CHAPTER-1

Chapter 1 Introduction

Chapter 1 Introduction
1.0 General introduction
Chemical technology necessitates a paradigm shift from traditional concepts of process
efficiency, that focus largely on chemical yield, to one that assigns economic value to
eliminating waste at source and avoiding the use of toxic and/or hazardous substances [1-9].
Catalysis is a growing need for environmentally acceptable process to improve sustainability of
the chemical processes in chemical industry due to their eco-friendly nature [1,10,11]. A
catalyst is that which accelerates chemical reactions by opening alternative mechanisms with
lower activation energies [12]. Catalysis play a key role in petrochemical industries and
manufacture of a wide variety of speciality chemicals such as pharmaceuticals, agrochemicals,
and fragrances. The other examples include catalytic cracking, hydrocracking, alkylation,
isomerization, oligomerization, hydration/dehydration, esterification, hydrolysis and a variety
of condensation reactions [13,14]. However, a serious issue concerned with use of
homogeneous catalysts in these processes form a large amount of inorganic salts as by-products
whose disposal is a solemn problem due to the strong environmental consciousness and
stringent regulations. Heterogeneous catalysis is most often used in modern industry that can
provide significant advantages over homogeneous catalysts in terms of stability, corrosion, ease
of handling, recovery, regeneration, and less contamination. They can also be designed to give
increased activity, selectivity, longer catalyst life, and reusability [13,15]. The fast development
of catalyst design, however, made it possible to apply various heterogeneous catalysts in
industrially important organic transformations.
Acid catalysis is one of the most important areas for the application of heterogeneous
catalysis. Industrially a wide variety of solid acid catalysts including zeolites, silica-alumina
mixed oxides, acidic clays, heteropoly acids, sulfated metal oxides, acidic resins were examined
for acid catalyzed reactions [16,17]. High product selectivity can depend on the fine-tuning of
solid acid properties. Among the solid acid catalysts, polyoxometalates familiarly known as
heteropoly acids (HPAs) show appreciable acid catalytic properties that are of practical
importance [18,19]. HPAs exhibit a variety of structures and properties that make them useful
in catalysis, material science and medicine [20]. The HPAs are widely used as acid, redox, and
bifunctional catalysts in homogenous and heterogeneous system because of their high solubility
in polar solvents and fairly high thermal stability in the solid state [18-22]. The pore size and
acidity of the heteropoly acid can be controlled by the counter ions. The tunable redox

1
Chapter 1 Introduction

properties of HPAs made them as both heterogeneous and homogeneous catalysts. Hence they
can be used in solution as well as in the solid state [23]. As the acid HPAs are non porous they
need to be supported on a porous solid or altered into microporous insoluble salts [24].
Concerted efforts have been made towards developing a new type of modified heteropoly acids
as heterogeneous catalysts for acid catalyzed reactions such as Friedel-Crafts benzylation
reaction.
1.1 Polyoxometalates
Polyoxometalates (POMs), composed of early transition-metals of group V and VI (V,
Nb, Ta, Mo, W etc.) in their highest oxidation states, are a vast class of metal-oxygen clusters
with a variety of chemical composition and definite structures [25]. Generally, there are two
specific families of POMs, namely, (i) isopolyoxometalates and (ii) heteropolyoxometalates.
Isopolyoxometalates consists of a metal-oxide cluster with only the d0 metal cations (Mo6+,
W6+, V5+ etc.) with a general formula [MmOy]n-. Heteropolyoxometalates are composed of a
metal-oxide framework together with one or more p-, d- or f- block heteroatoms (P, Si, B, Mn,
Co, Gd etc.) often in different oxidation states with general formula [XxMmOy]p-, where x < m
[26].
Based on the well-defined pioneering work, polyoxometalate chemistry has become one
of the fastest developing areas, in virtue of their fascinating architectures [27,28], excellent
physicochemical properties, including strong Bronsted acidity, fast reversible multielectron
redox transformations, high proton mobility and high solubility in polar solvents and fairly high
thermal stability in the solid state [20]. They find rapid development in various applications
such as optics, electronic materials, magnetic materials, medicine (antiviral, anti-HIV activity),
electronics, and catalysis [18,21,26,29-40]. Since the first polyoxoanion [PMo12O40]3- was
reported by Berzelius in 1826 [41], they have drawn attention since 1933 when the first X-ray
crystal structure of POM was discovered by Keggin [42]. Most of the researches on POMs
chemistry focused on the two systems: tungsten based POMs (polyoxotungstates) and
molybdenum based POMs (polyoxomolybdates).
1.1.1 Classification of heteropolyoxometalates
Heteropolyoxometalates are with complex structure, which consists of metal-oxygen
octahedral as basic structure unit [21]. Their general formula is [XxMmOy]n- (x < m). M is
usually Mo or W and to a lesser extent V, Nb or Ta. The heteroatom X, can be one of 64
elements that belong to a various groups of the periodic table except noble gases [43].

2
Chapter 1 Introduction

According to the molecular architectures, ratio between polyatom and heteroatom

polyoxometalate structures are classified. Several structures were proposed for heteropoly
acids, the most important three classes of heteropoly ions are shown in Figure 1.1 [44,45].
These are Keggin, Wells-Dawson and Anderson structures. The general chemical formula and
structures of heteropoly ions are listed in Table 1.1.

Figure 1.1 Structure of heteropoly ions (A) Keggin, (B) Wells-Dawson, and (C) Anderson.

Table 1.1 Different types of heteropolyoxometalates

Chemical formula (M = W) Heteroatom (X) Structure

[Xn+M12O40](8-n)- P5+, As5+, Si4+, Ge4+ 1:12 Keggin [41]

[Xn+M11O39](12-n)- P5+, As5+, Si4+, Ge4+ 1:11 lacunary Keggin

[X25+M18O62]6- P5+, As5+ 2:18 Dawson [46]

[Xn+M6O24]n- Te6+, I7+ 1:6 Anderson [47]

The important features of each type of heteropoly ions are explained briefly,
i) Keggin heteropoly ion
Keggin type heteropoly anion can be represented as, XnM12O40(8-n)-, where X = heteroatom. The
ratio between addenda atom and heteroatom for these compounds is 12, (M/X =12). These are
the well-known and widely studied compounds for various applications among which catalytic
applications are most important due to their relatively high thermal stability, redox and acidic
properties. The heteroatom X is usually either P5+ or Si4+ and hardly ever Co3+, Ge4+ and many
others have been reported to act as heteroatom and M is usually W6+ or Mo6+.

3
Chapter 1 Introduction

In Keggin heteropoly anion a subclass called lacunary Keggin anion which are formed
by the removal of one MO6 octahedron (stoichiometrically one MO unit is lost) from the
Keggin anion with the formation of XM11O39n-. The formation of lacunary compounds is
obtained by the raising pH of the solution at which the Keggin structure is unstable, and is
hydrolyzed with progressive loss of one or more MO entities.
ii) Wells-Dawson heteropoly anion
General formula of the Wells-Dawson heteropoly anion is X2n+M18O62(2n-16)-, (X is P5+, S6+,
As5+; M is W6+, Mo6+). The ratio of addenda and heteroatoms for these compounds is 9 (M/X =
9). These HPAs are formed via dimerization of two XM9O34 moieties under increased pH at
which the parent Keggin compound forms the corresponding tri lacunary compounds by the
loss of MO groups [48,49].
iii) Anderson heteropoly anion
The general formula of Anderson HPA compounds is XM6O24n- (X = Mn4+, Ni4+, Pt4+,
Te6+; M = Mo6+, W6+). The ratio between addenda and heteroatoms is 6 (i.e., M/X = 6). These
compounds possess a hexagonal plane structure composed of a central X ion surrounded by six
octahedral MO6 groups. Each MO6 shares an edge with each of its two neighbouring MO6 and
another edge with the XO6 octahedron [50].
1.1.2 Structure of heteropoly acids
The first heteropoly anion [PMo12O40]3- was reported in 1826 by Berzelius [41]. Several
conjectures were made on the structure of HPAs, particularly by Alfred Werner followed by
Linus Pauling. Finally a century later in 1933, J.F. Keggin from the University of Manchester
performed powder X-ray diffraction studies on the similar free acid H3PW12O40 and determined
its structure, which is known as the Keggin structure [51].
The primary structure of H3PMo12O40 is the well-established Keggin unit (KU), in
which a central P atom in tetrahedral co-ordination (PO4) is surrounded by 12 metal-oxygen
octahedral (MO6) units [25,41]. The Keggin unit contains a negative three charge which is
neutralized in the acid form by three protons. There are four types of oxygen atoms in a KU
(Figure 1.2). There are 4 central oxygen atoms (Oa), 12 oxygen atoms that bridge two
molybdenum atoms sharing a central oxygen atom (edge-sharing Oc), 12 oxygen atoms that
bridge molybdenum atoms not sharing a central oxygen atom (Ob), and 12 terminal oxygen
atoms (Od) bound to a single molybdenum atom.

4
Chapter 1 Introduction

Figure 1.2 Ball and stick representation of Keggin anion (Red: Oxygen, Magenta:
Molybdenum, Yellow: Phosphorus).

The examples of Keggin type heteropoly acids are:

H3PMo12O40 - 12-phosphomolybdic acid
H3PW12O40 - 12-phosphotungstic acid
H4SiMo12O40 - 12-silicomolybdic acid
H4SiW12O40 - 12-silicotungstic acid
These different Keggin HPAs are known based on their central and addenda atoms.
HPAs based on P and Si central atoms and Mo and W as addenda atoms are available. The
Keggin structure is not rigid and has five geometrical rotational isomers, also known as Baker-
Figgis isomers. These ions are known to exist in form and this term is frequently used in
several applications including heterogeneous catalysis [46]. Although occasionally employed in
heterogeneous catalysis, atleast in part as a result of their instabilities, the , , and isomers
of the Keggin anion (Figure 1.3) are of some interest.
The -Keggin structure is identical qualitatively to the -Keggin unit but with one of the
three edge-shared M3O13 triplets of the latter rotated by 60 [52]. The inter nuclear separations
between the two M atoms in the form are shorter than those in the structure and the M-O-M
angles are smaller, which may account for the lower stability of the former structure.
Consequently, columbic repulsions between peripheral metal atoms in the edge sharing should
be more substantial than those in the corner sharing structures, possibly accounting for the
relative stabilities of the and forms [53].

5
Chapter 1 Introduction

Figure 1.3 Different rotational isomers of the Keggin ion starting from the parent -isomer.
Red octahedra: MO6 groups, green octahedra: MO6 groups belonging to a rotated triad, green
ball: heteroatom.

1.1.3 Primary, secondary and tertiary structures of heteropoly acids

Generally, heteropoly acids and their salts form ionic crystals composed of heteropoly
anions (primary structure), counter cations (H+, H3O+,H5O2+), hydration water, and other
molecules. The hierarchical structure of solid HPAs is important for the understanding of their
catalytic activity and the substructures were denoted as primary, secondary and tertiary [47]. A
schematic model for the microstructure of heteropoly acid is shown in Figure 1.4.
The primary structure is the heteropoly anion itself [PW12O40]3- i.e., Keggin structure.
The arrangement of primary structure together with counter cations forms the secondary
structure (Eg. Cs2.5H0.5PW12O40). The secondary structure is flexible which depends on the
amount of hydration water, counter cation and heteropoly anion.
The aggregates of secondary structures in three dimensional manner give the tertiary
structure. It explains the formation of solid particles and relates to properties such as particle
size, surface area, pore structure, and distribution of protons in particles [54]. This hierarchical

6
Chapter 1 Introduction

structure of HPAs plays a crucial role in understanding and designing these as heterogeneous
catalysts. This may appear a very simple idea, but enormously helps the progress of research in
HPA catalysis.

Figure 1.4 Primary, secondary and tertiary structures; hierarchical structure of heteropoly acids
in the solid state.

1.1.4 Location of protons in Keggin heteropoly acids

Two types of protons have been determined in solid heteropoly acids. They are hydrated
protons [H(H2O)n]+ and non-hydrated protons. The location of protons in heteropoly anions has
been the subject of many studies [55-58]. The hydrated protons possess a high mobility and
they are responsible for extremely high proton conductivity of crystalline heteropoly acid
hydrates. Non-hydrated protons have much less mobility and it has been suggested that they
localize on the peripheral oxygens of the polyanion in one of three positions i.e., on M=O and
bridging oxygens M-O-M (edge sharing and corner sharing) [59]. They may also exist as free
protons without a well-defined location. In solid crystalline heteropoly acids, the protons,
hydrated or non-hydrated, take part in the formation of the crystal structure, linking
neighbouring heteropoly anions. In the relatively stable crystalline hexa hydrate

7
Chapter 1 Introduction

H3PW12O40.6H2O, bulk proton sites are represented as diaquahydrogen ions (H5O2+), which are
almost planar, quasi-symmetrical hydrogen bonded species that link four neighbouring
heteropoly anions by forming hydrogen bonds with the terminal W=O oxygen as shown in
Figure 1.5 [60,61].

Figure 1.5 Schematic structures of proposed for the states of acidic protons and water in solid
H3PW12O40nH2O (0 < n < 6).

1.1.5 Properties of heteropoly acids

The general characteristics of heteropoly ions are as following:
i) Heteropoly acids are usually very strong acids.
ii) Possess high molecular weight (oxide clusters with molecular weight ~ 2000).
iii) The lattice energies of heteropoly compounds are low thus the solvation energies of
heteropoly anions are also less. The solubility of the HPAs depends on the solvation
energy of the cation.
iv) In aqueous solution they are stable at lower pH values, but tend to be hydrolyzed at
higher pH values. The stability is elevated in organic media.
v) Heteropoly ions are multielectron oxidants and those are having Mo and V as
polyanions are relatively strong oxidants.
vi) Free acids and their salts with small metal ions (Eg. Na+, Ni2+, Cu2+, Co2+ etc.) are
extremely soluble in water and polar solvents. Salts with large ions (Cs+, Ag+ and NH4+)
are insoluble or faintly soluble. The solubility depends up on the water content of the
compounds.

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Chapter 1 Introduction

1.1.6 Acidic properties of heteropoly acids

In aqueous solution HPAs are strong acids. These are stronger than the usual mineral
acids such as H2SO4, HCl, HNO3, etc. and sometimes called as super acids [62]. The protons
present in the secondary structure of HPAs are considered as mobile protons. Thus the high
mobility of these protons made HPAs as super acids. The acid strength of HPAs vary in a wide
range depending on the polyanion structure and its constituent elements (both hetero and
addenda atoms), as well as on the extent of hydration and reduction. Among the Keggin type
HPAs phosphotungstic acid is much stronger and acidity is close to that of super acid [18,21].
The acid strength of crystalline heteropoly acids decrease in the series H3PW12O40 >
H4SiW12O40 > H3PMo12O40 > H4SiMo12O40. This order is same as to that for HPAs in solution
(Table 1.2). The tungsten acids are markedly stronger than molybdenum ones. Although, the
effect of the central atom is not as great as that of the addenda atoms, phosphorus based
heteropoly acids are slightly more acidic than silicon based heteropoly acids.

Table 1.2 Dissociation constants of heteropoly acids in acetone at 25 C [63].

Acid pK1 pK2 pK3

H3PW12O40 1.6 3.0 4.0

H3SiW12O40 2.0 3.6 5.3
H3PMo12O40 2.0 3.6 5.3
H4SiMo12O40 2.1 3.9 5.9
H2SO4 6.6
HCl 4.3
HNO3 9.4

Strong Bronsted acidity of HPAs is due to strong polarization of the outer electrons of
surface oxygen (Ot) towards M6+ ions, which results the shift of equilibrium reaction strongly to
the right to create a high concentration of protons in the form of H3O+ [64].
H

O O
H2O H3O+
M M M M

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Chapter 1 Introduction

However, when the HPA is fully dehydrated, the location of the protons is not easily
defined. The terminal (M=Ot) and bridging (M-O-M) atoms of oxygen are the most probable
positions for the protons. The calculation was proved that most energetically favourable site for
the acid proton is a bridging oxygen atom [52].
1.1.7 Catalytic applications of heteropoly acids
The applications of heteropoly compounds are based on their unique properties
including size, mass, electron and proton transfer/storage abilities, thermal stability, and
mobility of lattice oxygen and Bronsted acidity [65]. The heteropoly acids are widely used as
acid, redox, and bifunctional catalysts in homogenous and heterogeneous systems because of
their high solubility in polar solvents and fairly high thermal stability in solid state [19,21]. The
thermal stability of hydrogen forms of heteropoly acids is as follows: H3PW12O40 >
H3PMo12O40 > H4SiMo12O40 > H4SiW12O40. HPAs provide a good basis for the molecular
design of mixed oxide catalysts and they have high capability for practical uses. HPAs are used
as catalysts in solution as well as in the solid state for acid and oxidation reactions [66]. The
reasons for the heteropoly compounds to be the suitable materials for both catalyst design and
practical processes are listed below;
i) Systematic variations of acid and redox properties are possible for catalyst design.
ii) Molecular nature of solid heteropoly compounds originating from heteropoly anion
molecules enable precise design of catalysts and molecular description of catalytic
process.
iii) They can be used as bifunctional catalysts by modification.
iv) HPAs are unique as they exist in a pseudo liquid phase and can act as a phase transfer
catalysts.
v) The soft basicity of the poly anion helps in stabilizing the reaction intermediates.
Acid and redox properties of Keggin type HPAs can be controlled by the substitution of
constituent elements without changing the fundamental structure. The HPAs with Keggin-type
primary structure are polynuclear complexes principally constituted by molybdenum or
tungsten as polyatoms (M) and phosphorus, silicon or germanium as central atom or heteroatom
(X). They could be either multielectron oxidants or strong acids with an acid strength higher
than that of the classical ones.
Many of the known and new HPAs have been used for a variety of reactions, for
instance, formation of carboxylic acids from the corresponding aldehydes, as well as the

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Chapter 1 Introduction

dehydrogenation of alcohols, aldehydes and carboxylic acids to form C=C and C=O bonds [25].
HPAs have been developed and commercialized for oxidation of methacrolein to methacrylic
acid, hydration of olefins such as propene and butene, polymerization of tetrahydrofuran etc.
[66]. A commercial plant for production of ethyl acetate from ethylene by using a silica
supported HPA catalyst with 50 kt/year capacity started in Indonesia, in 1998 [67]. The
bifunctional HPA catalysts can be used for sequential hydroformylation and oxidation of
olefins [68]. HPAs also exhibit homogeneous oxidative catalytic activity such as water splitting
processes and oxygen transfer to alkanes [69]. The oxidation of alkenes and the coupling of
aromatics known as the Wacker process utilizes molybdovanadates as catalysts [70]. Catalysts
containing polyoxomolybdates are widely used in hydrodesulfurization, hydrodenitrification of
fossil fuels [71]. The latest commercial process, the direct oxidation of ethylene to acetic acid
catalyzed by palladium and HPAs produces 100,000 tons per year of the product [18]. Other
applications including ion exchange materials, ion-selective membranes and inorganic resistant
materials have also been reported [72]. It is evident that the research activity on heteropoly
compounds is very high and still growing.
1.1.8 Need for the modification of heteropoly acids
Heteropoly acids have been identified as efficient solid acid and oxidation catalysts.
Bulk form of Keggin heteropoly acids have limited number of catalytic applications since they
have associated with certain drawbacks [73]. Pure heteropoly acids have surface areas as low as
< 10 m2/g, which hinders accessibility to their strong acidic sites. Due to their relatively low
specific surface area, catalytic activity of HPAs is limited in gas solid phase reactions. High
solubility of heteropoly acids in polar solvents such as alcohols, water, and ethers cause them to
be leached during catalytic reactions involving polar molecules as reactants or products.
Furthermore, the thermal stability of pure heteropoly acids are very low and cannot be used in
vapor phase reactions.
In order to overcome these drawbacks and extend their catalytic applications for wide
range applications of these materials need to be modified.
1.1.9 Modification of heteropoly acids
Modification of heteropoly acids can be done in the following ways,
(i) By exchange of HPAs protons with different metal cations
(ii) By supporting HPAs on suitable solid supports

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Chapter 1 Introduction

(iii) By incorporation of various types of transition metal ions like V5+, Nb5+, Ta5+, and Sb3+
etc. into the primary structure of Keggin ion.
1.1.9a Metal exchanged Keggin heteropoly acids
HPAs can be modified by exchanging the protons in their secondary structure
completely or partially with metal ions without affecting the primary structure. Keggin type
metal exchanged heteropoly acids, described by formula M1xHy-xM2M312O40, where M1 = Cs+,
Rb+ etc. M2 = P or Si, M3 = W or Mo, x = 2.5 and y = 3 or 4 if M2 is P or Si respectively, are
produced by partially exchanging the protons of heteropoly acids. The HPAs modified by this
way can be used as catalysts [21,74,75]. Metal exchanged heteropoly acids can be classified
into two groups [76].
(1) Group A are the HPAs whose protons are exchanged with small metal ions like Na+, Cu2+.
These group A HPAs posses
low surface area (1-15 m2/g),
high solubility in water,
absorption capability of polar or basic molecules.
(2) Group B are the HPAs with large cations like Cs+, Rb+ and these exhibit
high surface area (50-200 m2/g),
insoluble in water,
unable to absorb molecules.
Exchange of protons with metal ions would enhance the thermal stability and surface
area of the catalyst. The catalytic behaviour of metal exchanged HPAs has received
considerable interest, because of its multifunctional catalysis [77]. Various metal ions such as
Cu2+, Fe3+, Ag+, Al3+, Sn4+ etc. have been used to exchange the protons of different Keggin
HPAs [78-82]. The Keggin structure of HPA remains stable even after exchanging of its
protons with different metal ions. The acidic properties of HPAs depend up on the number of
protons exchangeable in the secondary structure of the Keggin ion. It has been reported that
partially exchanged HPAs exhibit high acidity compared to fully exchanged or parent acid due
to high mobility of the protons [83].
Partial exchange of protons of heteropoly acids with large cations such as Cs+, Rb+,
NH4+, K+ etc. converts a water-soluble acid with low surface area (<5 m2/g) into a water-
insoluble acid salt with surface area exceeding 100 m2/g [84,85]. Heteropoly salts are more
stable than the parent acid. However, the relative stabilities depends up on the counter cation

12
Chapter 1 Introduction

[60]. The thermal stability varied generally in the order of metal ions Ba2+, Co2+ < Cu2+, Ni2+ <
H+, Cd2+ < Ca2+, Mn2+ < Mg2+ < La3+, Ce3+ < NH4+ < K+, Tl+, Cs+ [18]. The acidic cesium salt
Cs2.5H0.5PW12O40 is more stable than parent H3PW12O40. No decomposition of the salt was
observed even at 500 C, while the parent acid decomposes at relatively lower temperatures
(300 C). In the case of metal exchanged HPAs, polar molecules like water and alcohol can
easily enter and exit the bulk, which leads to expanding or contracting the distance between the
Keggin anions in the crystal lattice. While non polar molecules like hydrocarbons cannot enter
into the bulk. Due to this nature of the secondary structure, some reactions may proceed in the
bulk at the state called the pseudo liquid phase. Unlike polar molecules, non polar reactants are
incapable of being absorbed in the bulk of a heteropoly acid. They interact only with the surface
of the catalyst [18].
The formation of certain HPA salts of metal ions (Mn+) of PW12O403- (M3/nPW12O40)
exhibit Lewis acidity [82,86-89], originating from the metal cation as electron pair acceptor
apart from the characteristic Bronsted acidity of HPAs.
1.1.9b Supported Keggin heteropoly acids
One of the methods to modify the HPAs is to support them on high surface area acidic
or neutral supports such as silica, zirconia, niobia, titania, tin oxide, ceria, mesoporous materials
(MCM-41, SBA-15) etc. When HPA is supported on acidic support, a strong interaction
between heteropoly acid and oxide surface results in the formation of species such as [M-
OH2]n+[H3-nPW12O40]n-3. Therefore, one can overcome the solubility problem. On the other
hand, support enhance the surface area of active HPA. The number of active sites on the surface
of solid material will also increase along with thermal stability and thereby its catalytic activity.
Basic supports are not suggestible because HPAs readily decompose on basic supports. As the
supported samples are heterogeneous, these can be easily separable from the reaction mixture in
liquid phase applications and stability increases during high temperature gas phase applications.
Keeping this in view, several studies were made on immobilization of HPAs into different
acidic supports and evaluated their physicochemical properties and catalytic applications
[21,74].
1.1.9c Incorporation of metal ion into Keggin heteropoly acids
Another method for the modification of Keggin HPAs is incorporation of transition
metal ions into primary structure of heteropoly anion. Redox properties of the HPAs can be
tuned by incorporating the metal ions such as V5+, Nb5+, and Ta5+ into the primary structure of

13
Chapter 1 Introduction

the heteropoly anion [90,91]. For example, Keggin type heteropoly tungstate can be represented
as H3PW12O40, which consists of 12 addenda atoms (W) in the primary structure. The
modification of heteropoly tungstate can be done by substitution of other metal ions Mn+ for
one or more W atoms into the Keggin frame work of heteropoly anion. The redox potentials of
metal incorporated HPA catalysts depend up on the number of substituted metal atoms in the
primary structure of the heteropoly anion.
Many studies have been focused on substitution of vanadium in place of Mo or W into
the Keggin structure of heteropoly anion [21,63]. Substitution of V into the primary structure of
heteropoly anion resulted in the change in properties of Keggin HPAs from acid dominated
functionalities to redox nature of the catalyst [92]. However, substitution of more number of
vanadium atoms in primary structure leads to the destabilization of Keggin structure [93].
1.2 Modified Keggin heteropoly acid catalysts for benzylation of aromatics
Friedel-Crafts alkylation reaction is one of the important reactions in synthetic organic
chemistry and is usually carried out by the use of various conventional mineral acids such as
H2SO4, HF, H3PO4, HCl etc. The growing awareness of the unacceptability of these
conventional homogeneous catalysts and the resulting legislation give a major impetus to the
search for greener and cleaner technology. Such cleaner technology could be possible by
making use of solid acid catalysts. Heterogeneous catalysts have applications which include
simplified product isolation, easy recovery, reuse, and reduction in generation of waste as by-
products [94,95]. Among the existing solid acid catalysts, heteropoly acids have been proved to
be alternative to the traditional acid catalysts owing to their tunable acid-base, redox properties
and flexibility in structure. Presently, HPAs are used as catalysts in several industrial processes
[60]. The reactions catalyzed by HPAs in both homogeneous and heterogeneous systems have
been reviewed by many researchers [18,21,96,97]. Application of modified HPAs has
demonstrated high catalytic activity as an acid and oxidation catalyst for a variety of organic
transformations [21,98-100], due to their unique features such as high proton mobility, exhibits
strong Bronsted/Lewis acidity and high oxidation ability.
Satam and co-workers [101] reported liquid phase Friedel-Crafts benzylation of
aromatics with benzyl alcohol over polymer supported TPA catalysts under mild reaction
conditions. Mohan Reddy et al. [102] described the hydroarylation of vinyl arenes using AlTPA
catalyst under solvent free conditions. This catalytic system provides a wide range of substrate
applicability under solvent free conditions. Yadav et al. [103] synthesized mono alkylated

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Chapter 1 Introduction

biphenyl over cesium substituted dodecatungstophosphate acid supported on hexagonal

mesoporous silica. Kamalakar et al. [104] studied the structural features and catalytic activities
of heteropoly acid supported on mesoporous silica and revealed that TPA showed high activity
among TPA, STA, and MPA. High dispersion of HPA on silica with higher surface area
enhanced the benzylation activity. Influence of substituent on benzene ring on rate of
benzylation also studied; Electron donating groups increased the rate of reaction and retarded
by electron-withdrawing groups. Kumber et al. [105] reported TPA supported on titania for
benzylation of phenol with benzyl alcohol. Optimum conversion of benzyl alcohol obtained for
the catalyst with 20 wt% TPA on TiO2 and calcined at 700 C.
1.3 Aims and objectives
The main aim of present study in the thesis is modification of Keggin type heteropoly
tungstate and understanding the acidic properties of these modified catalysts as environmentally
benign heterogeneous catalysts for the benzylation of anisole/arenes with benzyl
alcohol/dibenzyl ether. The objective is to modify HPAs to generate Lewis acidity along with
its Bronsted acidity. The increase in thermal stability and surface area is also one of the
objective. These modifications may be helpful in providing best alternative to traditional acid
catalysts. The main aims and objectives of the thesis are,
Modification of Keggin heteropoly tungstate to make use them as efficient
heterogeneous acid catalysts.
Generation of Lewis acidity by exchange of protons of tungstophosphoric acid with
different metal ions.
Preparation of supported metal exchanged heteropoly acid catalysts and evaluation of
their catalytic properties for Friedel-Crafts benzylation reaction.
To study the role of exchanged metal and support of HPA catalysts towards the activity
for benzylation of anisole with benzyl alcohol.
Understanding the influence of location of metal in the modified HPA catalysts and
thereby its catalytic properties.
Evaluation of surface and structural properties of modified tungstophosphoric acid
catalysts by using different spectroscopic and non spectroscopic techniques.
Establishment of plausible mechanism involving both Lewis and Bronsted acid sites in
benzylation reaction.
Optimization of reaction parameters using active catalysts for benzylation reaction.

15
Chapter 1 Introduction

1.4 Organization of the thesis

Chapter 1
This chapter deals with the general introduction about the heteropoly compounds and
their significance. A particular prominence has been given to Keggin heteropoly acids and its
modification. A brief introduction to modified Keggin heteropoly acids particularly on their
salts, niobium substituted and supported tungstophosphoric acid catalysts along with their
catalytic applications for benzylation of aromatics is discussed. The aim and objective of the
thesis is discussed.
Chapter 2
It describes the recent literature dealing with the method of preparation of modified
heteropoly acids. Various methods for the preparation of supported, metal exchanged and
incorporated heteropoly acid catalysts are discussed. The study related to physico-chemical
properties of the HPAs by various spectroscopic and non spectroscopic techniques like FT-IR,
Laser Raman, X-ray photoelectron spectroscopy, X-ray diffraction, pyridine adsorbed FT-IR
spectroscopy and temperature programmed desorption of ammonia are also reviewed.
Generation of Lewis acidic sites along with Bronsted acidity in modified HPAs such as
Zn1.2H0.6PW12O40, TPA/SnO2, TPA/MCM-41 etc. are reviewed. Various catalytic systems
reported in literature for liquid phase benzylation of aromatics is reviewed.
Chapter 3
This chapter illustrates the detailed experimental procedure for the preparation of
modified Keggin heteropoly acids. It involved the preparation of various metal exchanged
tungstophosphoric acid, supported TPA, supported metal exchanged TPA catalysts and niobium
incorporated 12-tungstophosphoric acid and supported niobium containing tungstophosphoric
acid catalytic systems. The basic concepts and the experimental procedures of catalyst
characterization techniques are described. The reaction procedure for liquid phase benzylation
of anisole with benzyl alcohol and dibenzyl ether reaction carried is also presented.
Chapter 4
This chapter deals about the modification of 12-tunstophosphoric acid (TPA) by
exchanging the protons of TPA with different metal ions such as Sn2+, Sm3+ and Hf4+. Chapter
4 divided into three sections.
Section 4.1 describes the heteropoly tungstate modification by exchanging of its protons with
Sn2+ ions. The catalysts characteristics after modification of TPA with Sn2+ derived by different

16
Chapter 1 Introduction

spectroscopic methods were discussed. The generation of Lewis acidic sites with exchange of
Sn2+ is discussed in detail. Catalytic activity was evaluated for benzylation of anisole with
benzyl alcohol. The effect of Sn content in TPA on catalytic activity is discussed. The catalytic
activity of the catalyst has been explored for benzylation of various aromatics with benzyl
alcohol and substituted benzyl alcohols.
Section 4.2 involves the modification of TPA by exchanging the protons of it with Sm3+ and
characterization of modified catalysts by different spectroscopic and non-spectroscopic
techniques. The catalytic activity was investigated for benzylation reaction. Variation of the
catalytic activity with Sm3+ content also discussed. The thermal stability of SmTPA was studied
by treating the catalyst at various temperatures. Comparison of the catalytic activity of SmTPA
with Cs salt of TPA is also discussed. Various reaction parameters such as effect of reaction
temperature, catalyst weight, and anisole to benzyl alcohol molar ratio are studied to optimize
the reaction conditions.
Section 4.3 deals with the acidic properties of the hafnium exchanged TPA catalysts for
benzylation of anisole with dibenzyl ether. Variation in catalytic activity with Hf content in the
secondary structure of TPA is also studied. Reaction parameters such as effect of temperature,
catalyst weight and anisole to dibenzyl ether ratio also studied. The correlation between
structural features derived from characterization results such as XRD, FT-IR, Raman, pyridine
adsorbed FT-IR, temperature programmed desorption of ammonia and XPS with that of activity
is discussed.
Chapter 5
This chapter describes about the modification of 12-tungstophosphoric acid by supporting on
various metal oxides such as SnO2, TiO2, ZrO2, Nb2O5 etc. This chapter is divided into four
sections.
Section 5.1 describe about the TPA supported on tin oxide catalysts for benzylation of anisole
reaction. The influence of TPA dispersed on the tin oxide towards benzylation reaction is
studied. Structural changes in the catalysts with calcination temperature, optimization of
reaction parameters and catalyst reusability is also studied.
Section 5.2 deals with studies on benzylation of anisole over Al exchanged phosphotungstic
acid supported on titania catalysts. The generation of Lewis acidity in the catalyst also
explained. Influence of AlTPA loading on titania, effect of support and calcination temperature
on the structural characteristics also elucidated.

17
Chapter 1 Introduction

Section 5.3 describes the Ga exchanged TPA supported on zirconia catalysts for benzylation
reaction. The influence of GaTPA loading on zirconia on the conversion of benzyl alcohol is
discussed. Comparison study has been made for TPA/ZrO2 and GaTPA/ZrO2 catalysts in order
to know the influence of Ga present in TPA.
Section 5.4 explores the structural and catalytic evaluation of Cs exchanged TPA supported on
acidic supports such as Nb2O5, ZrO2, SnO2 and TiO2. The effect of support in conversion of
benzyl alcohol is studied. The correlation between structural features derived from
characterization results such as XRD, FT-IR, Raman, pyridine adsorbed FT-IR, temperature
programmed desorption of ammonia and XPS studies with that of activity results is discussed in
detail.
Chapter 6
This chapter deals with the niobium containing TPA catalysts and its activity for
benzylation of anisole reaction. This chapter is divided into two sections.
Section 6.1 deals with the study of location of niobium ion in the primary and secondary
structure of the Keggin type heteropoly tungstate. Catalytic activity was tested for benzylation
of anisole with benzyl alcohol and dibenzyl ether also investigated in order to know the effect
of benzylating agent. Thermal stability of the catalysts is examined by in- situ Raman analysis.
The influence of niobium location in the primary and secondary structure of tungstophosphoric
acid (TPANb1, NbTPA) on catalytic activity and selectivity are discussed. The activity of these
Nb containing TPA catalysts is compared with that of TPA supported on Nb2O5.
Section 6.2 presents silica supported niobium containing catalysts for benzylation of anisole
with benzyl alcohol. Surface and structural changes of the catalyst with calcination temperature
and their influence on the conversion of benzyl alcohol is also studied. Reaction parameters
such as effect of catalyst weight, reaction temperature and anisole to benzyl alcohol molar ratio
are studied to optimize the reaction conditions.
Chapter 7
This chapter discloses the main conclusions drawn from the results obtained in the
present work.

18
Chapter 1 Introduction

1.5 Highlights of the thesis

Keggin type tungstophosphoric acid is modified to tune their acidic properties for the
benzylation reaction.
Tungstophosphoric acid modified by adopting different techniques such as exchanging
the protons of TPA with metal ions, incorporation of metal ions into the primary
structure of the Keggin ion and supporting on acidic supports.
Generation of Lewis acidic sites in 12-tunstophosphoric acid by exchanging the protons
of TPA with metal ions such as Sn2+, Sm3+, Hf4+ etc. as heterogeneous catalysts for
liquid phase benzylation of anisole reaction.
Enhancement of acidic properties of 12-tungstophosphoric acid by exchanging the
protons of TPA with metal ions.
Studies on influence of benzylating agent in benzylation of anisole reaction.
Modification of TPA by supported metal exchanged TPA catalysts (AlTPA/TiO2,
GaTPA/ZrO2, TPA-Cs/Support) for benzylation of anisole.
Evaluating the influence of the support on acidic properties of aluminium exchanged
tungstophosphoric acid catalysts.
Role of Lewis acidity in supported metal exchanged tungstophosphoric acid catalysts
for benzylation reaction.
Investigation of role of support for the benzylation of anisole reaction over supported
cesium exchanged tungstophosphoric acid catalysts.
Development of supported 12-tungstophosphoric acid by impregnating on SnO2
catalysts and study of surface, structural feature of the catalysts.
Study of incorporation of niobium ion into the primary and secondary structures of
Keggin ion and evaluation of the acid properties for benzylation of anisole with benzyl
alcohol and dibenzyl ether.
Evaluating the surface structural properties of the silica supported niobium containing
catalysts and their acidic functionalities.

19
Chapter 1 Introduction

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