matriaux, Surfaces et Procds pour la Catalyse, CNRS UMR 7515, Universit de Strasbourg, 25 rue Becquerel, F-67087 Strasbourg, France
b
State Key Laboratory of Physical Chemistry of Solid Surfaces and National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry
and Chemical Engineering, Xiamen University, Xiamen 361005, PR China
c
Laboratoire de Ractivit de Surface, CNRS UMR 7197, Universit Pierre et Marie Curie, 4 Place Jussieu, F- 75252 Paris, France

a r t i c l e i n f o a b s t r a c t

Article history: This review highlights key catalytic discoveries and the main industrial catalytic processes over the last
Received 18 January 2012 300 years that involved commodities, ne chemicals, petrochemicals, petroleum transformation for fuels
Received in revised form 4 April 2012 and energy supply, emission control, and so forth. In the past, discoveries have often followed events such
Accepted 5 April 2012
as wars or embargos, whereas the current driving forces of studies, researches and then discoveries aim
Available online 10 May 2012
at a better understanding of catalytic processes, at reducing the costs of raw materials and processes, at
developing new catalytic materials and at addressing environmental issues. This review focuses on the
Keywords:
history of many catalytic industrial processes, environmental issues, catalytic materials, especially their
Heterogeneous catalysis
History
expected catalytic properties, on catalyst characterisation by physical methods and development of in situ
Industrial realisations conditions, i.e., characterisation under actual working conditions with reactants and products analyzed
Future on-line. Emphasis is also placed on high selectivity in catalytic reactions and the major challenges for the
Challenges future, such as environmental issues, energy supply, pollution control for vehicles and industrial plants,
New materials air/VOCs/water purication, hydrogen sources and carbon dioxide storage/up grading, transformation of
Chemicals biomass as a promising source of raw materials, and catalytic water splitting perspectives.
Energy This review is a survey of heterogeneous catalysis and is not comprehensive but leads to the conclusion
Environment
that, although many catalysts and catalytic processes have already been discovered and developed over
the past century, many opportunities nevertheless exist for new developments, new processes and new
catalytic materials. It follows that substantial challenges exist for the younger generation of researchers
and engineers, as emphasized at the end of the manuscript.
2012 Elsevier B.V. All rights reserved.

1. Introduction Our aim in this manuscript is to highlight the major catalysis-

Catalysis is an important eld in chemistry, with some 90% of
chemical processes involving catalysts in at least one of their steps
[1]. At present, because of environmental issues, catalysis appears
to be even more important than before and to constitute one of
the major sources of improvements in our society [2,3]. A survey
of U.S. industries revealed that the annual revenue from chemical
and fuel production topped all other industrial sectors. The survey
also showed that more than 60% of the 63 major products and 90%
of the 34 process innovations from 1930 to 1980 have involved
catalysis, which illustrates the critical role of this eld in the fuel
and chemical industries.
This review is intended to present some historical background
of catalysis and the major challenges that this eld has faced in the
last half century and that it still must face in the future. This review
is focused only on heterogeneous catalysis.
Corresponding author. Tel.: +33 144275514.
E-mail address: jacques.vedrine@upmc.fr (J.C. Vdrine).
related discoveries and processes that have been developed over
the past three centuries. The history of catalysis and its contribu-
tion to chemical industries has already been widely described in
the literature, e.g. [46]. We intended to review some historically
signicant steps in the development of catalysis and catalytic pro-
cesses. Without discussing ancient beer or wine fermentation, it is
interesting to recall some old processes, as summarized in Table 1
[713].
Some of these processes have been developed in response to
driving forces designated as pullers like the expected Chilean
embargo on saltpeter as a nitrate source, which motivated Haber
and Bosch to develop a process for the xation of atmospheric
nitrogen in ammonia synthesis (1909). Similarly, the need for a
more energetic gasoline inspired racing driver and French mechan-
ical engineer Eugne Houdry to develop the oil (hydrocarbon) acid
cracking process (1930), and catalytic reformation and alkylation
(1940), which have allowed the Allied forces to access a powerful
fuel for air planes during World War II.
More recently, driving forces (pullers) have changed and now
correspond more to a market-driven strategy, in which simpler

0920-5861/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2012.04.003
 I. Fechete et al. / Catalysis Today 189 (2012) 227 3

Table 1
Historical aspects in heterogeneous catalysis [713].

Catalytic process Catalyst Main author Year

Sulfuric acid Lead chamber Roebuck 1746

Dehydration of alcohols Acid Priestley 1778
Esterication of organic acids Acid Scheele 1782
Dehydrogenation of alcohols (ethanol) Metal Van Marum 1796
Oxidation of alcohol Pt black Priestley & Dbereiner 1810
Decomposition of H2 O2 and NH3 Metals Thnard 1813
Hydrolysis of starch to glucose Acid Kirchoff 1814
Combustion Pt Davy 1817
Decomposition NH3 Fe > Cu > Ag > Au > Pt Dulong 1823
Oxidation Pt Fusinieri 1824
Oxidation SO2 to SO3 (contact process) Pt Phillips 1831
Denition of catalysis Berzelius 1836
Oxidation of NH3 to nitric acid Pt Kuhlmann 1838
HCl + O2 Cl2 Cu Deacon 1875
Esterication of acid Acid Bertholet 1879
Hydrolysis of esters Acid Bertholet 1879
Sulfuric acid V2 O5 1875
Friedel-Crafts reactions Lewis acids (AlCl3 ) Friedel & Crafts 1877
Nitric acid synthesis Pt gauzes 1904
NH3 synthesis from N2 and H2 under high pressure Fe Haber 1909
Hydrogenation Ni Sabatier 1912
Active site concept Michaelis 1913
Theory of adsorption Langmuir 1915
Industrial process of NH3 synthesis under pressure Fe Haber 1918
CO + H2 CH3 OH ZnO-chromia BASF 1923
CO + H2 hydrocarbons Fe, Co Fischer & Tropsch 1923
Contact catalysis theory Taylor 1925
Hydrogenation vegetable oils Ni Raney 1926
Catalytic cracking of petroleum Acid Houdry 1930
Synthesis gas Bergius & Bosch 1931
Alkylation reaction for gasoline fuel Acid Ipatieff & Pines 1940
Synthetic zeolites Barrer & Breck 1946
Exhaust gas treatment General Motors & Ford 1976

and less-capital-incentive processes and the use of cheaper feed
stocks are preferred. Since the end of the twentieth century, soci-
etal concerns have also become an important modern motivation,
with intensive research being devoted to convert by-products to
useful products and to treat all kinds of wastes for the preserva-
tion and protection of the environment. More stringent legislation
has been established which has led to research on new catalytic
materials and more efcient processes. More specically, with
respect to environmental issues, hydrodesulfurization started in
the 1960s as an important method for the removal of sulfur from
fuels. Hydrodesulfurization has resulted in a considerable reduc-
tion in global emissions of sulfur oxides, while creating increased
demand for the selective methane reaction (SMR) for H2 produc-
tion; auto emission control catalysts developed in 1974 (oxidation),
1978 (three-way), and in the 1990s (Pd three-way); the selec-
tive catalytic reduction of NOx by NH3 or N2 H4 (SCR) for power
plants in 1980 using V, W, and Ti oxides extruded into mono-
lith forms [14]; ozone emission control catalysts developed by
Engelhard (now BASF); the replacement of CFCs by HCFCs for the
reduction of topospheric ozone concentration (ozone holes), the
catalytic destruction of volatile organic compounds from the con-
sumer products industry; the production of foods and chemicals;
the development of diesel oxidation exhaust catalysts in 1990 using
cerium salt as additive; a variety of solutions that use metal oxides
for catalytic decomposition of N2 O (which resulted in an 81% reduc-
tion of all N2 O emissions from the world adipic acid plants); the
development of PtRh-alkali NOx storage catalysts; the develop-
ment of the Toyota Motor in 1994; the development of diesel
particulate elimination catalysts in 2003; the development of urea
SCR for NOx emissions control in vehicles in 2004; the development
of NOx removal in FCC regenerator units in 2007, and so forth.
New studies have also appeared in the past two or three decades
under driving forces considered as pushers for the development
of a molecular-level understanding of catalyst function, sur-
face sensitive spectroscopies, in situ/operando characterisation
techniques, scientic computing, quantum chemistry, molecular
modelling, thermodynamics and kinetics, reaction and reactor
modelling, high-throughput catalyst screening and testing, and
so forth. Signicant improvements have been made in all of these
domains, and further developments should continue in the future.
2. The catalysts
Since ancient times, the development and use of materials have
been one of the basic objectives of our world. Eras, the Stone Age,
the Bronze Age, and the Iron Age, have been named after the funda-
mental material used by mankind to construct their tools. Materials
science is the modern activity that provides the raw material for this
endless need, demanded by the progress in all elds of industry and
technology, for new materials for the development of society.
The International Union of Pure and Applied Chemistry (IUPAC)
has dened a catalyst as a substance that increases the rate of
a reaction without modifying the overall standard Gibbs energy
change in the reaction [15]. The chemical process of increasing
the reaction rate is called catalysis, and the catalyst is both a reac-
tant and a product of the reaction, i.e., the catalyst is restored after
each catalytic act. Furthermore, the catalyst does not inuence the
thermodynamical equilibrium composition after the cessation of
the reaction.
More efcient catalytic processes require improvements in the
catalytic activity and selectivity. Both aspects can be improved
by the tailored design of catalytic materials with the desired
structures and the desired dispersion of active sites. Materials
such as zeolites, AlPO, SAPO, mesoporous materials, PILC, MOFs,
etc. offer such possibilities in this regard, with controlled large and
accessible surface areas of the catalysts but without standalone
4 I. Fechete et al. / Catalysis Today 189 (2012) 227
ne particles. Moreover, one of the most important applica-
tions of these novel porous solid catalysts is the replacement
of environmentally hazardous, corrosive, difcult-to-separate-
and-dispose-of homogeneous catalysts (viz. mineral and Lewis
acids, organic and inorganic bases and toxic metallic compounds)
employed in the liquid-phase synthesis of bulk and ne chemicals
(vide infra) [16]. There are many families of solids catalysts like
metals, oxides, suldes, carbons, etc. as bulk materials or supported
on a more or less catalytically active support like silica, alumina,
zirconia, titania, ceria, carbons, etc. These materials may possess
specic chemical properties, such as acid-base or redox or dehy-
drogenating or hydrogenating or oxidizing, and physical properties
like porosity, high surface area, attrition resistance, thermal and/or
electrical conductivity, etc. The largest family corresponds to
oxides whatever zeolites, clays, mesoporous materials, mixed
oxides as catalysts or as supports. Among them porous materials
present some fascinating properties, which are described below.
2.1. Zeolites
In the petrochemistry and organic synthesis elds, zeolites have
played a major role in the twentieth century. Zeolites are inorganic
crystalline aluminosilicates which structures consist of a three-
dimensional arrangement of TO4 tetrahedra (where T is usually
Si4+ and Al3+ tetrahedrally coordinated atoms) assembled together
through the sharing of oxygen atoms to form subunits, which repeat
to form an innite lattice [17], consisting of three-dimensional,
fourfold interconnected TO4 tetrahedra linked via TOT bridges.
The TOT angles are ideally 140150 and rarely over 180 . The
existence of Al in a tetrahedrally coordinated Si structure leaves a
negative framework charge, which requires the existence of com-
pensating cations, located in the porous system.
Consequently, an interesting feature of zeolites is the versatility
of their structures that arises from a large number of modica-
tion procedures which also tailor their catalytic properties. The
catalytic activity is associated with the presence of active centres
in the framework. Such centres may be acid, their strength and
number (Brnsted, Lewis) being adjusted in a controlled manner
either during synthesis by isomorphous replacement of the central
Si atom in tetrahedral sites in the zeolite lattice, by for example
trivalent elements like Al, B, Fe, Cr, Sb, As, or Ga, and tetravalent
elements like Ge, Ti, Zr, or Hf; and/or post-synthesis including the
steam procedure, chemical vapor deposition, ion exchange of inter-
stitial cations, reduction of exchanged metal ions to a lower valence
state.
A distinction has been made between small-, medium- and
large-pore zeolites. In the case of small-pore zeolites, such as zeo-
lite A, eight SiO4 tetrahedra form a ten member ring (10MR) with
a diameter a 0.41 nm and in the case of large-pore zeolites, such
as Y-zeolite (Fig. 1), a cavity with a diameter of 0.74 nm is formed
Fig. 1. Framework of Faujasite (FAU) zeolite (Y or X-Type Si/Al = 2.5 or 1).
by twelve SiO4 tetrahedra. The medium-pore zeolites, such as pen-
tasil zeolites, contain a ten member ring with an ellipsoidal tubular
diameter of 0.55 0.56 nm. The system of channels and cavities in
these molecular sieves produces solids with very high surface areas
and pore volumes, which are capable of adsorbing large amounts
of hydrocarbons.
Zeolites can be used as sorbents and as catalysts in some cat-
alytic processes. The major breakthrough in zeolite catalysts arose
from the uid catalytic cracking (FCC) process for oil transforma-
tion to fuels and chemicals. The addition of zeolites (FAU and MFI)
to acid clays and silicaalumina cracking catalysts in the mid-1960s
resulted in a drastic increase in conversion and gasoline yields as
well as in lower quantities of coke and dry gas [18]. The new cata-
lysts gave gasolines with lower octane numbers, primarily because
of their lower olenicity [1921]. The rst octane-enhancing FCC
catalysts were introduced by catalyst manufacturers in USA in the
mid-1970s. Octane FCC catalysts consist of two major components,
and the zeolites can be used to boost gasoline octane. Chester et al.
[22] have reported that, in addition to MFI (ZSM-5), different mem-
bers of the MFI family of zeolites (MEL, ZSM-12, ZSM-23, ZSM-35,
ZSM-38) have octane-boosting abilities. Zeolites beta (BEA) [23]
and offretite (OFF) [24] have been reported to produce higher gaso-
line octane numbers than conventional Y (FAU) zeolites and can be
used as octane-boosting additives.
Major milestones in this domain are summarized below:
R. Milton (Union Carbide in 1950s), D. Breck, R. Barrer and E. Flani-
gen developed commercially viable routes to various zeolites and
MeAPOs.
J. Rabo, working at Union Carbide, applied the use of zeolites to
petroleum rening (isomerization, 1959), whereas C. Plank and E.
Rosinski of Mobil Oil applied zeolites to catalytic cracking (1962)
of heavy oil fractions.
P. Weisz and V. Frilette of Mobil Oil developed the concept (1960)
of shape-selective catalysts, and W. Haag applied shape selectiv-
ity to the production of aromatics.
G. Kerr of Mobil Oil discovered high silica zeolites in 1967 (ZSM-5,
subsequently designated as MFI) and the rst large scale commer-
cial cracking trial was run in 1983.
W. R. Grace discovered the steaming of Y zeolite to produce ultra-
stable Y (USY) zeolite in 1969.
Mobil Oil developed the siliceous mesoporous-type materials
designated as MCM, HMS, and so forth in the late 1990s.
M. Taramasso, G. Perego, and B. Notari discovered TS-1 (titanium
silicalite-1 with the MFI structure), a selective oxidation catalyst
for the epoxidation of olens, at ENI-SNAM Progetti in 1983.
UOP/HYDRO (1995) developed SAPO-34, a silicoaluminophos-
phate molecular sieve applied for methanol to olens (MTO
process).
Another fascinating property of zeolites arises from their molec-
ular size porous network, which allows certain reactants to enter
and products to easily leave the pores or cavities, or to remain
trapped, or to leave the pores with difculty if they are too bulky.
This concept, of shape selectivity, pioneered by Mobil scientists
[25], has been developed to explain reactions that do not obey
the classical laws of thermodynamics and that are strongly inu-
enced by the size of the pores or cavities relative to the size of
the reactant or product molecules. Matching the size and cong-
uration of reacting molecules, intermediates and products with
the geometry and tortuosity of the zeolite channel/cavity system
provides the basis for controlled shape selectivity. Diffusion and
shape-selectivity catalysis in zeolites have been reviewed in sev-
eral publications [2628]. However, the shape selectivity in zeolites
can manifest itself through: reactant selectivity, product selec-
tivity, transition-state selectivity, molecular trafc control, etc.
 I. Fechete et al. / Catalysis Today 189 (2012) 227 5

Fig. 2. Illustration of a molecule in a pore and shape selectivity in dealuminated mordenite zeolite.

The reactant selectivity, results in the exclusion of molecules too
large to diffuse into the zeolite pores; a simple example is the dehy-
dration of alcohols. Over the narrow-pore zeolite (CaA), n-butanol
is dehydrated, and isobutanol is not. Conversely, as expected, isobu-
tanol is more readily dehydrated than n-butanol over NaX (which
has wider pores). The former result is readily explained because
both forms can enter NaX, but the bulkier isobutanol is excluded
from CaA product selectivity. In addition to size exclusion, entrance
to zeolite crystals may hinder when the unfavorable orientation of
a reactant is caused by electrostatic effects. In this case, the align-
ment of a zeolitic electrostatic eld (perpendicular to the plane of
the window) and a molecule dipole may restrict entry by electro-
static repulsion, which allows only small molecules formed during
the reaction to diffuse out of the zeolite pores. For example, in the
alkylation of toluene by methanol over H-MFI, yields of p-xylene are
enhanced because the diffusivity of p-xylene is much greater than
that of o- and m-xylenes (vide infra). Even if the primary product of
alkylation is not rich in p-xylene, its more rapid exit from the zeo-
lite allows further isomerization of o- and m-xylenes and results in
increased yields of the p-isomer. Restricted transition-state selec-
tivity occurs when certain reactions are prevented because the
corresponding transition state would require more space than is
available in the pores. Molecular trafc control [29] occurs in zeo-
lites with two types of channel systems. The relationship between
the length of the molecules and the size of the zeolite cage as well
as variations in molecular oscillations [30] also affect zeolite shape
selectivity. In addition to geometric factors, shape selectivity can
be due to electrostatic effects [31] which result from the interaction
between the electric eld at the pore mouth and the dipole moment
of the reactant molecule. Such an interaction can favour or inhibit
the diffusion of the reactant molecule into the zeolite.
The shape selectivity of zeolites can be modied by ion
exchange, dealumination, changes in the framework Si/Al ratio, or
by any modication that affects the pore size or geometry [3245].
The shape selectivity of a zeolite is often characterized by its con-
straint index, which is the ratio of the cracking rate constants for
n-hexane and 3-methylpentane [46]. Large-pore zeolites have con-
straint indices less than 1; medium-pore zeolites have constraint
indices between 1 and 12; small-pore zeolites have constraint
indices higher than 12.
The shape selectivity phenomenon is illustrated in
Fig. 2 for the synthesis of 4,4 -di-isopropyl-biphenyl and 2,

Fig. 3. Principe of connement A and anti-connement C, dimensionality [4749].

6 I. Fechete et al. / Catalysis Today 189 (2012) 227
Fig. 4. Variations of van der Waals energy W and the force between a spheri-
cal molecule (radius d) and a spherical micropore (radius a) vs. curvature (s = d/a)
[4749].
6-di-isopropyl-naphthalene compounds that are intermediates
for polyesters or liquid crystals, by alkylation of naphthalene by
propylene on dealuminated mordenite. The narrow size of the
mordenite (10-membered ring) zeolite favours the formation
of the less-bulky para isomer of the di-isopropyl naphthalene,
followed by the ortho isomer relative to the meta isomer, as is
expected from the thermodynamic equilibrium of approximately
25:25:50, respectively.
Another aspect of zeolite properties is the connement effect, as
developed by E. Derouane [4749], which simply considers van der
Waals forces, i.e., neglecting Pauli repulsive forces, as illustrated in
Fig. 3.
Derouane et al. have proposed the following equation of the
van der Waals energy (W) of a spherical molecule of van der
Waals radius (d) conned in a spherical micropore of a radius (a):
W(s) = (C/4d3 ) (1 s/2)3 with C = h /2, where = e2 /m2 is the
polarizability of an atom seen as a punctual dipolar momentum,
uctuating at a frequency , and s is the surface curvature. This
latter parameter, s = d/a, can vary between 0 and 1, depending on
the relative sizes of the conned molecule and the micropore. The
van der Waals force is F = (3C/4d4 )[(1 s)/(1 s/2)4 . The extreme
cases correspond to a at surface (s = 0) and to a molecule with the
same size as the pore (s = 1); this latter case has been referred to by
Derouane et al. as a oating molecule which should diffuse very
rapidly because its motion is not hindered by its interaction with
the wall, as compensated by the van der Waals force. It also follows
from the van der Waals equation that Ws=1 = 8Ws=0 , which means
that, according to this model, the adsorption energy due to the van
der Waals connement factor within the zeolite pore can be up to
8 times greater than that corresponding to a at surface. The type
of variation of W versus s can be found in Fig. 4.
As a consequence, molecules within the pores may interact more
or less strongly with their environment depending on their size
relative to that of the pores, e.g., 90 kJ mol1 for p-xylene in SAPO-
11. They can also contract themselves to enter the pores, whereas
the zeolitic lattice may also slightly contract upon adsorption, as
shown by XRD [50].
At present, more than 300 different types of zeolite frameworks
are known, with only a few (BEA, FAU, MFI, MOR, SAPO-34) having
important industrial catalytic applications; however, many more
Fig. 5. Adipic acid processes using the old process (left) and the new process (right).
have applications for the manufacture of ne chemicals. Some stud-
ies are described below to exemplify some of their properties.
The synthesis of adipic acid is an interesting example. The clas-
sical process (annual production of 0.7 Mt, off-gas concentration of
2540%) uses nitric acid as an oxidizing agent with the formation of
N2 O, which has to be re-oxidized further to nitric acid and which is
an important greenhouse gas. A catalytic process was subsequently
developed for N2 O decomposition. However, a process that uses a
Fe-MFI catalyst, which is able to oxidize benzene directly to phenol
[5158] has been discovered at the Boreskov Institute of Catalysis
in Novosibirsk, RU, and a process was developed with Monsanto
Co in a spin-off company called Solutia, but does not appear to be
commercialised, according to our knowledge. This process is much
more environmentally friendly because N2 O is used instead of oxy-
gen to oxidize benzene to phenol. The scheme for this process is
presented in Fig. 5.
Another interesting example is FriedelCrafts reactions on
acidic zeolites. The rst mention of acylation related to the later
Al2 Cl6 method of Friedel and Crafts appeared in 1873 in a prelim-
inary communication by Grucarevic and Merz [59], as reported by
Olah in a historical review about FriedelCrafts chemistry [60,61]
on the metal-catalyzed acylation of aromatic compounds. The
FriedelCrafts acylation reaction consists primarily of the produc-
tion of an aromatic ketone by reaction of an aromatic substrate
with an acyl component in the presence of a catalyst. Many papers
and books have been published and numerous patents have been
granted on this topic, as summarized in a recent review [62]. Inter-
ests in electrophilic acylation studies and in the optimization of
preparative processes were spurred by the considerable practical
value of the aromatic ketone products, which constitute important
intermediates in the pharmaceutical, fragrance, avour, dye and
agrochemical industries. The electrophilic acylations are catalyzed
by Lewis acids (such as ZnCl2 , AlCl3 , FeCl3 , SnCl4 , and TiCl4 ) or pro-
tic acids (such as HF or H2 SO4 ). However, the use of metal halides
causes problems associated with the hydrolysis of the complex,
which results in the loss of catalyst and the generation of large vol-
umes of corrosive waste streams. Great efforts have thus been made
to achieve the goal of making the Lewis acid using heterogeneous
solid catalysts, in particular acid zeolites. A detailed description of
FriedelCrafts reactions for arenes (e.g., benzene, toluene, xylenes),
aromatic ethers (e.g., anisole) with acetic anhydride or other acy-
lating agents on zeolites and on clays, metal oxides, and so forth is
given in Ref. [60]. The roles of shape selectivity and deactivation by
the products and hydrophobicity versus hydrophilicity for zeolites
have been emphasized. For example, acylation of anisole or toluene
with acetic anhydride was performed on BEA zeolite at 90 C, to
replace the classical AlCl3 catalyst which led to many salts in the
efuents, corrosion problems, low selectivity and a short lifetime
 I. Fechete et al. / Catalysis Today 189 (2012) 227
Fig. 6. Scheme of the effect of the adsorption rate of reactants on the reactivity,
depending on the polarity of the reactants versus that of the zeolite [63,64].
of the catalyst, as already discussed. At variance, the use of H-BEA
zeolite resulted in 6 times fewer steps, 10 times less solid and 100
times less aqueous discharge, primarily because the hydrophilicity
versus the hydrophobicity of the zeolite, for more or less polar reac-
tants, which allowed the reactant molecules to enter more or less
easily within the pores while the solvent molecules were prevented
from entering. The relative adsorption rates of reactant molecules
within the pores regulate the stoichiometry of the reaction inside
the pores, i.e., depending on the relative adsorption rates of the
reactants, and one has thus to choose a stoichiometry in the liq-
uid medium surrounding the zeolite particles that is different from
that expected from the reaction. For example, a 20:1 stoichiom-
etry might be chosen for a 1:1 reaction for toluene (non polar
reactant) acylation by acetic anhydride (polar reactant). This helds
true particularly for gas phase reactions with solid zeolites, but also
for liquid phase reactions on solid zeolites, which is an important
aspect of ne chemical reactions in zeolites, as schematized in Fig. 6.
Another interesting example relates to the production of
para-xylene (p-xylene). Xylenes, especially the para isomers, are
compounds in high demand in the organic chemical industry
for the production of polyethyleneterephtalate (PET) bres, plas-
tics, resins, lms, and so forth because p-xylene is a chemical
intermediate in these processes. The main source of xylenes is
the C8 cut produced by catalytic reformation and steam cracking
[6568]. However, a convenient way to increase p-xylene produc-
tion is to transform less-valuable C7 and C9 methylaromatics by
catalytic alkylation of toluene with methanol followed by dispro-
portionation and transalkylation with trimethylbenzene. Catalysts
for these reactions range from common Brnsted acids (H2 SO4 ,
Fig. 7. Historical view of functions of coordination polymers reported from 1990 to 2005. Structures of 3-D porous coordination polymers, [Cu(SiF6 )(4,4 -bpy)2 ]n (1, left),
[Zn4 O(BDC)3 ]n (2, right), and the 1-D oxygen array are listed [124].
7
H3 PO4 , HF) to Lewis acids (metal halides) and further to solid
acids (Al2 O3 , SiO2 Al2 O3 , zeolites). It must be noted, that as a con-
sequence of environmental concerns, the zeolite-based catalysts
currently play a signicant role in the production of alkyl aromat-
ics. Studies reported in the literature describe a wide variety of
zeolitic catalysts that are active in the alkylation of toluene with
methanol [36,38,39,6978], toluene disproportionation [7984],
transalkylation of toluenetrimethylbenzene [8589], and xylene
isomerization [9092]. In general, the catalytic properties (espe-
cially the selectivity) and the surface deactivation of zeolites
during these reactions strongly depend on the nature, number
and strength of the acid centres in the catalyst. For example, the
catalysts with strongly acidic sites have been reported to be less
selective and easily deactivated by coke [93]. Modication of the
acidity and structure of zeolites (with large and medium pores)
can be considered a way to reduce by-reactions and improve
the selectivity to p-xylene. High activity and predominant shape
selectivity was observed on ZSM-5 [9497], and the reaction is
effective above 450 C. The high p-selectivity of modied ZSM5
has been attributed to the restricted diffusion inside the chan-
nels, i.e., the p-xylene, which rapidly diffuses out of the narrow
channels, is preferentially produced. Large-pore zeolites with 12-
member channel systems, particularly mordenite [98,99], have also
emerged as shape-selective catalysts. Although the size of pores is
important for the para selectivity, this phenomenon was observed
on large-pore zeolites when the acidity was modied by isomor-
phous substitution or ionic exchange with rare-earth metals. The
formation of p-xylene was also investigated on the zeolite MCM-
22 [100102], discovered by Mobil, which has a unique crystal
structure [103]. It is composed of two channel systems, both of
which are accessed through a 10-membered ring (10-MR) window.
One system consists of two-dimensional, sinusoidal channels with
10-MR opening, whereas the other contains large supercages that
consist of 10-MR and 12-MR openings with an inner free space
of 0.71 0.71 1.82 nm. These channel systems are independent
of each other, and molecules cannot pass from one to the other
within the same crystallite. The catalytic properties, such as the
shape selectivity of MCM-22, have been shown to be intermedi-
ate between 10-MR and 12-MR zeolites in various reactions. The
results for MCM-22 highlight the inuence of cages and windows
on the shape selectivity. In such cases, the experimentally observed
shape selectivity was attributed to variations in the Si/Al ratio and
the nature of the extra framework cations. Toluene disproportion-
ation over dealuminated MCM-22 was found to occur mainly in
the supercages of MCM-22 but not in the 10-MR channels of MCM-
22 at the investigated temperatures. The fraction of p-xylene was
higher than its equilibrium value and increased further by the
8 I. Fechete et al. / Catalysis Today 189 (2012) 227

Fig. 8. Self-assembly of polymetallic cluster nodes (left; top: m4-oxo {M4 O(-CO2 )6 }; bottom: {M2 (-CO2 )4 } paddlewheel) and organic linkers (right) yielding metalorganic
frameworks (center) [125,126].

dealumination. p-Xylene formed within the supercages as a pri-
mary product would be isomerized to o- and m-xylene by the acid
sites not only on the external surface but also within the 10-MR
channels. The improvement in the para selectivity by dealumina-
tion resulted from the suppression of isomerization activity; the
dealumination treatment probably eliminated framework Al atoms
predominantly on the external surface and inside the 10-MR chan-
nels compared with those inside the supercages [102].
Many other ne-chemical reactions have been developed by
Corma, Garcia and their teams [2] at ITQ, Universidad de Valencia,
Spain. These reactions pertain largely to the eld of applications of
zeolites in catalysis, which has previously been limited to petro-
chemical reactions.
2.2. AlPO4 -n SAPO4 -n, Me-AlPO4 -n, Me-APSO4 -n
In the early 1980s, the discovery of a new family of molecu-
lar sieves was reported by researchers at Union Carbide. Wilson
et al. [104,105] described the microporous aluminophosphates pre-
pared hydrothermally from alumina, phosphoric acid and an amine
or quaternary ammonium salt as organic templates. The product
composition for these materials is xRAl2 O3 1.0 0.2 P2 O5 yH2 O,
where R is an organic template located in the intracrystalline
pore system. The crystallized materials consist of alternating AlO2
and PO2 tetrahedra joined together into electrovalently neutral,
three-dimensional frameworks whose structure depends upon the
preparation conditions. These frameworks contain no Al O Al
or P O P bonds. The AlPO4 -5 structure consists of 4- and 6-
membered rings joined together to form the unidimensional
cylindrical channels of 12-membered rings with a free diame-
ter of approximately 0.8 nm [106,107,50,108,109]. The porosity
of the structures described by Union Carbide researchers varies
from very small pores (0.3 nm) to relatively large pores (0.8 nm).
Because AlPO4 frameworks are neutral, they have no ion-exchange
capacity. They exhibit good thermal and hydrothermal stability
and have weakly acidic catalytic properties. The absence of strong
acidity limits the application of these materials in cracking catal-
ysis. By isomorphic substitution of a series of elements into the
AlPO4 framework, a new generation of crystalline molecular sieves
was prepared [110]. The elements include framework cationic
species that range from monovalent to pentavalent, such as Li,
Be, B, Mg, Si, Ga, Ge, As, Ti, Mn, Fe, Co, and Zn. The addition of
silicon to the aluminum and phosphorous framework elements
results in silicoaluminophosphate (SAPO) molecular sieves [111].
The SAPO structures are mildly hydrophilic and have low-to-
moderate acidity, depending upon the silicon concentration and

Fig. 9. MOFs structures: Left: MIL-53, metal terephtalate (with Al, Cr, Fe ou V), which captures hydrogen into the framework formed of tunnels. Centre and right: MIL-100,
whose octahedra, constituted by chromates (CrO6 ), organise in tetrahedra and form cavities of diameter 23 nm as observed by electron microscopy from [127].
 I. Fechete et al. / Catalysis Today 189 (2012) 227 9

the structure type. According to Martens [112], even the highly

siliceous SAPOs have a lower catalytic activity as compared with
zeolites, such USY. SAPO-37 is very active cracking catalyst [113].
Several patents describe the use of SAPO-5, SAPO-11, SAPO-37 and
SAPO-40 in octane FCC catalysts [114]. The isomorphic substitution
of metal ions into AlPO4 frameworks results in metal aluminophos-
phates (MeAPO), whereas the isomorphic substitution of metal
ions into SAPOs results in metal silicoaluminophosphate frame-
works (MeAPSOs). Their properties are similar to those of the
parent molecular sieves. The thermal and hydrothermal stability
of MeAPSO is somewhat lower than that of AlPO4 and SAPO molec-
ular sieves. MeAPSOs exhibit weak to strong acidity, depending on
the metal type and the framework structure.

2.3. Pillared interlayer clays (PILCs)

Pillared interlayered clays (PILCs) have been studied since

the late 1970s as microporous materials with larger pore size
(0.42.0 nm, but less uniform) and more tunable compositions
than those of zeolites [115117]. PILCs were identied as good
candidates for heterogeneous catalysis because their pore size
distribution is quite broad and is still largely in the micro-
porous range [2]. The parent clay materials are composed of
charge-balancing cations sandwiched between negatively charged
aluminosilicate sheets. PILCs are prepared by swelling the clay
sheets, ion exchanging the cations with [AlO4 Al12 (OH)24 (H2 O)]7+
aluminum polyoxocations, and calcining the material to create alu-
minum oxide pillars within the clay sheets. The result is a highly
porous structure with a large intracrystalline surface area suit-
able for molecular sieving, adsorption and catalysis [118]. PILC-like
materials, termed PCHs (porous clay heterostructures) have been
prepared using surfactant templating within the clay sheets [119].
The PCHs have controllable, uniform pore sizes of 1.42.2 nm and
retain the sheet-like characteristics of the original clay material.
Fig. 10. MOF: MIL-101 metal terphthalate with cages of 3.2 nm [128].
Descriptions of the structures and porosities of several MOFs are
illustrated in Figs. 911 for better comprehensiveness of their spe-
cic properties. According to Fig. 11, some MOFs may expand upon
adsorption (breathing motion) or be distorted, which may result
in different catalytic and adsorptive properties [130135]. Desorp-
tion may be slow without pumping; this property was suggested
by Ferey et al. to be used for the slow delivery of a drug into the
blood stream when inoculated to a sick person, e.g., for diabetes
[127].
For a catalytic point of view one can distinguish three aspects of
MOFs properties related to: (1) framework atoms or ions activity,
(2) encapsulation of active species and (3) post synthesis modica-
tion/functionalisation. Fig. 12 shows the relative sizes of different
zeolites and MOFs compared to organic molecules. It is clear that big

2.4. Layered double hydroxides (LDHs)

Layered double hydroxides (LDHs), also known as hydrotalcite-

like compounds, are ionic lamellar compounds that consist of
positively charged hydroxide sheets with their interlayers lled
with anions and water molecules. Their structure is linked to
that of the natural mineral brucite, Mg(OH)2 [120,121]. The most
common group of LDHs can be represented by the general for-
mula [M2+ 1x M3+ x (OH)2 ] [An x/n mH2 O], where M2+ and M3+ are
di- and tri-valent metal cations that occupy octahedral positions
within the host layers of hydroxide sheets, and An is an interlayer
anion that compensates for the charge on the layers. Positive charge
on the host layers arises from isomorphous replacement of a frac-
tion of the divalent cations with trivalent cations. The combination
of Mg and Al has been studied most frequently, with a variety of
Mg:Al ratios and interlayer anions.

2.5. Metal organic frameworks (MOFs)

The metalorganic frameworks, designated MOFs, are new

materials that were discovered approximately 40 years ago by poly-
mer scientists. The rapid proliferation of papers in the literature
started only approximately 20 years ago [122,123]. Their synthesis
corresponds to the reaction of organic and inorganic groups, such
as arsenates, silicates, sulfates, phosphates, phosphonates, etc. This
reaction builds up three-dimensional frameworks formed of inor-
ganic and organic moieties linked by strong bonds. The organic
part is variable in nature, length and amount of space occupied
Fig. 11. Schematic behavior observed upon adsorption, desorption of guest
because it includes more- or less-branched carboxylic acids, amino molecules (a) induced pores (b) breathing pore; (c) pores exchanging guest with
complexes, etc. The history of MOFs is schematized in Figs. 7 and 8. deformation, (d) annealing pores [129].
10 I. Fechete et al. / Catalysis Today 189 (2012) 227

Table 2
Comparison of MOFs with zeolites for some properties relevant to catalysis [131].

Properties Zeolites MOFs

Lewis acidity High Low to medium

Brnsted acidity
Surface area
Pore volume
Thermal stability
Chemical stabilility
Diffusion
Basicity
Metal site density
Framework defects
Active site environment
Poisoning of active sites
Chirality
Bridging Si(OH)Al hydroxyl groups Introduced by post synthesis
200500 m2 g1 Up to 5000 m2 g1
0.10.5 cm3 g1 Over 1 cm3 g1
>450 C 300 C
High Limited, depends on solvents
High for small molecules in gas phase, slow in liquid phase High but strongly inuenced by linkers
Arises from framework oxygens Introduced post synthesis or through linkers
Low High
Important role in many reactions Expected to play a minor role
Mostly hydrophilic, but may also be hydrophobic Considerably hydrophobic
Reactivation by thermal treatment Thermal treatment not valid
Not possible or difcult Homochiral solid from chiral linkers or post synthesis modications

molecules can access the large pores, which should be important for
catalytic purposes, if the MOF structure has been functionalised or
has active sites and presents accessible framework atoms or metal
cationic sites (Table 2).
Garcia et al. have described [131] the use of metalorganic
frameworks (MOFs) as heterogeneous catalysts for oxidation reac-
tion using hydroperoxides or molecular oxygen. The authors have
limited themselves to the oxidation of cycloalkanes, oxidation of
benzylic positions, oxidation of cycloalkenes and aerobic oxidation
of alcohols, but many more oxidation reactions may be imagined
and studied. The use of MOFs as catalysts for enantioselective oxida-
tions has also been considered with the peculiarity of the required
oxidants and the advantages of having homo chiral MOFs.
Main applications of MOFs concern: adsorption, gas storage
(H2 , CO2 , etc.), gas separation, acid (Lewis; Brnsted), basic, redox
and enantioselective (chirality) catalyses, biomass transformation,
biomimetism, enzymes, drug delivery, magnetism, non linear optic,
lasers, sensors, luminescence, etc. In catalysis, the thermal stability
and leaching have been a big problem for many years and restrained
researches, but now some new systems have been claimed to be sta-
ble up to 500 C. The MOFs may not replace zeolites in petrorening
but well for ne chemistry under more gentle reaction conditions.
Already many papers have appeared for some reactions such as
oxidation, Lewis-type reaction of cyanosilylation of acetaldehyde
[137], etc.
It is clear that catalytic studies with MOFs are in their infancy.
It is certainly possible to go into more sophisticated materials with
organic ligands between the metals could be formed by transition
metal complexes with one or two metals at controlled distance.
Such types of materials will allow synthesis of heterogeneous cat-
alysts based not only on transition metal complexes but also by the
combination of mono- or multimetallic sites. Such design may lead
to materials having a catalytic behaviour similar to that observed
with enzymes.
The possibility to synthesise MOFs with a large variety of transi-
tion metals could be largely exploited for Lewis acid-type catalysis,
provided that the metal is accessible (free valency available) and
able to accept electrons from the reactant. In addition, the organic
component of the MOF should support acid, base, or acid-base
pairs and should allow one to perform successive reactions. There
may be interest in the chemical industry in exploiting MOFs as
heterogeneous catalysts. Examples include epoxide ring aperture
with alcohols by zinc carboxylates, ne chemical reactions as Fries
rearrangements, acylations, alkylaromatic oxidation using cobalt
salts in acetic acid, etc. MOFs offer also some promises as enan-
tioselective catalysts, a topic that has not been possible to develop
using zeolites. Asymmetric syntheses are routinely practiced in the
synthesis of drugs, and these reactions are almost completely per-
formed using expensive homogeneous catalysts. By using chiral
ligands, a vast number of new MOFs could be available and tested
in this eld. Considering the simplicity of the synthesis of MOFs and
their affordability, it will be important to know if MOFs can outper-
form in large-scale or asymmetric reactions to replace expensive
homogeneous processes.
Finally, there is a need for theoretical studies in this new eld,
assisting the design of MOFs and providing insight into the interac-
tion of the substrates and MOFs. Clarifying the reaction mechanism,
the geometry of the transition states, and the controlling step in the
reaction mechanisms may help to develop MOFs in which each of
the components plays the expected role, as catalytic sites of natural
enzymes.

2.6. Hierarchical zeolites

Hierarchical and mesoporous zeolites and mesoporous oxides

Fig. 12. Comparison of sizes of cavities and organic molecules diameters [132].
(alumina, titania, etc.) have received increasing attention because
of their improved performance in catalyzed reactions with respect
to conventional (purely microporous) zeolites or common metal
oxides [59,138,139]. The principle involves the creation of meso-
porosity within the zeolite or within any metal oxide particles.
Combined micro- and mesoporous materials have been claimed to
 I. Fechete et al. / Catalysis Today 189 (2012) 227
Fig. 13. World energy consumption in 2005 (13 TW or 87 Gbarrels oil) [245].
have advantages compared with the exclusively micro- or meso-
porous materials. The reactant molecules are thus expected to
diffuse more easily [140] within these pores to reach the active
zeolite sites. These materials provide better hydrothermal stability
[141], better multifunctionality to process a large variety of feed-
stocks, more controlled leaching rates for a constant and gradual
release of active components, and are more capable of encap-
sulating wastes in the micropores [142144]. Different porous
materials that combine micro- and meso-pores, such as SBA-15,
plugged hexagonal templated silica (PHTS), mesoporous aluminum
silicates (MAS), mesoporous titanium silicates (MTS), UL-ZSM-5,
and zeolites, have been developed within the last few years. Of
these materials, the latter four are mesoporous materials built up
from zeolite precursors. Such porosity in the mesoporous mate-
rials with zeolite character can be created after synthesis by
chemical treatments, including hydrothermal, acidic, basic, desili-
cation/dealumination [2] or recrystallization treatments [145,146],
or templating [147149] or carbon-based [150153] approaches.
Desilication in alkaline media has become a widely applied prepa-
ration method to tailor these modied zeolites because of the
methods optimal combination of efciency and simplicity. Alka-
line treatment is also a key step in strategic combinations with
other post-synthesis modications.
2.7. Carbon materials
Carbon nanotubes (CNTs) constitute another class of porous
materials. They have been widely studied since their discovery
in 1991 [154]. CNTs have highly unique electronic, mechanical,
catalytic, adsorption, and transport properties, which make them
interesting for a variety of applications. Carbon multiwall nano-
tubes (MWNTs) and single-wall nanotubes (SWNTs) should be
distinguished. They are easily fabricated and may be employed
either as catalyst supports, by entrapping active moieties within the
pores, or to improve photoconversion and electrical energy storage
(vide infra) [136,155160]. Other forms of nanographitic carbon
may also prove to be promising in the development of renewable
energy devices. For example, graphene, which consists of a sin-
gle sheet of graphite, is considered a promising form of carbon for
device engineering applications and catalysis [161165]. A signi-
cant volume of literature devoted to graphene and other forms of
carbon, including graphitic nanobers, has suggested that CNTs are
not the only promising nanostructures for either photoconversion
or electrical energy storage applications. The highly unique physical
properties of carbon nanotubes have been demonstrated for a vari-
ety of photovoltaic devices as well as for improved Li-ion batteries
and electrochemical capacitors.
11
2.8. Mesoporous materials
Many mesoporous silica-type materials have been synthesized
in the years after the pioneering works by Mobil researchers
on the M41S family (MCM-41, MCM-48, MCM-50) [166168].
MCM-n mesoporous materials are synthesized using surfactants
as structure-directing agents and can be characterized by well-
dened pores of tunable sizes in the range between 2 nm and 10 nm
and by specic surface areas between 600 m2 g1 and 1300 m2 g1 .
The most representative M41S materials are MCM-41 and MCM-
48. MCM-41 consists of regular pseudo-one-dimensional pores
in a honeycomb arrangement, whereas MCM-48 exhibits cubic
symmetry that consists of two interwoven but unconnected three-
dimensional pore systems of cylindrical pores. MCM-48 is more
difcult to synthesize and high-quality materials can typically be
obtained in the pore-size range between 2 and 5 nm [169]. MCM-50
comprises a lamellar phase. Independently, a family of mesoporous
silica materials with properties similar to those of MCM-41 was
discovered [170,171]; an important member of this family is FSM-
16 [171]. At the microscopic scale, these materials are essentially
amorphous. Whereas the pore diameter range of MCM-41 mate-
rials is restricted to 10 nm, ordered mesoporous silica with pore
diameters up to approximately 30 nm (SBA-15) can be obtained
using an amphiphilic block copolymer as a template [172,173].
SBA-15 (similar to MCM-41) consists of a hexagonal packing of
cylindrical channels; however, depending on the details of the
synthesis procedure, this material can possess irregular intrawall
micropores that connect adjacent channels [174,175]. Moreover,
a great variety of mesoporous materials have been synthesized,
such as SBA-1, SBA-2, SBA-12, SBA-16, HMS [176], MSU [177],
KSW-2 [178180], TUD-1 [181], periodic mesoporous organosilicas
(PMOs) [182184], nanoporous carbon with ordered mesostruc-
tures [CMK-1, CMK-3) [185,186]. Pure-silica mesoporous materials
are known to exhibit low catalytic activity because of the absence of
active sites, which typically require heteroatoms. Therefore, one of
the emerging trends in the area of mesoporous materials synthe-
sis is the incorporation of heteroatoms that serve as catalytically
active sites. Considerable research interest currently exists in the
preparation and use of heteroatoms that contain mesoporous sil-
icas as heterogeneous catalysts. Several elegant procedures have
been reported for the incorporation of heteroatoms that also per-
mit the design of the catalysts with active sites located on highly
accessible internal surfaces of the pore channels. These proce-
dures include impregnation [187190], grafting by liquidsolid
reaction [191196], grafting by gassolid reaction [197], graft-
ing by solidsolid reaction [198,199], isomorphous substitution
[200210], molecular designed dispersion approach [211213] and
12 I. Fechete et al. / Catalysis Today 189 (2012) 227
template ion exchange method [214,215]. The objective was to syn-
thesize porous materials able to accommodate bulky molecules and
thus treat heavier petroleum feedstocks. For example, the intro-
duction of Al into such silica frameworks led to medium-strength
acidity compared with the acidity of normal zeolites because of
larger Si O Al bond angles. The applications of such materials in
petrochemistry were subsequently limited. At present, research is
focused on the introduction of catalytically active functions within
the mesopores (i.e., functionalization of the walls) or of nanopar-
ticles of metals or oxides. Interesting results were obtained;
however, to our knowledge, no study has yet produced a break-
through in catalytic processes. H-Al-MCM41 materials have been
used as catalysts for the conversion of a large variety of substrates
in reactions as diverse as hydrocarbon cracking, hydrocracking and
hydroisomerization, olen polymerization, oligomerization and
isomerization, FriedelCrafts aromatic and phenol alkylations and
acylations, acetylazations, Beckmann rearrangements, glycosida-
tion, aldol condensations, and Prins condensations. Several reviews
on the subject have been published [2,216,217].
Interesting results for the metal-mesoporous materials were
reported with respect to the FischerTropsch reaction [218,219],
hydrodesulfurization [220222], the conversion of methylcy-
clopentane [199,201], the acylation of phenol [223], the naph-
thalene hydrogenation [224], the hydrogenation of arenes [225],
cyclohexane hydrogenation [226], NO reduction with CO [227],
the acylation of aromatic compounds [228], the benzoylation of
benzene [229], the metathesis of oct-1-ene [230], and the photocat-
alytic decomposition of NO [231], the oxidation reactions [232,233]
and soforth.
2.9. Versatile heterogeneous catalytic systems
Combining connement and synergy effects has appeared
recently as a promising way to synthesise efcient and versatile
heterogeneous catalytic systems. For instance, many studies have
been performed in the past half century to immobilize homo-
geneous catalysts on solid supports to synthesize heterogeneous
catalysts [234], known to result in easy separation of the catalyst
from the reactants and products. Originally, the active centres were
designed to be away from a support surface in order to minimize the
support destructive inuence on the catalytic sites and to maintain
the homogeneous metal complexes environment of ligands with
a long spacer and thus catalytic properties [235]. Later on, it was
observed that a support can even have some benecial effects on
the anchored homogeneous catalysts [236] such as connement
[237] and synergy effects [238240]. Heterogeneous bifunctional
and even trifunctional catalysts could then be prepared and stud-
ied because a synergy between multifunctional groups could be
developed within conned spaces. An important further objective
was to try to synthesise heterogeneous catalysts with enantioselec-
tivity enhanced after chiral catalysts are introduced into conned
spaces. For example, Raja and Thomas [241] have shown that,
compared with the racemic products obtained in homogeneous
catalysis, improved enantioselectivity (ee% 5394%) in asymmetric
hydrogenation reactions was obtained after chiral RhI complexes
were introduced into the channels of mesoporous silica. He et al.
[242] have also shown that after a bifuntional catalyst, 9-thiourea
epi-quinine, was incorporated in the channels of mesoporous silica
SBA-15, the heterogeneous catalyst exhibited improved selectiv-
ity and enantioselectivity (92.5% selectivity and 99.2% ee versus
83.8% selectivity and 93.2% ee) in asymmetric FriedelCrafts reac-
tion between indoles and imines.
Layered compounds, with two-dimensional exible interlayer
regions, are also promising supports for the immobilization
of homogeneous catalysts. For instance, the immobilization of
copper complexes in laponite clay was found [243] to increase the
ee from virtually zero to values ca. 40% in the reaction of methyl
phenyldiazoacetate with tetrahydrofuran.
The idea is to graft, anchor or thether catalytic active entities
to mesoporous silica. These species may be identical or different
which may lead to bifunctional, trifunctional entities within the
pores. Their proximity may result in synergistic effect for some
reactant within a conned space and opens an important eld of
discovery of new catalysts, by taking advantage of continuum range
of distance between anchored functional groups and intrinsic active
sites on the support surface. Synergistic effects within anchored
bifunctional catalysts, between two anchored functional groups,
and between the anchored groups and hydroxyl groups on solid
surface have been used to synthesise multifunctional catalysts. Lets
also remind that synergistic effects are widely utilized in nature
such as for enzymes which with limited functional groups can cat-
alyze many reactions smoothly with high activity and selectivity at
near room temperature. [244]
3. Energy resources
Currently, petroleum and natural gas represent more than 60%
of the primary energy supplied to 7 billions inhabitants on earth.
Coal also remains an important source of energy, primarily in Asia.
Whether used for energy production, transport, heating or as a
source of chemical raw materials, the consumption of oil, natu-
ral gas and coal is expected to rise in the near future, while the
development of alternative sources is expected to rise rapidly after
a slow development in the past 20 years. The signicant increase
in energy demand over the past twenty years has primarily been
satised by increasing the production of fossil sources. Because of
this situation, several governments are approving new laws aiming
to reduce CO2 emissions by promoting the utilization of renewable
energy sources and biofuels. The total world consumption in 2005
was of 13 TW (87 Gbarrels of oil), of which 81% came from fossil
resources, as shown in Fig. 13.
Ten percent of the world energy use is derived from biomass,
and 7% is derived from nuclear power. Nuclear power is desirable
as long as the isotope uranium-235 (235 U) is employed. However,
a less than twenty-year supply of U235 , which may be recovered
at a reasonable cost, is available. When the supply of 235 U will be
exhausted, it will then be necessary to employ breeder reactors.
Unfortunately, the by-product of this reaction is the very hazardous
element, plutonium-239, 239 Pu (238 U 239 Pu). Moreover since the
disaster following the tsunami in Japan in 2011 and the collapse of
the nuclear plant in Fukushima, the construction of nuclear plants
have been hardly questioned in many countries, although nuclear
power is non CO2 producer and non fossil resource consumer.
3.1. The case of oil
It is difcult to evaluate the exact oil reserves because it cor-
responds to rough estimations called current reserves, which are
contingent resources (conventional and extra-heavy + bitumen)
concentrated in a limited number of countries (Saudi Arabia, with
20%, Iran, Iraq, and Venezuela; these four countries possess 50%
of the world reserves), with 75% in concentrated in 11 countries.
The current reserves correspond to approximately 1000 Gbarrels
therefore, approximately 35 years of production at actual consump-
tion level, but less than the oil already extracted) and one may
add 200 Gbarrels for conventional resources and 200300 Gbarrels
more for extra-heavy oil and bitumen. Oil is extracted either by
simple pumping (20% of world production), by the injection of
water (2/3 of oil produced), or by the injection of water + chemicals
or gas (air, CO2 or gas produced (15%)). Efforts to discover new
resources are clearly important, and the substitution of oil by
 I. Fechete et al. / Catalysis Today 189 (2012) 227 13

3.3. Biomass as a source of raw materials and future energy

Biomass, i.e., all products from plants (crops, algaes, wood, agri-
cultural wastes, etc.), has emerged as an important future source
of energy and raw chemicals to replace, at least in part, coal, oil
and natural gas. The origin of biomass from CO2 and water under
solar photons and chlorophyll to produce sugar blocks at the ori-
gin of cellulose, hemicellulose, lignin, and so forth is well known.
Lignin constitutes one of the three major components of ligno-
cellulosic biomass; the other two components consist of cellulose
and hemicellulose. Lignin is a three-dimensional amorphous poly-
mer that consists of methoxylated phenylpropane structures. In
plant cell walls, lignin lls the spaces between cellulose and hemi-
cellulose and acts as a glue that holds the lignocellulose matrix
together. Cross-linking with the carbohydrate polymers then con-
fers strength and rigidity to the system [245,247].
In 2005, more than 3% of the total energy consumption in the
United States was supplied by biomass, and it recently surpassed
Fig. 14. Some perspectives of oil demand in a near future from WEO 2006. Note that hydroelectric energy as the largest domestic source of renewable
billions tonnes should read giga tonnes. energy. Similarly, the European Union receives approximately 66%
of its renewable energy from biomass, which surpassed the total
combined contribution from hydropower, wind power, geother-
mal energy, and solar power. In addition to energy, the production
renewable energies is vital. Some prospects are presented in of chemicals from biomass is also essential because it is the only
Fig. 14. renewable source of liquid transportation fuel.
Over the last 30 years, three generations of biomass products
have emerged [248,249], which are distinguished by their nature.
3.2. Perspectives with natural gas (NG) Whereas oil was the principal source of energy in the twentieth cen-
tury, the 21st century is expected to bring new sources of energy,
Natural gas constitutes the largest reserves of fossil resources. particularly renewable energies such as bioenergies [248].
Eleven countries possess 75% of world gas resources, with 45% for Three strategies for biomass valorization can be followed [249].
Russia, 28% for Iran, and 25% for Qatar. The current reserves are In the rst strategy, biomass is gasied to syngas or degraded by
estimated to reach 175200 Tm3 (T = tera = 1012 ); however, large pyrolysis to a mixture of small molecules, which can be used to
resources exist in the form of methane hydrates, which are located produce chemicals using technologies developed for petroleum
primarily in Polar Regions or in deep-water acreage. Natural gas feedstocks. In the second strategy, extensive removal of the func-
can be used as an energy source (in power plants or as a heating tional groups present on the lignin monomers yields simple
source, for instance), but it can also be transformed into many aromatic compounds, such as phenol, benzene, toluene and xylene.
basic materials for chemicals. Nevertheless, currently, only its These platform chemicals are then reacted in a second step using
conversion to syngas via steam reforming, partial oxidation or existing catalytic technology developed for petroleum reneries
autothermal oxidation appears to be industrially viable [246]. All to produce bulk and ne chemicals. In the third strategy, biomass
direct transformations to, for instance, methanol, dimethyl ether, is converted directly to valuable chemicals in a one-pot process,
formaldehyde, aromatics, or olens are still not economically which requires highly selective catalysts that eliminate functional-
viable. This lack of viability constitutes a real challenge for the ities and linkages. This strategy is best suited for the production of
future, although many approaches have been attempted over the ne chemicals with a high degree of functionality, such as vanillin,
past 50 years, starting with the dimerization reaction in the 1970s, that already resemble the lignin structure; however, more com-
without commercialization success. The main possible reactions plicated target molecules may also be produced with additional
are summarized below: improvements in catalytic technology. Indeed, this approach could
yield a plethora of complex aromatics that are not otherwise read-
Steam reforming H0 298 (kJ mol1 ) ily available via conventional petrochemical routes. Because none
1. CH4 + H2 O  CO + H2 206
2. Cn Hm + nH2 O  nCO + (n + m/2) H2 1175 (for nC7 H16 )
of these strategies is expected to yield a single product in high
3. CO + H2 O  CO2 + H2 (WGS) +41 yield, product separation is an important component of each pro-
cess. In each case, after the catalytic processing of the lignin stream,
CO2 (dry) reforming
4. CH4 + CO2  2CO + 2H2 247 the chemicals or fuels produced must be puried, which obviously
must be taken into account in evaluations of the environmental
Autothermal reforming (ATR)
impact of the whole process. Components from the cellulose and
5. CH4 + 1 O2  CO + 2H2 O +520
6. CH4 + H2 O  CO + 3H2 206 hemicelluloses streams are integrated within the lignin framework,
7. CO + H2 O  CO2 + H2 +41 but the process arrows are not fully depicted for clarity [245]
Catalytic partial oxidation (CPO)
Fig. 15.
8. CH4 + 1/2O2  CO + 2H2 +38 The transformation of cellulose, which is the main constituent
of the most abundant renewable lignocellulosic feedstock and is
Total oxidation
9. CH4 + 2O2 CO2 + 2H2 O +802 non-edible, into chemicals and fuels has attracted signicant atten-
tion in recent years. Compared with other conversion routes, such
Boudouard reaction
10. 2CO  C + CO2 +172
as high-temperature gasication and pyrolysis and enzymatic fer-
mentation, a low-temperature and selective catalytic route for the
The main chemical products from natural gas are summarized transformation of cellulose in, e.g., a water medium, into a plat-
in Table 3. form molecule, which may be facilely transformed into valued
14 I. Fechete et al. / Catalysis Today 189 (2012) 227
Table 3
Main chemical products from natural gas.
Products Production (Mtons/y)
Ammonia 120
Ethylene 100
Propylene 55
Methanol 30
Hydrogen 20
Synfuel 15
Source: IFP Energies Nouvelles.
chemicals and fuels in the subsequent step, is more desirable. Glu-
cose, polyols, organic acids, and 5-hydroxymethylfurfural (5-HMF)
are all promising platform molecules. Some bifunctional catalysts
and catalytic systems that contain both acidity for the hydrolysis
of -1,4-glycosidic bonds in cellulose and metal nanoparticles for
the hydrogenation or oxidation of monosaccharide to polyols or
organic acids have been developed [250256].
Some analogies can be drawn between the twentieth century
petroleum renery and the twenty-rst century biorenery. In the
beginning, the petroleum renery made few products and incor-
porated little chemical and energy components. The development
of the petroleum renery required considerable effort-spanning
decades-to become the highly efcient, integrated system that
exists today. Many of the breakthroughs that allowed this remark-
able transformation involved advances in catalysis. Similarly,
current bioreneries, which are still in their infancy, produce rel-
atively few chemicals (primarily ethanol or bio-oils) with little
chemical and energy integration. Analogous to the history of the
petroleum renery, with the development of catalytic technology,
the biorenery may become an efcient, highly integrated system
to meet the chemical and fuel requirements of the twenty-rst cen-
tury. To realize this system, in addition to the catalytic conversions
of cellulose and hemicellulose, the lignin fraction of biomass should
be transformed from a low-quality, low-price waste product into a
high-quality, high-value feedstock for bulk and specialty chemicals
by the development of the appropriate catalytic technology. The
direct transformation of lignin into valued chemicals appears to be
more difcult than the transformation of cellulose. However, this
transformation is critical because lignin represents the only viable
renewable source for the production of the aromatic compounds
on which society currently depends.
Fig. 15. Lignocellulosic biorenery scheme with particular emphasis on the lignin stream [245].
Energy consumption (GJ/t) CO2 (t/t) Main technology
29 1.6 Syngas/synthesis
15 0 .65 Steam cracking of C2 H6
0.28 Steam cracking
28 9.0 Syngas/synthesis
12.6 1 Steam reforming
67 Syngas/synthesis
It can be concluded that biomass is currently the leading renew-
able energy source in the world. Moreover, the introduction of
biomass into energy systems presents certain advantages, such
as a reduction in greenhouse gas emissions, because its synthe-
sis uses CO2 and water. However, its mobilization still presents
many challenges relative to the competition between uses and
the management of local natural resources (e.g., water, soil, bio-
diversity, farmer land and forest private properties). Therefore, the
technologies involved should be structured so that this resource
is developed to be truly sustainable. Two technologies exist for
the production of diesel replacement fuels: vegetable-oil methyl
esters (VOME) and hydrotreated vegetable oils (HVO). The latter
oils, blended with kerosene, have begun to be used as aviation
fuel.
Crop yields depend on the nature of the biosource, as detailed
in Table 4. Wood is an important source for lignin. The production
and transformation of wood into biofuel is presented in Table 5.
Algae as oil seed appears to be particularly efcient (yield of
70 t ha1 and fuel efciency of 14 toe ha1 ), whereas sugar cane
and sugar beets have high yields (ca. 70 t ha1 ) but lower fuel ef-
ciency (ca. 3 toe ha1 ). For comparison, the majority of the other
biomass resources have yields of 1020 t ha1 and efciencies of
24 toe ha1 . The cultivation of microalgae to produce oil biomass,
cellulose or hydrogen is free of many terrestrial constraints. Such
microalgae are cultured in photobioreactors and need only be in
proximity to water, light, heat and CO2 . Microalgae constitute the
prevailing trend in current research.
In the future, solar, geothermal, wind and presumably nuclear
power plants will presumably be used for electricity; biomass,
natural gas, coal and oil will be used for syngas and chemi-
cals, hydrogen will be used for GTL and hydroprocessing, and
 I. Fechete et al. / Catalysis Today 189 (2012) 227 15

Table 4 change in the Gibbs free energy as a function of temperature and the
Crops mobilised for energy pruposes versus total production in 2007.
corresponding decreasing equilibrium constant as the temperature
Total harvest (Mt) % for bioenergies is increased. Low temperatures thermodynamically favour higher
Corn 606 0.3 CO conversion. For maximum efciency and economy of operation,
With USA 120 1 many plants operate both a high-temperature stage (350400 C)
Rape sunower 77 17 and a low-temperature stage (180240 C). The commercial cata-
With USA 23 51 lyst is composed of copper, zinc oxide, and alumina. The copper and
Soybean 221 1
zinc oxide forms are stable under WGS reaction conditions. Copper,
With USA 144 2
Palm oil 193 0.2 the active species, remains active at temperatures as low as 200 C.
With Asia 165 0.3 The zinc oxide provides some protection of the copper from sulfur
Sugar beet 247 4 poisoning by reacting with adsorbed sulfur compounds while also
With EU 115 8
acting as a support for the copper. Because of the relatively low
Sugar cane 1591 15
With South America 641 37 melting point of copper, the commercial low-temperature stage
Wheat 606 0.3 catalyst is more sensitive to deactivation caused by sintering. Dif-
With EU 120 1 ferent catalysts are employed in the WGS reaction, including Fe
From FAOSTA, FAPRI. [260,261], Ni [262,263], Cu [264,265], Ru [266,267], Au [268,269],
Pt [270].
The essential role of the industrial WGS reaction is to increase
reneries will be used to produce heat, electricity, transports, and the production of hydrogen for renery hydroprocesses, bulk stor-
bulk chemicals (CO2 sequestration). age and redistribution. This role includes the need for gases of
appropriate H2 /CO ratios in the production of organic bulk chem-
4. Hydrogen as a future energy source icals such as ammonia, methanol, and alternative hydrocarbon
fuels through FischerTropsch synthesis. These gas mixtures, when
The future supply of energy is dependent on hydrogen as a applied in industry, are usually referred to as synthesis gas, or
clean energy carrier. Hydrogen can be produced from fossil fuels, syngas, and are produced in large-scale facilities by the high-
water electrolysis and splitting or biomass. However, the current temperature reaction of carbonaceous materials in the presence
debates concerning hydrogen economy are intimately linked to the of water or oxygen and supported-nickel catalysts.
clean production of hydrogen from fossil fuels (e.g., natural gas,
coal propane, methane, gasoline, light diesel), from dry biomass 4.2. Hydrogen production by steam reforming of ethanol
and biomass-derived liquid fuels (e.g., methanol and biodiesel),
and from water. Because of the low cost and wide availability of Ethanol is an excellent candidate for the production of hydro-
coal, coal gasication to syngas and then to hydrogen through the gen. The aim of the procedure for the steam reforming of ethanol
watergas shift (WGS) reaction is a promising route to cheap hydro- is to generate a large amount of hydrogen and carbon diox-
gen. The success of such a hydrogen production route will only be ide by breaking the ethanol molecule in the presence of steam
possible if carbon dioxide is sequestered safely and economically. over an appropriate catalyst [271275]. However, numerous reac-
The key to the cost effective conversion of coal to hydrogen and car- tion pathways occur in the ethanol steam-reforming process that
bon capture is the development of nanomaterials, such as catalysts depends on the nature of the catalysts used. These pathways
for the WGS reaction and inorganic membranes for hydrogen/CO2 include the dehydration of ethanol to ethylene and water followed
separation. In the future, hydrogen will be the dominant fuel and by ethylene polymerization to form coke [276], the decomposi-
will be converted to electricity in fuel cells, leaving only water as a tion or cracking to methane followed by steam-reforming [277],
product. dehydrogenation to acetaldehyde [274] followed by decarboxy-
lation or steam-reforming of C2 H4 O, decomposition into acetone,
4.1. Watergas shift reaction (WGS) CH3 COCH3 , followed by steam reforming [278], and steam reform-
ing of ethanol to syngas [274]. These processes are accompanied by
Since the early 1940s, the WGS reaction has represented an the watergas shift reaction, coking reaction, and other reactions.
important step in the industrial production of hydrogen [257]. Tremendous progress is needed to obtain a highly selective catalyst
Interest in the study of WGS catalysts has recently been renewed to develop a process for hydrogen generation by ethanol steam-
because of the importance of such catalysts in PEM fuel cell appli- ing, which is a sustainable solution for the problem of hydrogen
cations [258,259]. The WGS reaction is an old industrial process in production.
which water in the form of steam is mixed with carbon monoxide to
obtain hydrogen and carbon dioxide. The WGS reaction is reversible 4.3. Water splitting as a hydrogen source [279]
and exothermic. Because of its moderate exothermicity, the WGS
reaction is thermodynamically unfavorable at elevated tempera- Pure hydrogen may be the nal destination in the evolution
tures, as illustrated by the continuous decline and eventual sign of fuel usage from coal to petroleum to natural gas, which has

Table 5
Commercial uses of wood (in Mm3 ) and breakdown of conventional energy uses in 2007.

Wood harvest Sawn wood Wood for paper Wood for board Wood for fuel Fuel wood %

World 3,591 1,007 354 266 1,886 53

Europe 729 330 102 84 153 21
North America 640 386 149 56 54 8
South America 366 82 36 15 184 53
Asia 1,027 150 55 105 787 77
Africa 672 25 6 3 603 90

Source: IFP Energies Nouvelles, D. Lorne, Panorama 2010 Source: FAOSTAT.

16 I. Fechete et al. / Catalysis Today 189 (2012) 227
followed a trail of increasing hydrogen content. A major bottleneck
for the hydrogen vehicle is the issue of hydrogen storage. Hydrogen
has the highest energy per unit mass, but occupies a large volume.
Even in liquid form, the energy density of hydrogen is only 8.4 MJ/L,
compared with 31.6 MJ/L for gasoline. MIL-53 is a potentially useful
material for hydrogen storage, as are graphene [280] and bimetallic
Pd-based alloys.
Because of its high energy capacity and environmental friendli-
ness, hydrogen has been identied as a potential energy carrier in
many low-greenhouse-gas (GHG) energy scenarios. In a proposed
hydrogen energy system, hydrogen-containing compounds, such as
fossil fuels (mainly methane), biomass, or even water, are potential
sources of hydrogen. When hydrogen is derived from hydrocar-
bons such as fossil fuels or biomass, the capture and sequestration
CO2 are required in a low-GHG scenario. Although hydrogen pro-
duced from water does not present the challenge of unwanted
emissions at the point of conversion, it does require that energy be
supplied from an external resource. If this energy can be obtained
from a renewable energy source, such as solar energy, hydrogen
can then be considered a green energy alternative, and it is becom-
ing increasingly relevant in our world. However, the technology
to produce hydrogen in a cost-effective, low-GHG manner has
not yet been developed. Since the discovery of hydrogen evolu-
tion through the photoelectrochemical splitting of water on n-type
TiO2 electrodes, the technology of semiconductor-based photocat-
alytic water splitting to produce hydrogen using solar energy has
been considered one of the most important approaches to solv-
ing the world energy crisis. Consequently, the development of the
necessary semiconductor photocatalysts has been the subject of
considerable research. Over the past 40 years, many photocatalysts
have reportedly exhibited high photocatalytic activities for split-
ting water into a stoichiometric mixture of H2 and O2 (2:1 by molar
ratio) in the UV-light region. These photocatalysts include La-doped
NaTaO3 , Sr2 M2 O7 (M = Nb, Ta), La2 Ti2 O7 , K2 La2 Ti3 O10, NiO/NaTaO3
and -Ge3 N4 , among others, photocatalyst, which shows the high-
est activity, with a quantum yield of 56% at 270 nm. However, these
oxide photocatalysts are only active under UV irradiation. With
respect to the solar spectrum, only a small fraction (ca. 4%) of the
incoming solar energy lies in the ultraviolet region, whereas the vis-
ible light in the solar spectrum is far more abundant (ca. 46%). It is
essential, therefore, as an alternative to UV-active photocatalysts,
to develop visible-light-driven photocatalysts that are stable and
highly efcient for the practical, large-scale production of hydro-
gen using solar energy. In recent years, continuous breakthroughs
have been made in the development of novel visible-light-
driven photocatalysts, which has led to the enhancement of
photocatalytic activity for water splitting and has inspired great
enthusiasm. A large number of semiconductor materials have been
developed as photocatalysts for the splitting of water to hydro-
gen under visible-light irradiation. Signicant process has been
achieved [281] with respect to semiconductor-based photocat-
alytic hydrogen generation through water in the hydrogen energy
system.
Photocatalytic systems for water splitting are classied as
one of two main kinds: sacricial-reagent-containing water-
splitting systems and overall water-splitting systems. Thus far, the
sacricial-reagent-containing water-splitting systems constructed
from the Pt/CdS, Pt-PdS/CdS, and Zn/Cr layered double-hydroxide
photocatalysts have demonstrated the best performance for hydro-
gen production and oxygen production, with highest quantum
yields of ca. 60%, 93%, and 60%, respectively, at 420 nm. How-
ever, the efciency of overall water-splitting systems based on
visible-light-driven photocatalysts is still quite low, with a max-
imum quantum efciency of ca. 5.9% over Rh2y Cry O3 /GaNZnO
in the range of 420440 nm. This result is still far from the
quantum efciency (ca. 30% at 600 nm) designated as the initial
starting point for practical applications or the critical conver-
sion efciency of light energy to hydrogen from photocatalytic
water decomposition (15%). Therefore, more efcient visible-
light-driven photocatalysts need to be developed to allow the
construction of the necessary high-efciency and cost-effective
water-splitting systems. To develop more efcient visible-light-
driven photocatalysts, the band gaps need to be narrowed to
harvest visible light in longer-wavelength regions of the spec-
trum and to enhance the photogenerated charge separation during
photocatalysis. Band-gap engineering for the modication of the
band structure of semiconductor photocatalysts using ion dop-
ing, semiconductor sensitization, or solid solutions all present
signicant opportunities to render such materials active in the
visible-light region. Computational predictions based on rst-
principles calculations could provide an efcient way to identify
candidates.
The loading of co-catalysts on the surface of the host photocat-
alysts has been shown to be rather effective in inhibiting charge
recombination. Alternative, more economical co-catalysts, such as
the non-noble metals and other derived metal-based compounds,
also need to be tested as possible substitutes for the most frequently
used noble metals, such as Pt, which is very efcient but expen-
sive. In addition, new insights are needed into the water-splitting
mechanism, particularly regarding the identication of any ther-
modynamic and kinetic bottlenecks. Such determinations would
facilitate the design of the most effective photocatalytic water-
splitting systems.
Presently, the available efciency for overall water-splitting
systems for the simultaneous production of hydrogen and oxy-
gen under visible-light irradiation is still low because of the
fast charge recombination and backward reactions. To achieve
enhanced and sustainable hydrogen production, the continuous
addition of electron donors is required to make up half of the
water-splitting reaction to reduce H2 O to H2 . These sacricial
electron donors can irreversibly consume photogenerated holes
and thus prohibit undesirable charge recombination. Taking into
account the decreasing cost of solar-to-H2 energy conversion, pol-
luting byproducts from industries and the low-cost renewable
biomass from animals or plants are preferential sacricial electron
donors in water-splitting systems. At little or no cost, they could
be exploited to simultaneously accomplish the task of hydrogen
production and that of waste treatment and biomass reforming.
Nevertheless, such an admirable goal for the practical applica-
tion of water-splitting systems is especially interesting considering
worldwide energy and environmental concerns, but is still in its
infancy.
The current lack of industrial applications of the semiconductor-
based photocatalytic hydrogen generation is largely due to two
reasons: the low photocatalytic efciency and the lack of exten-
sive studies for a successful scale-up of the laboratory setup to an
industrially relevant scale.
In addition to TiO2 , heterogeneous photocatalysts such as ZrO3 ,
NaTaO3 , BaTa2 O6 , SrTa2 O6 , K4 Nb6 O17 , and K3 TaSi2 O13 can decom-
pose water to evolve O2 and H2 without loading any co-catalysts
under UV irradiation [282]. The activities of the majority of these
photocatalysts are augmented by the loading of a co-catalyst, such
as NiOx, as a proton-reduction site. In this regard, high-donor-
doped layered perovskites loaded with NiO have demonstrated
photocatalytic ability for water splitting under UV irradiation.
These layered structures with a basic composition Am Bm O3m+2 ,
where m 4 or 5, A Ca or Sr, and B Nb or Ti, showed elevated
quantum yields and a stoichiometric evolution of H2 and O2 . How-
ever, SrTiO3 , KTaO3 , Ta2 O5 , Rb4 Nb6 O17 , K2 La2 Ti3 O10 , Rb2 La2 Ti3 O10 ,
Cs2 La2 Ti3 O10 , CsLa2 Ti2 NbO10 , Na2 Ti6 O13 , and BaTi4 O9 can also
evolve O2 and H2 with the aid of co-catalysts, such as Pt, Rh, and
RuO2 [282].
 I. Fechete et al. / Catalysis Today 189 (2012) 227 17

5. Challenges for reneries Recent developments in coreshell-structured catalysts that

contain conventional FT catalysts, such as Co/Al2 O3 as the core
In reneries, we expect the synthesis of clean fuels compo- and zeolite (H-ZSM-5) membrane as the shell, have increased the
nents (syngas to liquids, reformulated gasoline with solid acid selectivity to C5 C11 isoparafns because of the hydrocracking and
alkylation to obtain branched C8 alkanes of high octane number isomerization ability of zeolite [288]. The use of mesoporous zeo-
values), the reduction of S to less than 10 ppm after 2010 by the lite (meso-ZSM-5) as the support for Ru nanoparticles signicant
development of new catalysts and new reactor technologies and enhanced the selectivity to C5 C11 hydrocarbons to greater than
by bio-desulfurization, the reduction of aromatics (hydrogenation, 80%, which was signicantly higher than expected from the selec-
gasication, cracking), and the reduction of heavy metals from tivity based on the ASF distribution (45%) [289]. The use of CNTs
crude oil by bio-demetalization will predominate. High-octane can also increase the selectivity to a particular fraction of hydro-
non-aromatic blend stock that is sulfur and olen free will be carbons. For example, Ru/CNT gave a C10 C20 selectivity of 60%
needed to meet the new specications. The future production of [290]. The connement of iron oxide particles inside the CNTs or
hydrogen without the formation of CO2 should come from pho- carbon spheres could increase the selectivity to C5 + because of the
tocatalytic splitting of water (vide infra) and the conversion of facile transformation of iron precursors to iron carbides, which are
methane and light alkanes (C1 C3 ) to higher/aromatic hydrocar- believed to be responsible for CC coupling [291,292].
bons and hydrogen.
5.2. Hydrodesulfurization (HDS) and uid catalytic cracking
(FCC)
5.1. FischerTropsch synthesis (FT)
Gasoline has the highest concentration of sulfur compounds in
In 1922, Franz Fischer and Hans Tropsch converted a CO/H2
the FCC (uid catalytic cracking) stage of the renery process. Envi-
mixture to a mixture of hydrocarbons (HCs) and oxygenated com-
ronmental regulations are becoming increasingly stringent with
pounds using an iron-based catalyst. The cobalt catalysts for this
regard to the sulfur content in fuels. At the same time, olens
process were discovered a few years later. Although these pro-
present in the FCC naphtha make a major contribution to the octane
cesses are old technology, they are still relevant. FischerTropsch
number in gasoline [293295]. In this context, desulfurization must
(FT) synthesis is a heterogeneous catalytic process for the pro-
be performed to hamper olen saturation in FCC gasoline [293].
duction of clean hydrocarbon fuels or chemicals from synthesis
Hydrodesulfurization (HDS) of petroleum feedstock is one of the
gas, which can be derived from a variety of non-petroleum car-
most important processes in petroleum rening for the produc-
bon resources, such as natural gas, coal, biomass, oil sands, or
tion of clean, high quality fuels [296299]. Sulfur compounds in
oil shales [283]. During World War II, FT technology was used in
petroleum fractions include suldes, disuldes, polysuldes, mer-
Germany to produce synthetic fuel (16 kbarrels per day) on Co cat-
captans, thiophene, benzothiophene and dibenzothiophene, but
alysts [284] and later, in South Africa (SASOL), in synergy with
thiophene, benzothiophene and dibenzothiophene are used in HDS
coal gasication to produce synthetic fuel because of an embargo.
studies as model molecules. For example, hydrodesulfurization of
Later, SASOL switched to natural gas (NG) for the production of
thiophene is one of the most important reactions that occur in the
syngas for FT. The FT synthesis has received renewed interest in
second-stage hydrogenation of pyrolysis gasoline in olen plants
recent years because of the global demand for a decreased depen-
[300,301]. A two-stage hydrogenation process is usually used
dence on petroleum for the production of fuels and chemicals.
in industry to eliminate these impurities: (1) hydrogenation for
The product distributions with conventional FT catalysts usually
selective hydrogenation of diolens and (2) thiophene hydrodesul-
follow the AndersonSchulzFlory (ASF) distribution and are typ-
furization. Therefore, there is a strong incentive to develop catalytic
ically unselective with respect to the formation of hydrocarbons
systems for the FCC/HDS processes. Sulded CoMo or NiMo(W)-
from methane to waxes. Selectivity control is one of the formidable
based catalysts have been extensively used in industry for HDS
challenges in this area.
reactions [302,303] and have attracted attention as catalytically
The most common catalysts used in FT synthesis are still based
active sites where Co decorates the edge sites of highly dispersed
on iron or cobalt compounds that work at high pressures (16 MPa)
MoS2 crystallites [304308]. However, the precise structures of the
and at temperatures between 200 and 300 C. Under these con-
active sites and the HDS reaction mechanism still remain ambigu-
ditions, the fuel is of high quality because of the low aromaticity
ous. The active sites of the catalysts are considered to be extensively
and the absence of sulfur. The iron-based catalysts produce gaso-
promoted by their selective preparation. The use of a chelating
line, hydrocarbons, and linear alpha-olens, as well as a generally
agent in the preparation of HDS catalysts [309312] has been found
unwanted mixture of oxygenates, such as alcohols, aldehydes, and
to be highly effective in increasing the amount of Co(Ni)MoS by
ketones, and excessive amounts of carbon dioxide. With cobalt
increasing the coverage of Co(Ni) on the edges of MoS2 particles.
catalysts, high yields of long-chain linear parafns, which can be
The preparation of HDS catalysts using citric acid as a chelating
efciently transformed into valuable products (middle distillates)
agent signicantly improves their catalytic activity [313316].
by hydroprocessing, are possible. Moreover, the syngas step should
The literature contains reports of various attempts to develop
be adapted to the type of catalysts to be used to optimize the CO/H2
selective catalysts for this purpose including oxides [317322],
ratio in reference to the optimal ratio for the FT catalyst/reactor. To
zeolites [323326] and mesoporous materials [327329], clays
promote FT over methanation, the FT reactor typically operates at
[330332] and noble metal catalysts [300,324,333349]. Excellent
a low temperature (200240 C), a mild pressure (23 MPa), and
studies were conducted on the mild oxidation of thiophenes and
in the presence of a catalyst (Co- or Fe-based). However, various
thioethers using green oxidizing agents [350] on mesoporous
catalysts have been tested in the FT reaction [285287]. To opti-
materials [351,352].
mize the overall liquid production, it is necessary to produce high
molecular weight linear waxes for further hydroprocessing steps.
To explain the mechanism of the FT reaction, some authors have 6. CO2 emissions as a prospective source for fuels and
derived the LangmuirHinshelwood or EleyRideal types of rate chemicals [353358]
expressions for the reactant consumption, where, in the majority of
cases, the rate-determining step was supposed to be the formation CO2 is a major contributor to the so-called greenhouse effect,
of the building block or monomer, methylene. which supposedly leads to warming of the earth and thus to
18 I. Fechete et al. / Catalysis Today 189 (2012) 227
changes in the climate. The energy sector, which is the largest
source of CO2 emissions, is responsible for approximately 25% of
global CO2 emissions. Great efforts have been conducted in the past
to use carbon dioxide as a chemical raw material with a very low
or even negative cost rather than as a waste, e.g. CO2 reductions
under photoirradiation, or under electrolytic conditions, or produc-
tion of synthesis gas by reforming natural gas. However, many of
these reactions produce rather simple molecules such as carbon
monoxide and formic acid. CO2 has the advantages of being non-
toxic, abundant, and economical, attractive as an environmentally
friendly chemical reagent, especially useful as a phosgene sub-
stitute. The largest obstacle for establishing industrial processes
based on CO2 as a raw material is its low energy level. In other
words, a large energy input is required to transform CO2 . There
are several methodologies to transform CO2 into useful chemicals,
such as the use of high-energy starting materials such as hydro-
gen, unsaturated compounds, small-membered ring compounds,
and organometallics; the choice of oxidized low-energy synthetic
targets such as organic carbonates or the supply of physical energy
such as light or electricity. Selecting appropriate reactions can lead
to a negative Gibbs free energy of the reaction [353358].
Possibilities for the chemical recycling of carbon dioxide to fuels
have been studied largely as a complementary technology to car-
bon sequestration (CSS) and storage. CSS requires the minimization
of hydrogen consumption to produce fuels [29,258], which can be
easily stored and transported, and to use renewable energy sources.
From this perspective, the preferable option is to produce alcohols
(preferably C2) by use of solar energy to produce the protons
and electrons necessary for CO2 reduction. The chemical trans-
formation of CO2 includes a reverse watergas shift reaction and
hydrogenation to produce hydrocarbons, alcohols, dimethyl ether
and formic acid, a reaction with hydrocarbons to syngas (such
as dry reforming of methane), and photo- and electro-catalytic
and thermochemical conversions [257,258,359361]. CO2 can be
used as a building block in organic syntheses to obtain valuable
chemicals and materials has been discussed in many reports and
review articles. The main applications of CO2 as chemical raw
materials [353] are syntheses of polycarbonates and polyurethanes.
Organic carbonates are roughly categorized into cyclic and linear
carbonates, which both compounds have three oxygens in each
molecule, and are suitable from a thermodynamic point of view
as synthetic targets starting from CO2 . Four industrially important
organic carbonates are ethylene carbonate (EC), propylene car-
bonate (PC), dimethyl carbonate (DMC), and diphenyl carbonate
(DPC). EC, DMC and DPC are useful intermediates for manufac-
turing polycarbonates through a non-phosgene process [353]. In
addition, EC, PC and DMC are employed as electrolytes in lithium
ion batteries and are widely used as aprotic polar solvents. Fur-
thermore, the excellent properties of DMC as a fuel additive have
attracted much attention. DMC can be synthesised from methanol
and CO2 , over homogeneous catalysts or heterogeneous such as
solid acid catalysts of zirconia modied by Ce and acid additives
such as phosphoric acid, or as a support for heteropolyacids, or
via cyclic carbonates (CO2 with epoxides), the cycloaddition of oxi-
ranes and oxetanes and CO2 over e.g. CeO2 ZrO2 or homogeneous
metal complexes catalysts, or coplymerisation of CO2 and oxiranes
on metal complexes, the synthesis of urea (CO2 + NH3 ) and ure-
thane derivatives, e.g. CO2 + secondary or primary amines giving
carbamic acid which reacts with organic halides or alcohols giving
carbamates (urethanes) or are dehydrated to isocyanate without
using phosgene, the synthesis of carboxylic acids, e.g. acrylic acid,
the synthesis of esters and lactones by combining CO2 with unsat-
urated compounds such as vinyl ethers, the hydrogenation and
hydroformylation of alkenes by CO2 and H2 , and so forth [353].
Currently, the utilization of CO2 as a chemical feedstock is lim-
ited to a few processes, such as the synthesis of urea (for nitrogen
fertilizers and plastics), salicylic acid (a pharmaceutical ingredient)
and polycarbonates (for plastics). It is worth noting that the actual
use of CO2 corresponds to a small percentage of the potential CO2
that is suitable to be converted into chemicals; thus, a chemical
transformation of CO2 may signicantly contribute to a reduction
of its emissions, in particular for the fuel pool, the worldwide con-
sumption of which is two orders of magnitude greater than that
of chemicals. Note that CO2 transformation requires energy, which
may produce CO2 . Thus, the importance of the transformation of
CO2 into useful chemicals should be closely related to the impor-
tance of utilizing a renewable feedstock [353].
Different options exist in heterogeneous catalysis for the con-
version of CO2 . The hydrogenation of CO2 to form oxygenates
and/or hydrocarbons are the most intensively investigated area of
CO2 conversion. Methanol synthesis from CO2 and H2 has been
investigated at the pilot-plant stage with promising results. An
alternative possibility is the production of DME, which is a potential
diesel substitute. Ethanol formation, either directly or via methanol
homologation, and the conversion of CO2 to formic acid are also
potentially interesting routes. Methanol, ethanol, and formic acid
may also be used as feedstocks in fuel cells, which provide a route
to store energy from CO2 and then produce electricity.
The hydrogenation of carbon dioxide to hydrocarbons consumes
much more hydrogen (per unit of product) than the formation
of oxygenates. Therefore, this route is, in principle, only valuable
when hydrogen is made primarily from renewable or non-fossil
resources; however, other thermodynamic aspects must also be
considered. The dry reforming of methane with CO2 is a known
technology that is available on a nearly industrial scale, although
the positive impact on CO2 emissions is questionable [362364].
Specically, it is important to ensure that CO2 emissions due to
energy consumption are not greater than the amount of CO2 con-
sumed in the reaction. An improvement in the positive direction is
tri-reforming, which operates autothermically and does not require
a pure CO2 feed stream; however, large-scale demonstration units
are necessary [365,366].
The conversion of CO2 at room temperature and atmospheric
pressure using solar light represents a highly challenging approach
to close the CO2 cycle and develop approaches that mimic photo-
synthesis. An interesting solution could be a photoelectrochemical
(PEC) reactor that operates in the gas phase and uses nanoconned
electrodes that differ from those used in conventional PEC systems,
as described [247].
7. Activation and upgrading of light alkanes
Alkanes are currently two to three times cheaper than the corre-
sponding olens and are thus quite valuable for upgrading. Olens
are mainly used for polymerization processes. There are several
possibilities to up-grade to light alkanes (C2 C6 ). An isomerization
reaction on an acid catalyst can yield branched alkanes of higher
octane number. An acid catalyzed alkylation reaction on isobutane
with butene can yield trimethyl pentanes of high octane number
or other isomers, such as dimethyl hexanes, of much lower octane
number [367369]. The main industrial catalysts are HF and H2 SO4
in solution [370], although signicant efforts have been made in
the past 30 years to nd a solid substitute without yielding any
reliable/promising process. No industrial processes could emerge
as deactivation due to fouling by butene polymerization residues
was too important and selectivity to TMP versus dimethyl hex-
anes (DMH) of low octane number was too low (5060). Another
approach is to proceed by dehydrogenation, e.g., on Pt-Sn/Al2 O3 ,
or by oxydehydrogenation of alkanes on V-based mixed oxides.
The former reaction is endothermic and highly sensitive to deac-
tivation by coke deposits [371373]. The latter is exothermic with
 I. Fechete et al. / Catalysis Today 189 (2012) 227
low deactivation by coke fouling, but it may lead to total oxida-
tion and CO2 formation and, thus, to a lower selectivity to alkenes.
A third way is oxidizing/ammoxidizing the alkanes to the corre-
sponding oxygenates or oxynitriles such as aceto or acrylo-nitriles,
aldehydes, ketones or acids. Two processes have been developed
industrially, oxidation of butane to maleic anhydride on a vanadyl
pyrophosphate based VPO catalyst or ammoxidation of propane to
acrylonitrile on MoVTeNb mixed oxide catalysts. Maleic anhydride
is a raw monomer for resin and for THF an industrial solvent pro-
duced by Reppe process of maleic ahydride reduction pn Pd catalsyt
as well as a monomer for segmented polyurethanes (Lycra) and
copolyester elastomers (Hytrel). Vanadium-based catalysts [374]
and in particular, vanadium phosphates (VPOs) are very well known
as the only catalysts for industrial process of n-butane oxidation
to maleic anhydride [375378], which is a precursor of polyester
resins [379]. In general, VPO catalysts are inexpensive and attrac-
tive in selective oxidation processes since they are environmentally
friendly [380]. The reaction follows Mars van Krevelen mechanism
where the adsorbed organic molecule is oxidized by lattice oxygen
from the catalyst, which is subsequently restored by oxygen reac-
tion feed. Acrylonitrile was produced in ammoxidation reaction of
propylene using FeBiMoO and FeSbO systems as catalysts
but this process would be replaced in a near future by ammoxi-
dation of propane due to the lower cost and abundance of propane.
Acrylonitrile is the main raw material for production of synthetic
bers, plastics, elastomers and polymers as styreneacrylonitrile
and acrylonitrilebutadienestyrene. By polymerization of acry-
lonitrile with butadiene synthetic rubber is produced. This process
includes multifunctional molybdates and antimonates as catalysts.
However, propane conversion is about ten times lower than that
of propylene in the same conditions since the activation energy
of C H bond is higher. The more performing catalyst developed
recently by Japanese industrialists [381,382] is a mixed MoVNbTe
oxide active for the (amm)oxidation of propane to (acrylonitrile)
acrylic acid [381384]. A process, designated AlkyClean using a
solid acid catalyst (HY-zeolite based) and claimed to be compet-
itive with other two processes, was proposed [355] by Akzo Nobel,
ABB Lummus Global and Fortum with a demonstration unit con-
structed at Fortum facilities in Porvoo, Finland. The reaction is
carried out in liquid phase at 5090 C with isobutane to olen ratio
(i/o) of 8 to 10 against 410 C and i/o = 810 for H2 SO4 and 3238 C
and i/o = 1215/1 for HF respectively. Regeneration was realized at
250 C under hydrogen. For this research part see special issue of
Appl Catal A, Ed. G.S. Patience, J.M. Lpez-Nieto [385].
8. Waste air, water and VOCs treatments
Wet air oxidation (WAO) is a liquid-phase reaction between
organic material in water and oxygen. The WAO process is used
around the world to treat industrial wastewaters and sludges
at moderate temperatures (180315 C) and at pressures from 2
to 15 MPa. Under these conditions, complex organic compounds
are primarily oxidized to carbon dioxide and water, along with
simpler forms that are biodegradable. Unlike other thermal pro-
cesses, WAO produces no NOx , SO2 , HCl, dioxins, furans or y ash.
However, the efciency of aqueous-phase oxidation can be signif-
icantly improved by the use of catalysts, either heterogeneous or
homogeneous. Moreover, key points to be solved are the stability
of the heterogeneous catalysts and the recycling of the homo-
geneous catalysts. Commercial catalytic WAO (CWAO) processes
started as early as the mid-1950s in the USA. Several Japanese
companies developed CWAO technologies that relied on hetero-
geneous catalysts based on precious metals deposited on titania or
titaniazirconia. Compared with conventional WAO, CWAO offers
lower energy requirements and signicantly higher oxidation
19
efciencies. Further developments of this technology should
include highly durable and low-cost catalysts. CWAO provides an
environmentally attractive option to manage the growing problems
of the treatment of organic sludge and toxic wastewater [386,387].
The treatment of toxic nitrogen-containing compounds, which
are mainly produced in the chemical and pharmaceutical indus-
tries, is one of the major applications of the wet air oxidation
(WAO) process. Many studies have dealt with the oxidation of ani-
line, which is often chosen as a model molecule of a dye-industry
pollutant. Particular attention has been paid to selectivity toward
organic by-products (especially azo, nitroso and nitro compounds,
phenolic compounds and carboxylic acids) and inorganic forms of
nitrogen (NH4 + , N2 , NO2 , NO3 ). Usually, similar catalysts can be
used for the CWAO of oxygen-containing (phenol, carboxylic acids)
and nitrogen-containing organic compounds. Ammonia is one of
the most refractory by-products formed during catalytic WAO of
nitrogen-containing organic pollutants and is itself a pollutant.
Very high selectivities to dinitrogen have been obtained on certain
noble-metal catalysts. As a rule, catalysts that are active and selec-
tive for ammonia oxidation are different (nature of active phase,
support, etc.) from the solids proven to be the best catalysts for the
CWAO reactions of organic compounds. Multifunctional catalysts
are therefore required for the treatment of nitrogenous organic
compounds.
Volatile organic compounds (VOCs) are signicant atmospheric
pollutants due to their high toxicity and malodorous nature.
VOC emissions arise from mobile sources and industrial appli-
cations. In this context, the degradation of VOCs has become a
major area of research in environmental protection during recent
decades [388,389]. Common VOCs such as halogenated hydrocar-
bons, ketones, alcohols and aromatic compounds have been widely
used in many industries and are often found in the emissions ow
[390,391].
Traditional methods of removing VOCs from the polluted air
stream include adsorption onto activated carbon or zeolite and
thermal combustion. These methods have inherent limitations. The
adsorption process includes recovery treatments that require the
regeneration of the adsorbent and also requires durability, whereas
the high temperature of VOC degradation makes thermal degrada-
tion not economically feasible.
Many advanced technologies have been developed for the rapid
and economical removal of VOCs from indoor air. Among these,
catalytic oxidation is the most innovative and promising approach.
This oxidation process is promising for air purication because
the pollutants can be oxidized to H2 O and CO2 . The catalysts play
the most important role by converting polluting compounds into
relatively harmless compounds at low operating temperatures.
A series of catalysts were evaluated for VOC decomposition
[388,389,392402]. The most active catalysts are the noble metal
catalysts dispersed on high surface area supports. The dispersion
increases both the available metal surface area and the thermal
stability. Many researchers have suggested that the performance of
noble metal supported catalysts for the oxidation of VOCs is highly
dependent on the oxidation state of the metal. Some authors have
suggested that the oxide species are more active than the metallic
species for catalytic oxidation, while others argue the opposite.
In the case of catalysts with the same oxidation state, the particle
sizes may play a more important role in the catalytic activity [403].
Several studies have shown a correlation between the catalytic
activity and the oxidation state of the catalyst, the nature of the
support, the metal-support interaction, and the morphology of the
catalyst particles [389,403417]. However, the use of noble metals
leads to a high cost purication system and the natural reserve of
noble metals is limited. Therefore, the substitution of noble metals
with ubiquitous elements is required for environmental and
economic reasons. Metal oxides have been reported as relatively
20 I. Fechete et al. / Catalysis Today 189 (2012) 227
high activity catalysts for the complete oxidation of VOC [392,393].
Research efforts in this eld are oriented towards the development
of new catalytic materials with low manufacturing costs that show
high activities at moderate temperatures.
9. Photocatalysis
In the 1930s, the term photocatalysis was introduced as new
branch of catalysis. Photocatalysis is dened as a change in the rate
of a chemical reaction under the action of light in the presence
of photocatalysts that absorb light quanta and are involved in the
chemical transformations of the reaction participants [418,419].
The photocatalyst is dened as a solid that functions by pho-
toinduced electron transfer at moleculesemiconductor interfaces
[282,420423].
Among photocatalytic applications, photocatalytic oxidation
and the reduction of organic compounds in water have become
important and have received considerable attention during the last
few years [282,424427]. These applications involve the oxidation
or reduction of an organic compound to an intermediate that con-
tains oxygen or to carbon dioxide, water, and a mineral acid if a
heteroatom such as nitrogen or chlorine is present. The mecha-
nism of the photocatalytic decomposition of organic compounds is
supposed to follow these steps: under UV-light illumination, the
absorption of photons creates an electronhole pair if the photon
energy is greater than that of the band gap; thereafter, the pairs
migrate to the surface and are trapped by OH surface groups and
other surface sites, thereby forming hydroxyl (OH ), hydrosuper-
oxide (H2 O) and superoxide (O2 ) radicals; these free radicals
nally cause the oxidation of the organic compounds [425428].
This process can be used in various areas such as the elimina-
tion of odor from drinking water, the degradation of oil spills in
surface-water systems, and the degradation of harmful organic
contaminants, such as herbicides, pesticides, and refractive dyes.
One of the most widely studied metal oxides is semiconducting
TiO2 [423]. Three common TiO2 polymorphs exist in nature, which,
in the order of abundance, are rutile, anatase, and brookite. An
additional synthetic phase, called TiO2 (B), and some high-pressure
polymorphs are also known [428]. The rutile and anatase poly-
morphs are primarily used in photocatalysis. Both the rutile and
anatase crystal structures comprise distorted octahedra. In rutile,
a slight distortion from orthorhombic geometry occurs, where the
unit cell is stretched beyond a cubic shape. In anatase, the distortion
of the cubic lattice is more signicant, and thus, the resulting sym-
metry is less orthorhombic [429]. Titania, in anatase form, exhibits
a strong photocatalytic effect, which generates electronhole pairs.
As a result, the material can harvest photons in the near-UV region
(<410 nm) to provide its surface strong oxidizing power to decom-
pose organic molecules. Photocatalysis is a rapidly growing eld of
study that has attracted intense attention of chemical and materials
researchers in recent years.
Even though TiO2 exhibits excellent photocatalytic activities
in the decomposition of VOCs and other organic compounds, the
study new photocatalysts with different structures that exhibit
higher activity is desirable. In this regard, the novel photocata-
lysts made of highly donor-doped (110) layered perovskites, have
recently been developed and were found to be much more ef-
cient than bulk-type TiO2 . This higher activity results from the
highly donor-doped electronic structure, which leads to a nar-
rower depletion region and a more facile separation of the charge
carriers.
Selective photocatalysis can be achieved using proper molec-
ular sieves, such as the titanosilicate ETS-10, which provides
an alternative approach. The photocatalytic activity of ETS-10 is
due to the presence of photoexcitable TiOTi chains and the
three-dimensional interconnected pore system of large 12-
membered ring channels in its structure, which endow the material
with excellent diffusion properties [430]. This regular channel sys-
tem has a direct effect in determining the shape selectivity of the
degradation process [431]. Another approach is the introduction
of some transition metals, such as Cr, V, Fe, Cu, Mn, Co, Ni, Mo,
or La, into the synthesis mixture of the MCM-41 and MMS [432].
The authors then demonstrated that the presence of the transition-
metal salts in the gel during the hydrothermal synthesis process
hinders the action of the template, which results in MCM-41 pores
that are not well formed. These materials were then loaded with
TiO2 via the solgel method, and the activity of the TiO2 /TM-MCM-
41 catalysts toward the degradation of 4-chlorophenol was tested
in the presence of UV and/or visible light. The results showed that,
although some metals were deleterious, others improved the per-
formance of the photocatalysts and even enabled them to utilize
visible light. A wide range of other semiconductors and materials
have been tested for photocatalytic activity. In general, they have
been found to be less active than titanium dioxide; signicant work
has been conducted with V2 O5 , Fe2 O3 , ZnO, ZnS, CdS, Pt/CdS, ZnTe,
ZrTiO4 , MoS2 , SnO2 , Sb2 O4 , Sn/SbO2 , CeO2 , WO3 , and Nb2 O5 .
10. Solar photon conversion [433]
The efcient and cost-effective direct conversion of solar pho-
tons into solar electricity and solar fuels is one of the most
important scientic and technological challenges of this century. At
least 20 TW of carbon-free energy (1.5 times the total amount of all
forms of energy consumed today globally), in the form of electricity
and liquid and gaseous fuels, are estimated to be required by 2050
to avoid the most serious consequences of global climate change
and to ensure an adequate global energy supply that will avoid
economic chaos. However, for solar energy to contribute a major
fraction of future carbon-free energy supplies, it must be priced
competitively with, or perhaps even be less costly than, energy from
fossil fuels, nuclear power and other renewable energy resources.
The challenge of delivering very low-cost solar fuels and electric-
ity will require breakthrough advances in both fundamental and
applied sciences. These required advances include new concepts for
low-cost photovoltaic (PV) energy based on chemistry, solar water
splitting, redox catalysis for water oxidation and reduction, pho-
toelectrochemical energy conversion, and photoinduced electron
transfer. Note that the total energy capacity at the end of 2009 was
approximately 7 GW-years (0.2% of global electricity usage). Thus,
there is potential for the PV industry to grow substantially in the
future (by a factor of 100300) for it to provide a signicant frac-
tion of the total global electricity needs (currently approximately
3.5 TW).
Presently, solar-derived fuels are produced from biomass
(labeled as biofuels) and are generated through biological pho-
tosynthesis. The global production of liquid biofuels in 2009 was
approximately 1.6 million barrels/day, equivalent to a yearly
output of approximately 2.5 EJ (about 1.3% of global liquid fuel uti-
lization). The direct conversion of solar photons to fuels produces
high-energy chemical products that are labeled as solar fuels; these
fuels can be produced through nonbiological approaches, which
are generally referred to as articial photosynthesis. The feedstocks
for articial photosynthesis are H2 O and CO2 , which react either as
coupled oxidationreduction reactions, as in biological photosyn-
thesis, or by rst splitting H2 O into H2 and O2 and then reacting H2
with CO2 (or CO produced from CO2 ) in a second step to produce
fuels through the known chemical routes previously described such
as syngas, watergas shift reaction, or alcohol synthesis. The solar
generated H2 can itself be used as a gaseous fuel, such as in fuel
cells. However, currently, no solar-fuels industry exists. Signicant
 I. Fechete et al. / Catalysis Today 189 (2012) 227
Fig. 16. Major factors inuencing selectivity in catalytic reactions [455].
research and developments are required to create a solar-fuels
industry, which constitutes one of the key challenges for the future.
11. Green chemistry selectivity in catalysis
A new area of research emerged in the 1990s based on the 12
principles of green chemistry [434,435] including the atom econ-
omy, the use of reusable catalysts and the minimization of waste
[436]. The principle of green chemistry is that rather than using
every possible chemical process, only those that are environmen-
tally benign should be used [437]. Within green chemistry, there
is an increasing interest in developing novel materials that can be
applied as heterogeneous catalysts for chemical processes, replac-
ing effective but hazardous chemicals, such as H2 SO4 , HF and AlCl3 .
Processes using these novel compounds, such as zeolites, have very
high E-factors, a quantitative parameter that can be used to assess
the environmental acceptability of a process [438]. It corresponds
to the ratio of kilograms of waste divided by kilograms of product.
For example, the zeolites used in the petrochemical industry have
an E-factor of 0.1 (high greenness) and have been widely imple-
mented in very large scale industrial processes because they can
easily be separated from the products and reused. Because of their
lack of toxicity, they constitute a prime example of green chemistry.
Moreover, a challenge for the XXIst century is the control of
technological processes in the chemical, petrochemical, and phar-
maceutical industries to develop atom-economical, environmental
friendly processes without by-products [3,439441]. The chemical
and petrochemical industries have always attempted to improve
process efciency and reduce waste using heterogeneous catalysts
[293,442447]. High selectivity is the most important aspect of a
catalyst. The noble metal catalysts show high activity and selec-
tivity, but suffer from several drawbacks, including sensitivity to
metal site poisoning, the limited abundance, and the environmen-
tal impact of these metals. As a result, the tendency now is to
replace the noble metal catalysts [199,201,447449]. In light of the
ubiquitous restrictions imposed by environmental and economical
legislation, use of nanostructured porous molecular sieves, which
can be very selective for the desired products at low temperature
and are recyclable, is one alternative to the use of traditional noble
metal catalysts. We have summarized in Fig. 16 the main factors
that inuence selectivity in catalysis and that must be taken into
account in all processes.
21
12. Major challenges for the future
12.1. Scientic challenges
These challenges cover the design, preparation, evaluation, and
optimization of new catalytic materials, the probing/understanding
of catalyst behavior (activity and selectivity) at the molecular level,
the enhancement of technology transfer between academia and
industry (bridge the gap), the development of multifunctional reac-
tors, combinatorial catalysis, high-throughput catalyst testing, the
characterisation of catalysts using highly improved physical and
chemical techniques, particularly used under working conditions
and simultaneously with several other techniques together [451],
heterogeneisation of homogeneous catalysts (vide supra Section
2.9), the coupling of chemical and engineering kinetics, and so forth.
12.2. Environmental challenges
These challenges consist of minimizing and/or managing
by-products by converting them to useful products, replacing mul-
tistep processes by direct schemes to avoid exposure to dangerous
intermediates, reducing efuents (gases, solvents, salts), and using
sustainable sources of raw materials and energy supplies. The
development of biomass for raw chemical materials and energy
sources should become a key point for the future. The develop-
ment of bioreneries is in its infancy; however, with reference to
the past the in petroleum industry, one may imagine that great
improvements will be developed with continuous research in this
eld.
12.3. Economical challenges
Economical challenges naturally correspond to the use of
cheaper, readily available raw materials, increased productivity,
decreased lag-time between discovery to commercialization, the
discovery novel catalytic reactions, the development of processes
that are more selective and intensive, the accelerated discovery of
new catalysts-based on non noble metals [199,201], and the eval-
uation and scale-up of processes.
12.4. Energy challenges
Energy challenges correspond to reduce energy consumption,
e.g. by favouring of hydrogen production as a source of energy
and as an important chemical material, to develop efcient water-
splitting technologies, and to enhance uses [452] of biomass and
other renewable sources, such as solar, wind, hydroelectric, and
nuclear energies. All these technologies must be developed as alter-
native sources to fossil energies. One is still very far from replacing
fossil energies, and great effort is required on a short time scale. The
future will rely on solar energy and the implementation of efcient
methods for electrical energy storage [450,453]. However, signif-
icant scientic advancement is still required for the practical and
safe deployment of both of these technologies. In 2005, 7% of the
world energy use was derived from nuclear power (Fig. 13), 10% was
derived from biomass, 2% was derived from hydroelectric sources,
and a mere 1% of the energy consumed was obtained from alternate
renewable resources. Closer examination of the tiny 1% fraction
shows that both solar energy in the form of photovoltaics and wind
power are drastically underemployed (Fig. 13). These technologies,
of course, represent two renewable resources of an innite supply.
12.4.1. Challenges in automotive catalysis
Since the introduction of exhaust gas converters in cars in
1976 by Ford, many advances have been realized in reformulated
gasoline or diesel, in particulate emission/trapping control and in
22 I. Fechete et al. / Catalysis Today 189 (2012) 227
Table 6
Major problems and challenges in automotive car industry.
Challenge Drivers
Lean burn gasoline engine Efciency higher by ca. 25%
Dry particulate emissions from diesel engines DOC reduces SOF, HC, and CO; no
current catalyst/system to treat dry
soot
Diesel engine lean NOx Direct decomposition or reduction of
NOx in O2 -rich atmosphere
electronic devices to regulate the air/fuel ratio in the motors. The
initial three way catalysts for simultaneous CO oxidation, NO reduc-
tion, hydrocarbon total oxidation were improved further with the
use of Pd. Another presentation by R. Farrauto et al. [454] provides
details of the actual performances and of the future prospects. Only
some major issues are summarized in Table 6. Moreover, the devel-
opment of highly active HDS, FCC, Naphtha catalysts is one of the
most urgent challenges in the petroleum industry not only to pro-
tect the environment but also to efciently utilize limited natural
resources.
13. Conclusions
As we have described in this review, our dependence on fos-
sil fuels (coal, petroleum, and natural gas) is largely due to their
chemical energy being the most convenient and useful form of
transportable energy. However, the extensive use of fossil fuels
has dramatically inuenced the environment and peoples health,
while world reserves are diminishing inexorably, although new
elds are still being discovered and although methane hydrates
may provide a substitute for some time. This situation cannot last
for long, and substantial advances are urgently needed.
We have also shown that the solution to the challenge of clean
energy can arise from simple components: sunlight and water
[455]. Sunlight and water are innite resources and can provide the
required diversity of energy supplies. To store energy from sunlight,
water can be split to generate hydrogen, a clean and portable energy
carrier that can then be used to supply electricity when needed.
High-performance, light-weight batteries can be used to power
electric vehicles. However, such technological advances require
systems that are capable of producing electricity, breaking H2 O
bonds with the separation of H2 and O2 , and storing the energy
either in batteries or as molecular hydrogen. Currently, such sys-
tems pose formidable challenges in terms of the required materials,
efciency, cost, and design of practical devices.
The locus of activity in catalysis continues to move. In the
eighteenth and nineteenth centuries, major discoveries and devel-
opments were performed in Europe. In the twentieth century, both
Europe and the USA were the major contributors, although Japan
and Korea also provided important efforts and discoveries in the
second half of the century. For the twenty-rst century, China,
Korea, Japan and other Asian countries are expected to lead in the
eld of catalysis.
At the end of the last century, major large chemical industrial
companies have more or less abandoned large catalysis research
centres within their laboratories. They now rely on catalysts pro-
ducers, institutes and/or academic researchers to discover new
catalysts or develop new technologies.
The development of surface, bulk and in situ characterisation
techniques [451], molecular modelling, and advanced synthesis
methods have transformed the preparation of solid catalysts and
the characterisation of their physical and chemical (catalytic) prop-
erties from an art into a science. Such a trend should and will
continue in the future with the new generations of scientists, engi-
neers and researchers.
Problem
NOx trapping; SOx tolerant traps
Catalyst to lower lightoff T of soot;
addition of Cu and Ce-organometallics
to fuel
Larger operating window for PM or
BM-catalysts, NH3 or urea SCR.
Acknowledgement
Support from CNRS France is gratefully acknowledged by I.
Fechete.
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