77

Send Orders for Reprints to reprints@benthamscience.ae

Current Catalysis, 2017, 6, 77-89
REVIEW ARTICLE
ISSN: 2211-5447
eISSN: 2211-5455

Acid Catalysis by Heteropolyacids: Transformations of Alkanes

BENTHAM
SCIENCE

Frédéric Lefebvre*

Laboratory of Chemistry, Catalysis, Polymers and Processes (C2P2), University of Lyon 1, CNRS, CPE, UMR 5265, 43
Bd du 11 Novembre 1918, 69616 Villeurbanne, France.

ARTICLE HISTORY
Received: August 10, 2016
Revised: January 6, 2017
Accepted: January 25, 2017
DOI:
10.2174/2211544706666170203123816
Abstract: Background: Acid catalysis of alkanes is very important as it is the basis of refining. They
can be converted into other alkanes or alkenes by isomerization, cracking or alkylation. Heteropolyacids
have unique acid–base and redox properties, which render them valuable in a number of applications.
Their strong acidity makes them attractive candidates to tackle the current challenges in alkanes. The
aim of this review is to describe the state of the art in the transformations of alkanes catalyzed by heter-
opolyacids with and without addition of noble metal.
Methods: We undertook a structured search of bibliographic databases for peer-reviewed research liter-
ature using a focused review question. The quality of retrieved papers was appraised using standard
tools. The characteristics of screened papers were described, and a deductive qualitative content analy-
sis methodology was applied to analyze the interventions and findings of included studies using a con-
ceptual framework.
Results: More than one hundred and fifty papers were included in the review. After a general introduc-
tion describing the polyoxometalates and their properties, the generally admitted mechanisms of activa-
tion of alkanes by acid catalysts were described. The review was then presented by type of alkanes,
starting from propane to long chain paraffins. The activation of methane by heteropolyacids was also
described as it can be considered as the first step of the oxidation of methane, which is actually a very
important challenge.
Conclusion: Polyoxometalates are active for the isomerization/cracking of alkanes. If the first studies
were made on light hydrocarbons the most recent works are done on wax or heavy oil, in order to valor-
ize them in gasoline. The polyoxometalate reacts easily with the alkane and this reaction is not the ki-
netically limiting step.

Keywords: Heteropolyacids, alkanes, isomerization, cracking, alkylation, petroleum chemistry.

1. INTRODUCTION central ion surrounded symmetrically by twelve MO6 octahe-

In chemistry, a polyoxometalate (POM to use from now
on in the text) is a polyatomic anion that consists of three or
more transition metal atoms linked together by oxygen at-
Current Catalysis
dra, which form four groups of three edge-shared octahedra
(Fig. 1a). The central atom is usually phosphorus or silicon,
while the M atom is tungsten (W) or molybdenum (Mo). The
anion of a POM with the Keggin structure is close to a sphere

oms. The metal atoms are usually from groups 5 (vanadi-um,
niobium, tantalum) or 6 (molybdenum, tungsten) in their
higher oxidation state [1]. The POMs can be divided into
isopolyoxometalates (with only one transition metal) and
heteropolyoxometalates (with one transition metal and a
main group oxyanion often phosphate or silicate). These
POMs have a lot of properties in various domains such as
catalysis, physics or medicine [2-11]. Those usually used in
catalysis have in most cases the so-called “Keggin” structure
[12]. Indeed they are easy to prepare and commercially
available. Heteropolyacids of the Keggin type consist of a
*Address correspondence to this author at the Laboratory of Chemistry,
Catalysis, Polymers and Processes (C2P2), University of Lyon 1, CNRS,
CPE, UMR 5265, 43 Bd du 11 Novembre 1918, 69616 Villeurbanne,
France; Tel: ++0-3347-243-1807; Fax: +0-3347-243-1795;
E-mail: frederic.lefebvre@univ-lyon1.fr
in shape, with a diameter of about 1 nm. These heteropolyox-
ometalates with the Keggin structure possess acidic and redox
properties, which can be easily tailored by changing the com-
position of the Keggin units [4, 5]. Their formula is
[XM12O40]n- with X = P, Si, … and M = W, Mo. To our
knowledge most studies reported in this review were made
with this POM. There are only few reports on the use of two
other species, the Wells-Dawson [P2W18O62]6- (Fig. 1b) and
[P2W21O71(H2O)3]6- (Fig. 1c) [1].
All these compounds are highly acidic when the counter-
cation is a proton and they are sometimes considered as su-
peracidic. As a consequence, they were used in reactions
requiring such a high acidity, the best example being the
activation of the C-H bond of alkanes and its use for their
transformation of more valuable compounds, a challenge of
the petrochemical industry [7].

2211-5455/17 $58.00+.00 ©2017 Bentham Science Publishers

78 Current Catalysis, 2017, Vol. 6, No. 2
Fig. (1). Structures of some POMs: (a) Keggin [XM12O40]n-; (b)
Wells-Dawson [P2W18O62]6-; (c) [P2W21O71(H2O)3]6-.
Indeed, the petrochemical industry is nowadays urged to
produce gasoline with similar or better performances than
the current standard by avoiding the use of toxic compounds
[13]. The European directives limit vapor pressure, the level
of aromatics and olefins as well as the interdiction of lead.
These limitations impact the quality of fuels by a decrease of
the research octane number (RON). A high research octane
number allows for better fuel combustion which means bet-
ter performance of internal combustion engine. To achieve
this objective n-alkane isomerization is an interest-ing solu-
tion since, with this process, low-octane straight chain paraf-
fins are directly converted into high-octane branched mole-
cules. Thus, the skeletal isomerization of light species ap-
pears as an important refining process to obtain “clean gaso-
line”. On the other hand, the valorization of heavy fraction of
crude oil is also needed. It can be achieved by cracking, a
reaction which is made by the same catalysts which have
been used for isomerization. However, the development of
an ecofriendly and performant catalysts is required. The
monofunctional Friedel-Crafts catalysts (AlCl3 with additives
such as SbCl3 or HCl) were the first generation of catalysts
used industrially. These catalysts were abandoned due to
corrosion problems, their high sensitivity to water and sulfur
and due to coke formation poisoning the solid. The bifunc-
tional catalysts have been developed since 1950. The first
solid developed was platin-um (Pt) supported on alumina.
Their advantages are their stability and selectivity on alkane
isomers. However, these catalysts are less active than the
homogeneous Friedel-Crafts type, thus high temperatures
(300-450°C) are required and as well as high hydrogen pres-
sure (30-70 bar). To overcome the lower catalytic activity,
aluminum chloride was added in the feed to maintain high
catalyst activity thus operating at low temperatures (120-
160°C). However, the main objections against the utilization
of chlorides are corrosion problems and handling of envi-
ronmental hazards. The actual industrial catalysts contain
platinum supported on acidic zeolites. The zeolites have high
resistance to water and sulfur, making them stable catalysts
with respect to poisoning. Another advantage of zeolites
catalysts is their long lifetime. However, zeolites are less
acidic than Pt/Alumina doped chlorinated alumina and so
exhibit lower catalytic activity. Hence, reaction conditions
o
must be at high temperature (220-300 C) and high hydrogen
pressure (15-30 bar). Currently, a new generation of catalysts
has been developed at the laboratory scale. Among them,
sulfated zirconia, tungsten oxide supported on zirconia and
heteropolyacids are the most studied as viable alternatives to
Frédéric Lefebvre
replace Pt/zeolite catalysts [13]. The aim of this paper is to
give an overview of the use of heteropolyacids in this field.
After a description of the mechanisms commonly accepted
for this reaction, we will describe the literature data for each
alkane, starting from methane and ending by polymers and
heavy fractions. A general discussion will then conclude this
review.
2. MECHANISMS OF THE TRANSFORMATION OF
ALKANES BY ACID CATALYSIS
There are two reaction pathways for the skeletal isomeri-
zation of alkanes by acid catalysis, depending on the number
of molecules involved in the mechanism [13]: the monomo-
lecular and the bimolecular mechanisms. In the two cases,
the first step of the reaction is a reaction of the acidic proton
of the catalyst with the alkane, leading to the evolution of
hydrogen and the formation of the starting carbocation.
+
H+
+ +
H
+ +
+
+
+
H
+
+
Fig. (2). Monomolecular mechanism in the case of n-hexane.
In the case of the monomolecular mechanism (Fig. 2), this
carbocation will undergo an intramolecular rearrangement via a
protonated cyclopropane. The final step is the formation of the
isomerized alkane by a hydride-transfer reaction between the
carbocation and another alkane molecule and the restoration of
the carbocation. In that case the selectivity to isomerization is
100 %. This mechanism is depicted above in the case of n-
hexane:
The formation of the di-substituted isomers (2, 2- and 2,
3-dimethylbutane in the case of hexane) involves two suc-
cessive rearrangements. So it is less probable than the for-
mation of the mono-substituted ones (2-and3-methyl-
pentanes). No deactivation of the catalyst can occur via this
mechanism as only isomers of the starting alkane are ob-
tained.
+
H+
+
Isomerization
+
+
seven isomers Cracking
Fig. (3). Bimolecular mechanism in the case of n-hexane.
Acid Catalysis by Heteropolyacids: Transformations of Alkanes
In the case of the bimolecular mechanism (Fig. 3), there
is first formation of an alkene molecule by evolution of the
carbocation and then attack of it by another carbocation,
leading to a species with the double of carbon atoms. Con-
secutive rearrangements lead not only to the isomerization
products but also to cracking:
The selectivity to isomerization is not 100 % (due to
cracking) and the presence of olefins will lead to the for-
mation of coke which will deactivate rapidly the catalyst.
The two mechanisms are often present simultaneously and it
is difficult to determine their relative proportions. The bimolecu-
lar mechanism can be avoided in conditions where the olefin is
not stable (presence of hydrogen and of a hydrogenating metal
such as platinum). The conversion remains stable with a high
selectivity to isomerization. Another point is that the relative
proportion of cracking increases when the number of carbon
atoms of the alkane increases passing in the better cases from ca.
0 % in the case of butane to about 100 % when the molecule
contains more than 10 carbon atoms.
3. ACTIVATION OF METHANE
Methane, the simplest alkane, cannot undergo any direct
transformation by acid catalysis; its valorization is a chal-
lenge for the petrochemical industry as its stocks are very
important and it could replace oil if it could be valorized.
Various ways were studied for that purpose such as dimeri-
zation or aromatization, and one of them involves the oxida-
tion by oxygen (or air) which can be catalyzed by POMs.
However this reaction is difficult because oxidation products
(methanol or formaldehyde) can be oxidized more easily
than the starting methane. There are a lot of reports on the
oxidation of methane to formaldehyde catalyzed by POMs
[14, 15] however the reaction occurs at high temperature
(around 500°C) and so in conditions quite different of those
of isomerization/cracking. However there are two reports of
the oxidation of methane at low temperature [16, 17]. The
main result of these studies is that the oxidation products
formed during this reaction are mainly acetaldehyde and
acetic acid and so correspond to the insertion of carbon
monoxide in one reaction intermediate. Due to this observa-
tion a further study was needed to study in details the stoi-
chiometric reaction of methane with hetero-polyacids, pure
or supported on silica [18]. The main conclu-sions of this
study were the following:
- Contrary to what could be expected, the reaction of me-
thane with the heteropolyacid proceeds at low tempera-
ture with evolution of hydrogen by abstraction of an hy-
dride from methane.
- This reaction leads to the formation of a methyl cation
which is not stable alone and coordinates to the POM
leading to a methyl-POM (POM-CH3) species where the
methyl group is linked to an oxygen atom of the POM.
- This POM-CH3 complex is stable and cannot be decom-
posed, for example by addition of water, in order to re-
form the heteropolyacid and to evolve methanol.
- A proof of the above point is that this species can be ob-
tained by reaction of methanol with the heteropolyacid
[19, 20].
Current Catalysis, 2017, Vol. 6, No. 2 79
It can then be concluded that it is not possible to form di-
rectly methanol from methane on a heteropolyacid. Another
consequence is that it is necessary to destroy the POM struc-
ture in order to achieve it. It is what happens when the reac-
tion is made at high temperature where there is an equilibri-
um between the POM and its decomposition products. How-
ever, it has been reported that the POM-CH3 species reacted
with CO, leading to a POM-C(=O)-CH3 compound which is
less stable than the methoxy derivatives [19]. It is for this
reason that the main products of oxidation of methane were
reported to be acetaldehyde and acetic acid.
In view of the mechanistic considerations on the trans-
formation of alkanes catalyzed by POMs, the above conclu-
sions are important. Indeed, as we have described it above,
the first step of both monomolecular and bimolecular mech-
anisms is the reaction of a proton of the catalyst with the
alkane (or the alkene) leading to the formation of the first
carbocation. In the case of heteropolyacids, this step must be
separated in two steps:
First step: reaction of the heteropolyacid with the alkane (or
the alkene) leading to the formation of a POM-(Alkyl) complex.
This reaction is not the limiting step as it proceeds easily.
HPOM + Alkane Æ POM-(Alkyl) + H2
Second step: Decomposition of the POM-(Alkyl) comp-
lex leading to the formation of the starting carbocation. This
reaction is an equilibrium which is strongly displaced to the
left and is the limiting step:
POM-(Alkyl) Æ POM- + (Alkyl)+
This mechanism prevents the use of heteropolyoxo-
metalates at low temperature as there is no formation of car-
bocation. In addition, the use of a too high temperature is not
allowed as it will decompose the POM.
4. TRANSFORMATION OF PROPANE
There are only very few reports on the transformation of
propane catalyzed by heteropolyacids. The main reason is
that it is more valuable for industry to convert propane into
propene by selective oxidative dehydrogenation or to acrole-
in or acrylic acid by selective oxidation, two reactions which
can also be catalyzed by POMs. However the study of this
reaction can give interesting information on the mechanism
and allow a better understanding of some results such as se-
lectivity. To our knowledge, there are only two publications
where this reaction is described [21, 22]. The authors studied
the transformation of various alkanes including propane on
H3PW12O40 and its cesium salts. The results are reported in
Table 1 and led to the following conclusions:
- First of all, all catalysts deactivate rapidly due to the for-
mation of coke, as already observed with other acid cata-
lysts.
- When looking at the initial activity it is evident that the
reaction proceeds more slowly on propane than on the
other alkanes, the reaction rate increasing with the num-
ber of carbon atoms of the alkane chain. This will lead to
a modification of the selectivities of secondary products
during the cracking of higher alkanes (for example for
butane isomerization, propane and pentane will be
80 Current Catalysis, 2017, Vol. 6, No. 2 Frédéric Lefebvre

formed in the same proportions by the bimolecular 5.1. Isomerization of N-Butane in Absence of a Noble
mechanism but pentane will be transformed ca. 100 times Metal
more rapidly than propane by a secondary reaction).
In most cases the POM was H3PW12O40 or its salts and
- Another point is that the activity of H3PW12O40 is higher there are only few reports on the use of H4SiW12O40. The
than that of its cesium salts even if its surface area is reason is probably that the first compound is considered as
lower. This was attributed to a decrease of the acid site the most acidic heteropolyacid. To our knowledge, no stud-
density on the surface of the catalyst upon introduction of ies were reported with other POMs, with the exception of a
the cesium ions. paper where supported molybdenum Keggin acids were
found to be inactive.
- Finally, the reaction products (not listed in Table 1) are
n-butane (≈80 %), isobutane (≈15 %), propene (≈ 5 %) For phosphotungstic acid many studies were made on its
and pentanes (less than 2 %). This distribution was ex- acidic cesium salts (see for example [22] and [24-29]) with
plained by assuming that there was first formation of C9 results which could vary from one group to another, depend-
hydrocarbons by a trimerization process (by reaction of ing on the preparation method and on the pretreatment of the
the carbocation with two propene molecules), followed catalyst. Due to these conditions the protons will be localized
by isomerization and cracking. homogeneously in the solid (solid solution) or at the surface
of the crystallites, resulting in a different concentration of
Table 1. Comparison of the activities (in μmol.h-1.g-1) of different
active sites. However the best system seems to contain be-
POMs in the transformation of alkanes (reaction condi-
tions 250 °C, N2/alkane = 9 (in mol), WWH varying tween 2.0 and 2.5 cesium ions per POM. These systems were
from 0.3 for propane to 7 h-1 for hexane). active at 200 °C with a slow deactivation but the activity
decreased strongly at high temperature, probably due to the
loss of protons by dehydration. The selectivity to isobutane
Catalyst could reach ca. 90 %, in agreement with a great contribution
H3PW Cs2.0H1.0P Cs2.1H0.9P Cs2.4H0.6P of the monomolecular mechanism, at least at the first stages
12O40 W12O40 W12O40 W12O40 of the reaction.
Two studies were made with additional elements to the
BET area (m2.g-1) 4.1 46 81 135
cesium salt of phosphotungstic acid: Li et al. reported in
Transformation of propane 2011 the synthesis of GaxCs2.5-3xH0.5PW12O40 salts and their
use in the isomerization of n-butane [30]. The solids were
Activity (t = 0) 40 22 31 4 tested at 100 °C and were more active than the cesium salt
Activity (t = 2h) 1 1.2 9 1.4 with an optimum value x = 0.1. At the initial stages of the
reaction the mechanism was mainly monomolecular and then
Transformation of n-butane it became mainly bimolecular (the study was made in batch).
After 50 min the conversion could reach 60 % but the isobu-
Activity (t = 0) 1000 2450 3600 1400
tane yield was only 26 %, the other products being propane
Activity (t = 2h) 26 100 750 290 and pentanes. More recently Zhang et al. have reported the
synthesis of an aluminum promoted cesium salt of phospho-
Transformation of n-hexane tungstic acid [31]. The results were comparable to those
Activity (t = 0) 2300 5950 15400 9700 achieved with the gallium composite: increase of the catalyt-
ic activity, optimum value with 0.1 Al per POM and quite
the same conversion and isobutane yield. In the two cases
5. TRANSFORMATION OF BUTANE the results were explained by an increase of the Brönsted
In contrast to propane, the transformation of n-butane into acid sites of the solid upon substitution rather than an in-
isobutane is well documented due to its interest in industry as crease of the acid sites density.
shown by patents such as [23]. Indeed isobutane is used for the Phospho- and/or silicotungstic acids were supported on
production of di-tert-butyl peroxide, isobutene and methacrylic various supports such as clays, oxides, or silica, even modi-
acid. fied with cesium [32-38]. The main results were that the cat-
alysts supported on silica led to the higher activity for the
isomerization of n-butane [35] but as for the cesium salts, a
deactivation was observed. The isobutane selectivity was
also comparable to that observed on the cesium salts but a
study as a function of conversion showed that silicotungstic
Its alkylation with butene leads to iso-octane, which acid was inherently more selective that phosphotungstic acid
increases the octane value of fuel. [38]. It was also shown that the loss of acivity at high tem-
perature was due to dehydration, addition of water in the
+ feed leading to an increase of the activity [33]. Finally Bog-
dan et al. showed in 2004 that isomerization in supercritical
Various catalysts were used for these two reactions, butane resulted in a stable activity during 3 – 5 h but the
with or without the presence of a noble metal such as conversion was 20 – 25 % with a selectivity to isobutane of
platinum and hydrogen. only 80 %.
Acid Catalysis by Heteropolyacids: Transformations of Alkanes Current Catalysis, 2017, Vol. 6, No. 2 81

5.2. Isomerization of N-Butane in Presence of a Noble assuming that the supercritical solvent removed the oligo-
Metal and Hydrogen mers on the surface of the catalysts, preventing the poisoning
of the acid sites. Finally, He et al. reported that addition of
The too low selectivities attained on all the above sys- trace amounts of HF in the feed led to a significant increase
tems and the rapid deactivation prevented their use for indus-
of the selectivity to substituted octanes [65-67].
trial applications. However these limitations could be over-
came by addition of a hydrogenating metal in presence of The mechanism of the reaction, as it is generally admit-
hydrogen. Indeed the deactivation, in such reactions, is ted, is depicted in Fig. (4). The initiation step is the reaction
mainly due to the formation of coke, obtained by polymeri- of butene with the acidic proton, leading to the formation of
zation of olefins, while the secondary products are formed by the secondary carbocation which will isomerize rapidly to
cracking reaction in the bimolecular mechanism, which in- the tertiary one. This carbocation remains at the surface of
volves also olefins. Suppression of the olefins in the feed by the catalyst near the negative charge of the POM. It will then
hydrogenating them should increase the selectivity to isobu- react with another butene molecule, leading to a substituted
tane and the stability of the catalyst, even if this will lead to a C8 carbocation. This carbocation can continue to react with
decrease of the activity compared to the initial value without butenes, leading to the formation of the polymer which will
noble metal. deactivate the catalyst or it can react with isobutane, leading
the substituted octane and reforming the C4 carbocation.
Only cesium salts of phosphotungstic acid were studied in
When comparing this mechanism with the bimolecular one
presence of platinum or palladium [39-46]. Quite the same
for the alkane isomerization, one can see a great analogy,
results were obtained for the two metals. The catalysts were explaining why heteropolyacids are active for this reaction.
obtained by mixing a noble metal salt with the heteropolyacid
in solution and addition of the desired amount of cesium car-
bonate. They were then calcined and reduced under hydrogen.
As a consequence the metal particles and the acid sites are pre-
sent on the same crystallites. This point is important as shown
below, these systems being not the best ones. However even in
these conditions stable systems were obtained under low hy-
drogen pressure (0.05 atm) and with a platinum content of 1.5
wt. % [46]. The selectivity to isobutane was also very good as a
value as high as 95.6 % could be achieved at a 34 % conver-
sion.

5.3 Alkylation of Isobutane by Butenes

The alkylation of isobutane by butenes presents a consid-
erable economic interest as the branched isomers of octane
formed by this process have high research octane numbers,
are not volatile and present a low toxicity. Commercial pro-
cesses are based on the use of sulfuric or hydrofluoric acids
and have significant drawbacks. As a consequence numerous
studies were made on solid acid catalysts in order to find a Fig. (4). Mechanism of the alkylation of isobutane by butenes.
less toxic system. Acid zeolites and sulfated zirconia were
shown to be active but they deactivate rapidly. Heteropoly- 6. ISOMERIZATION OF PENTANE
acids were also studied and a patent reported that the alkyla-
The isomerization of pentane on heteropolyacids has
tion of isobutane with isobutene was catalyzed by heteropol-
been studied for a long time as the first report was made in
yacids at relatively low temperature [47]; In 1994 Okuhara et
1984 by Ono and coworkers [68]. They used a palladium salt
al. reported that the alkylation of isobutane with butenes was
of phosphotungstic acid supported on silica and studied the
catalyzed by a cesium salt of phosphotungstic acid [48]. A
reaction at 210 °C in presence of hydrogen at atmospheric
lot of reports were then done in the following years [49-61].
pressure. Isopentane was obtained with 90 % selectivity. The
In most cases the catalyst was an acidic cesium, potassium or
protons were formed during the reduction of the palladium
ammonium salt of phosphotungstic acid which has a high
ions into metal particles. There are some reports of the use of
surface area. In all cases the best amount of protons seemed
acidic cesium salts of phosphotungstic acid without addition
to be 0.5 per POM. There are also some reports of the use of
of a noble metal [69, 70] but most studies were made in
phosphotungstic acid supported on silica or MCM-41. No
presence of platinum or sometimes palladium in order to
other POM was studied if one excepts a study of the Wells-
suppress the bimolecular mechanism and the deactivation by
Dawson heteropolyacid H6P2W18O62 supported on silica
formation of coke. Very often the metal was introduced dur-
[51]. In all cases the system showed a good initial activity
ing the preparation of the acidic salt of the POM [23, 43, 71-
but it deactivated rapidly by formation of polyolefins by
73] but there is a report where the bifunctional catalyst was
polymerization of butene, leading to strongly adsorbed mol-
obtained by grinding the acidic salt of phosphotungstic acid
ecules on the acid sites. Further studies showed that, as ob-
and a Pt/SiO2 catalyst in the same amount [74]. However it is
served for the isomerization of n-butane the use of a super-
difficult to compare the effect of the incorporation of plati-
critical fluid was beneficial and could lead to an activity sta-
num as the solids were not used in the same conditions even
ble during time [52, 53, 62-64]. This result was explained by
82 Current Catalysis, 2017, Vol. 6, No. 2
if it has been reported that a mechanical mixture led to a bet-
ter catalyst than a direct incorporation of platinum [73].
There are some reports of the use of silica (or MCM-41)
supported phosphotungstic acid [75-77], the metal being
deposited on the same support. Later studies were done on
other oxides such as alumina [77, 78] and more recently on
zirconia, which appears as the best support [77, 79-81]. In all
cases the amount of noble metal was relatively low (ca. 1
wt.%) and high selectivities could be achieved at low tem-
perature (for example 97.6 % at 200 °C for a 65.9 % conver-
sion on a zirconia supported catalyst [77]). There is only one
report of the use of silicotungstic acid supported on silica in
presence of palladium (1 wt. %) [82]. A selectivity for iso-
pentane of 99.1 % could be achieved on this system at 250
°C, the conversion reaching ca. 44 %.
7. ISOMERIZATION/CRACKING OF HEXANE
The isomerization of n-hexane is well documented as the
use of branched isomers is required in order to increase the
octane number of fuel as it is also the case, in a lower
amount, for pentane.
7.1. Isomerization/Cracking of N-Hexane in Absence of a
Noble Metal
We reported in 1992 that some heteropolyacids (H3PW12-
O40, H4SiW12O40, H6P2W18O62 and H6P2W21O71 (H2O)3) pure or
supported on silica were active for the cracking of n-hexane
[83-85]. The study was made between 100 and 500 °C. The
best system was H4SiW12O40 supported on silica but in all cases
the catalysts deactivated rapidly and there was an optimum for
the reaction temperature, the catalyst being inactive at high
temperature due to the loss of protons by dehydration. Unfor-
tunately no data were given on the isomerization rates. Kuang
et al. gave more data on the activity at 225 °C of catalysts
based on phosphotungstic acid on silica: (i) the conversion
increases with the amount of supported polyacid; (ii) the selec-
tivity for isomerization decreases when the conversion increas-
es, the best value being ca. 80 % for a 3.7 % conversion and
(iii) the cracking products are mainly isobutene and isopentane
[86]. In presence of hydrogen quite similar results were ob-
tained [87]. Jalil et al. studied the craking of n-hexane on
H3PW12O40 pure or supported on MCM-41 [88-90]. As ob-
served by us the catalysts were not active at high temperature
and deactivated rapidly. At 300 °C the selectivity for isomeri-
zation was very low (the best value was 21.4 % for the unsup-
ported heteropolyacid). The distribution of cracking products
was strongly modified when the polyacid was supported on
MCM-41: while isobutane was the major product for unsup-
ported polyacid propane was mainly observed for the support-
ed catalysts. We have also studied the isomerization of n-
hexane on H3PW12O40 and H4SiW12O40 impregnated on or syn-
thesized in SBA-15 [91, 92]. The reaction was made at 200 °C.
For all catalysts the selectivity to isomerization decreased when
the conversion increased and silicotungstic acid was inherently
more selective than phosphotungstic acid whatever the conver-
sion. The repartition of the isomerization products was the
same in all cases, the major product being 2-methylpentane,
then 3 methylpentane, the dibranched isomers being formed in
smaller amounts (ca. 20 %). When the heteropolyacid was en-
capsulated in SBA-15 a completely different behavior was
Frédéric Lefebvre
observed for silico- and phosphotuns-gtic acid: while encapsu-
lated phosphotungstic acid led to results similar to those of the
impregnated solid encapsulated silicotungstic was inactive.
This result was interpreted as a deeper encapsulation of the
polyacid in the SBA-15 matrix.
There are only few reports on the use of Cs3-xHxPW12O40,
by the group of N. Essayem [21, 22]. The main results of their
studies are shown in Table 1. Finally there is a report on the use
of zirconia doped with phosphotungstic acid [93]. Isomeriza-
tion occurs only at 220 °C with formation of dibranched iso-
mers but unfortunately no indication was given on the conver-
sion and the presence or not of cracking products.
7.2. Isomerization of N-Hexane in Presence of a Noble
Metal and Hydrogen
The transformation of n-hexane in presence of hydrogen
and a noble metal is more documented as the objective is to
avoid cracking and to have selectivity towards isomerization
as high as possible. The first report was made by Suzuki et
al. who studied also the isomerization of pentane (see above)
but most of the work was made on n-hexane [68]. They used
a metal salt of phosphotungstic acid supported on silica and
treated it under hydrogen before reaction. The metal is re-
duced by this treatment and protons are formed during this
reaction. The best results were obtained with palladium. At
250 °C the conversion was 33.7 % and the selectivity to
isomerization 84.4 %. The catalyst showed only a very slow
deactivation.
In 2001, Essayem et al. studied the isomerization of n-
hexane on acidic alkali salts of phosphotungstic acid in pres-
ence of platinum supported on silica [94] or alumina [95]. A
selectivity to isomerization as high as 99 % could be
achieved but as reported by other authors it decreased when
the conversion increased. This system gave results quite
comparable to those obtained with the industrial Pt/H-
mordenite catalyst. Depending on the alkaline cation the
results were slightly different, the best system being obtained
with rubidium. The platinum content could be as low as 0.2
wt. %.
Misono et al. have studied in 1998 and 2000 the isomeriza-
tion of n-hexane on Cs2.5H0.5PW12O40 in presence of Pt/Al2O3
[73, 96]. At 180 °C the conversion was 58 % with a selectivity
to isomerization of 98.4 % The main products were 2-
methylpentane (47.2 %) and 3-methylpentane (33.9 %) but the
amount of 2,3-dimethylbutane was not negligible (13.7 %).
These proportions are very different from those given by ther-
modynamics.
Kuang et al. studied this reaction at the beginning of the
century by using a mechanical mixture of a silica supported
Keggin heteropolyacid and Pt/Al2O3 [87, 97]. As above the
selectivity was very high (99 % at a 50 % conversion) and
the distribution of products was very close to that obtained
on the cesium salts. Interestingly, they observed that sup-
ported H4SiW12O40 was more active than H3PW12O40 [97].
Later they used mixed oxides containing cerium instead of
platinum: nickel-cerium oxide [98], cerium oxide doped with
palladium [99] or platinum [100]. In all cases there was an
optimum for the amount of cerium oxide and very high se-
lectivities to isomerization products were achieved.
Acid Catalysis by Heteropolyacids: Transformations of Alkanes
In 2008 Chen et al. used phosphotungstic acid supported
on a Zr-MCM-41 silica in presence of platinum (deposited
on the support by impregnation) [101]. They studied the ef-
fect of zirconium on the catalytic activity and observed that
it increased with the zirconium content but high zirconium
amounts led to a decrease of the selectivity to isomerization
products. However at 240 °C a conversion of 46 % could be
achieved with 100 % selectivity to isomerization.
We have studied silicotungstic acid supported on SBA-15
in presence of platinum on the same particles or on separate
crystallites [102]. In all cases very good selectivities and
activities were achieved but the mechanical mixture led to a
slightly better system in terms of activity even if it was
slightly less selective.
There is only one example of isomerization of n-hexane
on heteropolyacids different from the silico- and phospho-
12-tungstates, on zirconia [103]. The heteropolyacids and
platinum were impregnated on the same support. In addition
to H3PW12O40, H5PW11ZrO40, H6P2W18O62 and H6P2W21O71
(H2O)3 were studied. The best system seems to be that ob-
tained by replacement of one tungsten atom by a zirconium
one in the Keggin structure.
Finally we must cite a paper by Macht et al. published in
2009 who studied the isomerization of n-hexane on support-
ed Keggin heteropolyacids but only in view of mechanistic
considerations and comparison with theoretical calculations
[104].
8. TRANSFORMATION OF HEPTANE
The transformation of heptane is also well documented,
for the same reasons than that of hexane (formation of
branched products with a higher octane number). Most stud-
ies were made in presence of a noble metal, in order to favor
the isomerization and to suppress the deactivation.
In 2010 A. Ouissi studied this reaction over H4SiW12O40
pure or supported on alumina [105]. The reaction was stud-
ied between 240 and 320 °C and it was claimed that the pure
heteropolyacid did not deactivate after 50 min. of time of
stream. This could be due to the fact that the reaction was
made in the presence of hydrogen. As observed for hexane
isomerization there is an optimum value for the reaction
temperature, at 300 °C. The selectivity to cracking was ca.
50 % whatever the temperature but interestingly he observed
the formation of cyclized products in a high amount (selec-
tivity ca; 40 % at 300 °C). The supported heteropolyacid was
found to be less active and less selective to cyclization than
the pure polyacid. A reason can be that when H4SiW12O40 is
deposited on alumina it reacts with the support by an acid-
base reaction leading to the formation of an aluminum salt of
the polyacid which does not have Brönsted acidity. Later this
study was extrapolated to other pure heteropolyacids,
H3PM12O40 (M = W, Mo), H4PMo11VO40 and Cu1.5PMo12O40
[106]. These different compounds were studied at 300 °C in
presence of hydrogen. The three heteropolyacids have a quite
similar behavior: conversion around 7 – 8 % selectivity to
cracking around 70 – 80 %, to cyclization ca. 10 % and to
isomerization ca. 15 %. Replacement of the protons by cop-
per in the phosphomolybdic compound leads to a decrease of
the conversion (from 8 to 3 %, probably due to the lower
Current Catalysis, 2017, Vol. 6, No. 2 83
amount of protons) but to an increase of the selectivity to
cyclization from 9 to 15 %.
There are few reports on the use of acidic salts of phos-
photungstic acid in the skeletal isomerization of n-heptane.
Liu et al. used Cs2.5H0.5PW12O40 in combination with
Pt/Al2O3 and observed that the catalyst was stable at 150 °C
(n-heptane/ hydrogen ratio = 4) but deactivated at 180 °C
[96]. At 150 °C the conversion was ca. 40 % and the selec-
tivity to isomerization ca. 90 %. In 2003 Miyaji et al. studied
also this cesium salt impregnated with platinum or supported
on silica, also in the presence of platinum [107]. The reaction
was studied at 180 °C but with a high hydrogen/n-heptane
ratio (around 20). In these conditions the catalysts were sta-
ble. The silica supported catalyst was less active than the
unsupported one but more selective to isomerization (97.1 %
for a 73.8 % conversion). As expected the amount of di-
branched compounds increased with the conversion. In terms
of selectivity, this catalyst compared well to Pt-H-E zeolite,
which is known to be efficient for this reaction, but it was
less active. Three years later Sugii et al. compared the per-
formances of Cs2.5H0.5PW12O40 + Pt (2 wt. %) and
Cs2.5H1.5SiW12O40 + Pt at 180 °C [108]. The first catalyst
was more active than the second one but less selective at the
same conversion, as observed by us for n-hexane.
The same authors studied also H4SiW12O40 supported on
silica in the presence of palladium (2 wt. %) [108, 109]. The
conversion increased with the POM loading but the selectivi-
ty decreased by the same way. The best system contained 10
wt. % H4SiW12O40 and was comparable to the Pt-H-E zeolite
in terms of selectivity.
There are a lot of reports using mesoporous silica, modified
or not, as a support for heteropolyacids and the use of the re-
sulting catalysts for the n-heptane hydroisomerization. In 2009
Liu et al. deposited phosphomolybdic acid on mesostructured
TUD-1 in the presence of 0.5 wt. % Pt [110]. The hydrogen to
heptane ratio was 26 and the temperature was varied between
200 and 350 °C. As observed for other molecules, the selectivi-
ty to isomerization decreased when the activity increased and
was ca. 85 % when the conversion was 55 %. In 2012 Yang et
al. used H3PW12O40 deposited on MCM-41 for this reaction
[111]. The Pt loading was 1 wt. % and the hydrogen/heptane
ratio was 13. The study was made between 220 and 320 °C and
here also the selectivity decreased when the conversion in-
creased, with for example a selectivity of 74.1 % when the
conversion was 44.7 %. Later this study was extended to the
use of MCM-41 containing aluminum [112-114] or zirconium
[115, 116]. In the two cases the main effect of the incorporation
of the heteroelement in the MCM-41 matrix was an increase of
the multibranched to monobranched heptane isomers in the
reaction products. More recently phosphotungstic acid has been
deposited on MCM-48 with nickel in presence of cerium [117].
The reaction temperature was 280 °C with a H2 to heptane ratio
of 12. A conversion of 41 % could be obtained in these condi-
tions with a selectivity for isomerization of 91 %.
Phosphotungstic acid has also be impregnated on zirconia
and tested in this reaction [118]. The catalysts were calcined
in air at 750 °C resulting in a partial decomposition of the
POM as shown by solid-state 31P MAS NMR. It was com-
bined to platinum and/or palladium. High conversions could
84 Current Catalysis, 2017, Vol. 6, No. 2
be achieved but here also the amount of cracking products
increased when the conversion increased and could reach
more than 80 % at 320 °C.
Phosphotungstic acid and its cesium salts were also sup-
ported on dealuminated Y zeolite, a solid which can be used
industrially for refining [119-122]. The main interest of the
zeolite is the presence of micropores which will increase
locally the concentration of reactants and so the catalytic
activity. Here also high selectivities could be achieved at
250 °C but increasing the conversion increased also the
cracking amount. When using the cesium salt a very good
selectivity was achieved (95.7 %) for high conversions (65.4
%). In contrast to the results on other molecules, the best
system contained two cesium ions per POM. Addition of a
small amount of chromium to the catalyst led to an increase
of both the activity and the selectivity [123].
9. TRANSFORMATION OF C8 AND C10 ALKANES
There are some reports on the transformation of n-octane
catalyzed by heteropolyacids [124, 125]. In 2005 Yori et al.
studied the reaction at 300 °C in presence of phosphotungstic
acid pure or supported on carbon, silica and zirconia, with
and without platinum, in presence of hydrogen [124]. The
best system was obtained by supporting H3PW12O40 on zir-
conia in the presence of platinum (1 wt. %), the less active
one being obtained on silica and a slow deactivation was
observed in all cases. Unfortunately no selectivities were
given, only the values of the Research Octane Numbers
(RONs) being given. In the second paper [125], the hydro-
conversion of n-octane was studied over nanoscale HZSM-5
zeolites promoted by phosphomolybdic acid (ca. 15 wt. %)
and nickel (ca. 2 wt. %). The reaction was studied between
280 and 340 °C with a hydrogen/octane ratio of 2.0 in moles.
At 320 °C the conversion reached 94.8 % (76.8 % in absence
of nickel). The distribution of products showed only a small
amount of isooctane (3.5 %), the main reaction products be-
ing butanes (28.6 %) and pentanes (32.5 %). Non-negligible
amounts of aromatics were also detected (11.8 %). These
aromatics are formed by oligomerization of the olefins fol-
lowed by naphthalene cyclization [126].
The transformation of n-decane is more documented.
There is only one report of the use of platinum, all other cat-
alysts comprising nickel in combination with the POM. In
2009 Gagea et al. have reported the synthesis of phospho-
tungstic acid incorporated into SBA-15 and its use in the
transformation of decane after addition of platinum (0.5 wt.
%) [127]. They compared the results to those achieved on
samples prepared by direct impregnation. The reaction was
studied between 170 and 300 °C where the conversion
reached ca. 100 %. The selectivity to isomerization was
greatly improved by direct incorporation of the POM in the
SBA-15 and reached ca. 70 % for a 80 % conversion. In
2008 Qiu et al. reported the use of Ni-H3PW12O40 supported
on silica in the hydrocracking of n-decane [128]. The nickel
loading was 5 – 15 wt. % (the best system being obtained
with 5 wt. %) while the POM loading was varied between 30
and 70 wt. %. The reaction was studied at 300 °C with a hy-
drogen/decane ratio of 1500. The best conversion (89 %)
was obtained for 50 wt. % POM while the selectivity to C 5+
isomers decreased continuously when the loading increased
Frédéric Lefebvre
(from 76 % at 30 wt. % to 60 % at 70 wt. %). The same
study was also made by supporting the heteropolyacid on
alumina with quite similar results [129]. In the two cases the
performances of the catalysts were also compared to those
obtained after sulfidation and the effect of N and S poisons
(thiophene and pyridine) was also studied. Later the same
group used acidic cesium salts of phosphotungstic acid sup-
ported on silica or alumina in presence of nickel [130, 131].
On silica the best system was obtained with 1.5 Cs per POM
(conversion 90.5 % selectivity to C5+ isomers 80.3 %) while
on alumina the best loading seemed to be with one cesium
ion per POM. In all cases, in presence of thiophene and pyri-
dine, the performances were better than those of an industrial
catalyst. Finally, H4SiW12O40 was supported, instead of
H3PW12O40, on silica in presence of Ni (5 wt. %) [132]. The
conversion reached 97 - 98 % with a selectivity to C5+ iso-
mers around 85 % in the same conditions than above. These
values decreased to 80 and 78 % respectively in presence of
thiophene (750 ppm) and pyridine (500 ppm).
10. TRANSFORMATION OF HIGH MOLECULAR
WEIGHT PARAFFINS
Jalil reported in 2002 the degradation of polyethylene
over phosphotungstic acid supported on MCM-41 at 420 °C
[133]. The results were compared to those achieved by ther-
mal degradation. The main difference was a lower amount of
residue and a higher proportion of gas compounds, mainly
isobutane and isobutene. More recently Hernandez et al.
studied also the transformation of low density polyethylene
on quite the same catalyst in batch at 450 °C (reaction time
40 min.) [134]. They observed that the thermal cracking pro-
duced nearly 90 % of solid products (waxes) while the sup-
ported heteropolyacid converted ca. 50 % of the polymer
into gas and liquid products. The gas products were mainly
ethane, propane and pentane with only a small amount of
butane in contrast to the above study while the liquid fraction
contained mainly gas oil (34 %) and fuel oil (25 %). The
discrepancy between the two studies is probably related to
the different experimental conditions.
Lee et al. reported in 2010 the production of middle dis-
tillate through hydrocracking of paraffin wax (formed by
Fischer-Tropsch synthesis) over Pd0.15CsxH2.7-xPW12O40 cata-
lysts [135]. The reaction conditions were T = 400 °C, P = 60
bar and reaction time 2 h. The best conversion (ca. 60 %)
was obtained for x = 2.5 and 2.7 with a selectivity for C5-C9
of ca. 60 % and for middle distillate (C10-C20) of ca. 13 %.
There is a linear correlation between the conversion and the
surface acidity of the catalyst.
More recently, in 2014, Eom et al. have reported the hy-
drocracking of extra-heavy oil (vacuum residue, boiling
temperature > 525 °C) by cesium salts of phosphotungstic
acid [136]. The reaction conditions were T = 420 °C, P = 70
bar and reaction time 4 h. Various systems were studied with
a cesium content x varying between 0.0 (H3PW12O40) and 2.9
per POM. The best system was obtained with x = 2.2. In
terms of liquid oil yield, the yield was higher than that ob-
tained with commercial NiMo catalyst, the fraction being
slightly heavier.
Acid Catalysis by Heteropolyacids: Transformations of Alkanes Current Catalysis, 2017, Vol. 6, No. 2 85

Table 2. General table with reactants, products, catalysts and references.

Alkane Catalyst Main Reaction References

product

Propane Cs3-xHxPW12O40 cracking [21, 22]

Butane Cs3-xHxPW12O40 isomerization [22, 24-29]

Cs3-xHxPW12O40 + Al(Ga) isomerization [30, 31]
Supported Keggin polyacids isomerization [32-38]
Cs3-xHxPW12O40 + Pt or Pd isomerization [39-46]

Isobutane Acidic salts of H3PW12O40 alkylation by butenes [47-64]

Cs3-xHxPW12O40 + HF alkylation by butenes [65-67]

n-pentane H3PW12O40/SiO2 + Pd isomerization [68]

Cs3-xHxPW12O40 + Pt or Pd isomerization [23, 43, 69-74]
H3PW12O40/SiO2 or MCM-41 + Pt or Pd isomerization [78]
H3PW12O40/ZrO2 +Pt isomerization [77, 79-81]
H4SiW12O40/SiO2 + Pd isomerization [82]

n-hexane Polyacids on silica cracking [83-87]

H3PW12O40/MCM-41 cracking [88-90]
Keggin polyacids on SBA-15 isomerization [91, 92]
Cs3-xHxPW12O40 isomerization [21, 22]
H3PW12O40/ZrO2 isomerization [93]
H3PW12O40/Al2O3 or SiO2 +Pt isomerization [94, 95]
Cs3-xHxPW12O40 + Pt isomerization [73, 96]
H3PW12O4/SiO2 + Pt/ Al2O3+ Ce isomerization [97-100]
H3PW12O40/MCM-41 + Pt isomerization [101]
H4SiW12O40/SBA-15 + Pt isomerization [102]
Keggin polyacids on ZrO2 isomerization [103]

n-heptane Keggin polyacids on Al2O3 cyclization [105, 106]

Cs3-xHxPW12O40 with or without Pt isomerization [96, 107, 108]
H4SiW12O40/SiO2 + Pd isomerization [108, 109]
H3PMo12O40/TUD-1 isomerization [110]
H3PW12O40/MCM-41 + Pt or Ni isomerization [111-117]
H3PW12O40/ZrO2 + Pt cracking [118]
H3PW12O40/Y zeolite isomerization [119-123]

n-octane supported H3PW12O40 with or without Pt iso-octanes [124]

H3PMo12O40/ZSM-5 cracking [125]

n-decane H3PW12O40/MCM-41 + Pt isomerization [127]

H3PW12O40/SiO2 + Ni cracking [128]
H3PW12O40/Al2O3 + Ni cracking [129]
Supported cracking [130, 131]
Cs3-xHxPW12O40 + Ni cracking [132]
H4SiW12O40/SiO2 + Ni

Polymers H3PW12O40/MCM-41 cracking [133, 134]

Pd0.15CsxH2.7-xPW12O40 cracking [135]
Cs3-xHxPW12O40 cracking [136]
Cs3-xHxPW12O40 + Co/Al2O3 cracking [137]
86 Current Catalysis, 2017, Vol. 6, No. 2
Finally Wang et al. have reported in 2015 that the com-
bination of a classical Fischer-Tropsch synthesis catalyst
(Co/Al2O3) and an acidic cesium salt of phosphotungstic acid
led to an increase of the gasoline selectivity, due to hy-
drocracking of the heavier hydrocarbon products on the
POM [137]. The effect of the amount of POM was studied,
the best result being obtained with 20 wt. %
Cs2.5H0.5PW12O40. In these conditions, the selectivity to gaso-
line could reach 46.4 % while it was only 21.3 % on the
catalyst without POM.
11. GENERAL DISCUSSION
Regarding the two reactions occur simultaneously, isom-
erization and cracking. The catalysts which will be used will
not be the same in the two cases: If cracking is needed, for
example for heavy molecules, the POM will be used alone. If
the desired products are branched isomers, the POM will be
used in combination with platinum or palladium in presence
of hydrogen. For heavy molecules and cracking, it will be
better to use heteropolyacids supported on an oxide support
such as zirconia or silica, the surface of acidic alkaline salts
being mainly due to the presence of micropores where these
molecules could not enter. For isomerization and light mole-
cules both classes can be used. However the platinum phase
must be used as a mechanical mixture and the POM should
be H4SiW12O40 instead of H3PW12O40.
From a mechanistic point of view, two facts must be con-
sidered: (i) the alkane molecule reacts easily with the hetero-
polyacid, leading a POM-(Alkyl) complex on the surface;
(ii) mechanical mixtures of platinum and POM lead to better
results than co-impregnated catalysts. One can then consider
that the surface of the catalyst is covered by alkyl groups
which will transform slowly into carbocations (an activation
period of some hours has been observed due to the increase
of the carbocation concentration until its equilibrium value).
The main difference between propane and higher hydrocar-
bons (see Table 1) is not related to a stronger acidity needed
for the activation of the C-H molecule but simply to the sta-
bility of the carbocation and so to its concentration: It is easy
to verify, for example by theoretical calculations, that ab-
straction of a hydride from propane or butane needs quite the
same energy and that immediately the secondary carbocation
is formed as it is the most stable. In the case of propane it
cannot evolve while in the case of butane it can transform
into the tertiary carbocation. So on the surface the carbo-
cation is mainly present as the carbocation. This carbocation
can then react with an alkene or alkane molecule from the
gas phase or transform into an alkene which will desorb. The
fact that a mechanical mixture gives better results is probably
related to a lower concentration of carbocations on the sur-
face, as they can react with the metal particles and reform the
alkane molecule.
The following table (Table 2) gives the list of the reac-
tions studied here with the corresponding catalysts.
CONCLUSION
This study has shown that heteropolyacids (and their acidic
alkaline salts) are active for the isomerization/cracking of al-
kanes. If the first studies were made on light hydrocarbons the
most recent works are done on wax or heavy oil, in order to
Frédéric Lefebvre
valorize them in gasoline. In this case no noble metal is added
and the reaction is made in batch at a high temperature where
thermal cracking is not negligible. In most cases the POM is
the Keggin phosphotungstic acid or its salts. If the first works
were made on light alkanes the most recent publications report
the valorization of heavy paraffins into more valuable fractions
for petroleum chemistry. It should also be noticed that as the
POM reacts easily with the alkane, it could be used not only for
cracking/isomerization but also for the valorization of alkanes
into more valuable molecules, for example by reaction with
carbon monoxide. The reaction occurs stoichiometrically and it
could be made catalytic by a proper choice of the conditions.
CONFLICT OF INTEREST
The author confirms that this article content has no con-
flict of interest.
ACKNOWLEDGEMENTS
Declared None.
REFERENCES
[1] Pope, M. T. Heteropoly and Isopoly Oxometalates; Springer-Verlag:
Berlin, 1983.
[2] Coronado, E.; Gomez-Garcia, C. J. Polyoxometalate-based molecular
materials. Chem. Rev., 1998, 98, 273-296.
[3] Katsoulis, D. E. A survey of applications of polyoxometalates. Chem.
Rev., 1998, 98, 359-388.
[4] Kozhevnikov, I. V. Catalysis by heteropoly acids and multicomponent
polyoxometalates in liquid-phase reactions. Chem. Rev., 1998, 98, 171-
198.
[5] Mizuno, N.; Misono, M. Heterogeneous catalysis. Chem. Rev., 1998, 98,
199-218.
[6] Müller, A.; Peters, F.; Pope, M. T.; Gatteschi, D. Polyoxometalates:  very
large clustersnanoscale magnets. Chem. Rev., 1998, 98, 239-272.
[7] Na, K.; Okuhara, T.; Misono, M. Solid acid catalyst for paraffin
conversion and process for paraffin conversion using the same. U.S.
Patent 5,750,457, May 12,1998.
[8] Rhule, J. T.; Hill, C. L.; Judd, D. A.; Schinazi, R. F. Polyoxometalates in
medicine. Chem. Rev., 1998, 98, 327-358.
[9] Sadakane, M.; Steckhan, E. Electrochemical properties of polyoxometa-
lates as electrocatalysts. Chem. Rev., 1998, 98, 219-238.
[10] Weinstock, I. A. Homogeneous-phase electron-transfer reactions of
polyoxometalates. Chem. Rev., 1998, 98, 113-170
[11] Lefebvre, F. Synthesis, characterization and applications in catalysis of
polyoxometalate/zeolite composites. Inorganics, 2016, 4, 13.
[12] Keggin, J. F. Structure of the molecule of 12-phosphotungstic acid.
Nature, 1933, 131, 908-909.
[13] Ono, Y. A survey of the mechanism in catalytic isomerization of alkanes.
Catal. Today, 2003, 81, 3-16.
[14] Banares, M. A.; Hu, H.; Wachs, I. E., Genesis and stability of
silicomolybdic acid on silica-supported molybdenum oxide catalysts: In
situ structural-selectivity study on selective oxidation reactions. J. Catal.,
1995, 155, 249-255.
[15] Sugino, T.; Kido, A.; Azuma, N.; Ueno, A.; Udagawa, Y. Partial
oxidation of methane on silica-supported silicomolybdic acid catalysts in
an excess amount of water vapor. J. Catal., 2000, 190, 118-127.
[16] Bar-Nahum, I.; Khenkin, A. M.; Neumann, R. Mild, aqueous, aerobic,
catalytic oxidation of methane to methanol and acetaldehyde catalyzed
by a supported bipyrimidinylplatinum-polyoxometalate hybrid
compound. J. Am. Chem. Soc., 1994, 126, 10236-10237.
[17] Sun, M.; Abou-Hamad, E.; Rossini, A. J.; Zhang, J.; Lesage, A.; Zhu, H.;
Pelletier, J.; Emsley, L.; Caps, V.; Basset, J. M. Methane reacts with
heteropolyacids chemisorbed on silica to produce acetic acid under soft
conditions. J. Am. Chem. Soc., 2013, 135, 804-810.
[18] Lefebvre, F.; Grinenval, E.; Putaj, P. Methane activation and
transformation on polyoxometalates. J. Catal., 2013,
[19] Luzgin, M. V.; Kazantsev, M. S.; Wang, W.; Stepanov, A. G. Reactivity
of methoxy species toward CO on Keggin 12-H3PW12O40: A study with
solid state NMR. J. Phys. Chem. C, 2009, 113, 19639-19644.
Acid Catalysis by Heteropolyacids: Transformations of Alkanes
[20] Zhang, H.; Zheng, A.; Yu, H.; Li, S.; Lu, X.; Deng, F. Formation,
location, and photocatalytic reactivity of methoxy species on Keggin 12-
H3PW12O40: A joint solid-state NMR spectroscopy and DFT calculation
study. J. Phys. Chem. C, 2008, 112, 15765-15770.
[21] Bichon, P.; Gnep, N. S.; Guisnet, M.; Essayem, N. Transformation of
short chain n-alkanes on dodecatungstophosphoric acid and its cesium
salts. NATO Sci. Series II, 2002, 69, 305-308.
[22] Guisnet, M.; Bichon, P.; Gnep, N. S.; Essayem, N. Transformation of
propane, n-butane and n-hexane over H3PW12O40 and cesium salts.
Comparison to sulfated zirconia and mordenite catalysts. Topics Catal.,
2000, 11/12, 247-254.
[23] Na, K.; Okuhara, T.; Misono, M. Solid acid catalyst for paraffin
conversion and process for paraffin conversion using the same. US
Patent 5,750,457, 1998.
[24] Essayem, N.; Coudurier, G.; Fournier, M.; Védrine, J. C. Acidic and
catalytic properties of CsxH3-xPW12O40 heteropolyacid compounds. Catal.
Lett., 1995, 34, 223-235.
[25] Ma, Z.; Hua, W.; Ren, Y.; He, H.; Gao, Z. n-butane isomerization over
Cs-salts of H3PW12O40: a mechanistic study by 13C MAS NMR. Appl.
Catal. A: Gen., 2003, 256, 243-250.
[26] Na, K.; Okuhara, T.; Misono, M. Skeletal isomerization of n-butane over
caesium hydrogen salts of 12-tungstophosphoric acid. J. Chem. Soc.,
Faraday Trans., 1995, 91, 367-373.
[27] Na, K.; Okuhara, T.; Misono, M. Skeletal isomerization of n-butane
catalyzed by an acidic salt of 12-tungstophosphoric acid. Chem. Lett.,
1993, 7, 1141-1144.
[28] Zou, Y.; Yue, B.; Zhang, B.; He, H. Solid synthesis of CsxH3-xPW12O40
salts and their catalytic activity for the isomerization of n-butane. Chem.
Lett., 2006, 35, 202-203.
[29] Gayraud, P. Y.; Essayem, N.; Védrine, J. C. H3PW12O40 acid dispersed
on its Cs salt: Improvement of its catalytic properties by mechanical
mixture and grinding. Catal. Lett., 1998, 56, 35-41.
[30] Zhang, L.; Yue, B.; Feng, S.; Qian, L.; He, H. Solid synthesis of GaxCs2.5-
3xH0.5PW12O40 salts and their catalytic activity in the isomerization of n-
butane. Chin. J. Catal., 2011, 32, 521-524.
[31] Zhang, L.; Yue, B.; Ren, Y.; Chen, X.; He, H. An aluminum promoted
cesium salt of 12-tungstophosphoric acid: a catalyst for butane
isomerization. Catal. Sci. Technol., 2013, 3, 2113-2118.
[32] Bogdan, V. I.; Klimenko, T. A.; Kustov, L. M.; Kazansky, V. B.
Supercritical n-butane isomerization on solid acid catalysts. Appl. Catal.
A: Gen., 2004, 267, 175-179.
[33] He, S.; Liu, X.; Xie, S.; Wang, Q.; Xu, Y.; Xu, L. Effect of steam on the
acid strength of H3PW12O40/SiO2.nH2O and its application in skeletal
isomerization of n-butane. Catal. Commun., 2003, 4, 585-590.
[34] Marme, F.; Coudurier, G.; Védrine, J. C. Acid-type properties of
heteropolyacid H3PW12O40 supported on various porous silica-based
materials. Microp. Mesop. Mater, 1998, 22, 151-163.
[35] Hino, M.; Arata, K. Reaction of butane to isobutane on silica-supported
12-tungstosilisic acid. Green Chem., 2001, 3, 170-172.
[36] Trolliet, C.; Coudurier, G.; Védrine, J. C. Influence of the nature and
porosity of different supports on the acidic and catalytic properties of
H3PW12O40. Topics Catal., 2001, 15, 73-81.
[37] Yang, W.; Billy, J.; Taarit, Y. B.; Védrine, J. C.; Essayem, N. H3PW12O40
supported on Cs modified mesoporous silica: catalytic activity in n-
butane isomerisation and in situ FTIR study. Comparison with
microporous CsxH3-xPW12O40. Catal. Today, 2002, 73, 153-165.
[38] Grinenval, E.; Garron, A.; Lefebvre, F. n-Butane isomerization over
silica-supported heteropolyacids: Study of some parameters. J. Catal.,
2013.
[39] Liu, Y.; Misono, M. Hydroisomerization of n-butane over platinum-
promoted cesium hydrogen salt of 12-tungstophosphoric acid. Materials,
2009, 2, 2319-2336.
[40] Okuhara, T.; Na, K.; Misono, M. Selective isomerization of n-butane
over bifunctional catalysts consisting of noble metals and acidic cesium
salt of heteropoly acid. Sci. Technol. Catal., 1995, 92, 245-250.
[41] Na, K.; Iizaki, T.; Okuhara, T.; Misono, M. Molecular design of solid
acid catalysts. Isomerization of n-butane catalyzed by acidic cesium salts
of 12-tungstophosphoric acid combined with platinum. J. Mol. Catal. A:
Chem., 1997, 115, 449-455.
[42] Na, K.; Okuhara, T.; Misono, M. Catalysis by heteropoly compounds.
34. Skeletal isomerization of n-butane over Pt- or Pd-promoted cesium
hydrogen salts of 12-tungstophosphoric acid. J. Catal., 1997, 170, 96-
107.
[43] Miyaji, A.; Echizen, T.; Li, L.; Suzuki, T.; Yoshinaga, Y.; Okuhara, T.
Selectivity and mechanism for skeletal isomerization of alkanes over
Current Catalysis, 2017, Vol. 6, No. 2 87
typical solid acids and their Pt-promoted catalysts. Catal. Today, 2002,
74, 291-297.
[44] Suzuki, T.; Okuhara, T. Direct evidence of intramolecular rearrangement
in skeletal isomerization of n-butane over bifunctional catalysts. Catal.
Lett., 2001, 72, 111-113.
[45] Okuhara, T.; Yamada, T.; Seki, K.; Johkan, K.; Nakato, T. Pore structure
and shape selective catalysis of bifunctional microporous heteropoly
compounds. Microp. Mesop. Mater., 1998, 21, 637-643.
[46] Na, K.; Okuhara, T.; Misono, M. Isomerization of n-butane over
bifunctional platinum-heteropoly compounds in the presence of
hydrogen. J. Chem. Soc., Chem. Commun., 1993, 18,1422-1423.
[47] Ohgoshi, S.; Kanai, J.; Sugimoto, M. Process for alkylating isoparaffin.
EP 0561284A1, 1993.
[48] Okuhara, T.; Yamashita, M.; Na, K.; Misono, M. Alkylation of isobutane
with butenes catalyzed by a cesium hydrogen salt of 12-
tungstophosphoric acid. Chem. Lett., 1994, 23, 1451-1454.
[49] Xie, W.; Fu, Q. Coke precursor as an intermediate during the alkylation
of isobutane/butene over a solid superacid. Sci. China B, 2004, 47, 173-
178.
[50] He, Y.; He, Y. Characterization of coke precursor deposited on the
surface of heteropoly acid catalyst in alkylation. Catal. Today, 2002, 74,
45-51.
[51] Baronetti, G.; Thomas, H.; Querini, C. A. Wells-Dawson heteropolyacid
supported on silica: isobutane alkylation with C4 olefins. Appl. Catal. A:
Gen., 2001, 217, 131-141.
[52] Gayraud, P.Y.; Stewart, I.H.; Hamid, S.B.D.-A.; Essayem, N.; Derouane,
E.G.; Védrine, J.C. Performance of potassium 12-tungstophosphoric salts
as catalysts for isobutane/butene alkylation in subcritical and supercritical
phases. Catal. Today, 2000, 63, 223-228.
[53] Gayraud, P.Y.; Essayem, N.; Védrine, J.C. Porous 12-tungstophosphoric
alkaline salts for isobutane/butene alkylation. Influence of protonic
density and surface polarity of the HPA: Effects of the supercritical
phase. Studies Surf. Sci. Catal., 2000, 130, 2549-2554.
[54] Zhao, Z.; Sun, W.; Yang, X.; Ye, X.; Wu, Y. Study of the catalytic
behaviors of concentrated heteropolyacid solution. I. A novel catalyst for
isobutane alkylation with butenes. Catal. Lett., 2000, 65, 115-121.
[55] Angelis, A.D.; Ingallina, P.; Berti, D.; Montanari, L.; Clerici, M. G. Solid
acid catalysts for alkylation of hydrocarbons. Catal. Lett., 1999, 61, 45-
49.
[56] Chu, W.; Zhao, Z.; Sun, W.; Ye, X.; Wu, Y. Isobutane/butene alkylation
over supported heteropoly acid catalysts: I. Influence of the structure of
silica. Catal. Lett., 1998, 55, 57-61.
[57] Essayem, N.; Kieger, S.; Coudurier, G.; Védrine, J. C. Comparison of the
reactivities of H3PW12O40 and H4SiW12O40 and their K+, NH4+ and Cs+
salts in liquid phase isobutane/butene alkylation. Studies Surf. Sci. Catal.,
1996, 101, 591-600.
[58] Asensi, M. A.; Corma, A.; Martinez, A.; Martinez, C. Catalytic activity
of microporous monovalent salts of H3PW12O40 heteropoly acid for
isobutane/2-butene alkylation. Preprints Div. Petr. Chem., 1996, 41,
692-696.
[59] Corma, A.; Martinez, A.; Martinez, C. Acidic Cs+, NH4+ and K+ salts of
12-tungstophosphoric acid as solid catalysts for isobutane/2-butene
alkylation. J. Catal., 1996, 164, 422-432.
[60] Blasco, T.; Corma, A.; Martinez, A.; Martinez-Escolano, P. Supported
heteropolyacid (HPW) catalysts for the continuous alkylation of
isobutane with 2-butene: The benefit of using MCM-41 with larger pore
diameters. J. Catal., 1998, 177, 306-313.
[61] Rossi, K. J. D.; Jablonski, J. A.; Kresge, C. T.; Kuehl, G. H.; Marler, D.
O.; Rav, G. S.; Rose, B. H. Supported heteropoly acid catalysts. US
5,475,178, 1995.
[62] Bogdan, V. I.; Kazanskii, V. B. Isobutane alkylation with butenes and
the oligomerization of C4 olefins in supercritical reagents. Kinet. Catal.,
2005, 46, 834-838.
[63] Sarsani, V. R.; Wang, Y.; Subramaniam, B., Toward stable solid acid
catalysts for 1-butene + isobutane alkylation: Investigations of
heteropolyacids in dense CO2 media. Ind. Eng. Chem. Res., 2005, 44,
6491-6495.
[64] Salinas, A. L. M.; Kong, D.; Taarit, Y. B.; Essayem, N. Continuous
iC4/C4= alkylation under iC4 supercritical conditions over
K2.5H0.5PW12O40 and H-Beta solid acids. Ind. Eng. Chem. Res., 2004, 43,
6355-6362.
[65] He, Y.; He, Y. The effect of trace amounts of promoter on the selectivity
of catalyst in the solid acid alkylation. Appl. Catal. A. Gen., 2004, 268,
115-119.
88 Current Catalysis, 2017, Vol. 6, No. 2
[66] He, Y.; He, Y. Behavior of trace amount of HF reaction promoter in
alkylation catalyzed by solid acid. I. Promotion effect of promoter on
reaction. Chin. J. Catal., 2004, 25, 349-352.
[67] He, Y.; Man, Z. Behavior of trace amount of HF reaction promoter in
alkylation catalyzed by solid acid. II. Interaction of promoter with
catalyst. Chin. J. Catal., 2004, 25, 353-356.
[68] Suzuki, S.; Kogai, K.; Ono, Y. Isomerization of alkanes over a palladium
salt of heteropolyacid. Chem. Lett., 1984, 13, 699-702.
[69] Bardin, B.B.; Davis, R.J.A comparison of cesium-containing heteropoly-
acid and sulfated zirconia catalysts for isomerization of light alkanes.
Topics Catal., 1998, 6, 77-86.
[70] Sun, Y.; Yue, Y. H.; Gao, Z. H3PW12O40 and its cesium salts as pentane
isomerization catalysts at ambient temperature. React. Kint. Catal. Lett.,
1998, 63, 349-354.
[71] Yoshimune, M.; Ohnishi, R.; Okuhara, T. Control of pore size and shape
selective catalysis of Pt-promoted acidic alkaline salts of dodecatungsto-
phosphoric acid. Microp. Mesop. Mater., 2004, 75, 33-39.
[72] Liu, Y.; Na, K.; Misono, M. Skeletal isomerization of n-pentane over Pt-
promoted cesium hydrogen salts of 12-tungstophosphoric acid. J. Mol.
Catal. A. Chem., 1999, 141, 145-153.
[73] Liu, Y.; Koyano, G.; Na, K.; Misono, M. Isomerizations of n-pentane
and n-hexane over cesium hydrogen salt of 12-tungstophosphoric acid
promoted by platinum. App. Catal. A. Gen., 1998, 166, L263-L265.
[74] Essayem, N.; Taarit, Y. B.; Feche, C.; Gayraud, P. Y.; Sapaly, G.;
Naccache, C. Comparative study of n-pentane isomerization over solid
acid catalysts, heteropolyacid, sulfated zirconia, and mordenite:
dependence on hydrogen and platinum addition. J. Catal., 2003, 219, 97-
106.
[75] Bardin, B.B.; Davis, R.J. Effect of water on silica-supported
phosphotungstic acid catalysts for 1-butene double bond and alkane
skeletal isomerization. Appl. Catal. A. Gen., 2000, 200, 219-231.
[76] Xu, Y.; Qi, Y.; Lu, G.; Li, S. Skeletal isomerization of n-pentane over
platinum-promoted tungstophosphoric acid supported on MCM-41.
Catal. Lett., 2008, 125, 83-89.
[77] Xu, Y.; Zhang, X.; Li, H.; Qi, Y.; Lu, G.; Li, S. The support effect over
Pt-H3PW12O40 based metal-acid bifunctional catalysts on the catlytic
performance in n-pentane isomerization. Catal. Lett., 2009, 129, 215-
221.
[78] Ivanov, A. V.; Vasina, T. V.; Masloboishchikova, O. V.; Khelkovskaya-
Sergeeva, E. G.; Kustov, L. M.; Houzvicka, J. I. n-alkane isomerization
on heteropolyacids. 1. The influence of acid-base properties of alumina
systems on the state of supported 12-tungstophosphoric heteropolyacid
in Pt-containing catalysts and their activity in n-pentane isomerization.
Russ. Chem. Bull., 2000, 49, 1726-1731.
[79] Xu, Y.; Zhang, X.; Li, H.; Qi, Y.; Lu, G.; Li, S. Promotion effect of
lanthanum addition on the catalytic activity of zirconia supported
platinum and tungstophosphoric acid catalyst for n-pentane
isomerization. Appl. Surf. Sci., 2009, 255, 6504-6507.
[80] Xu, Y.; Zhang, X.; Li, H.; Qi, Y.; Lu, G.; Li, S. A highly effective Pt and
H3PW12O40 modified zirconium oxide metal-acid bifunctional catalyst
for skeletal isomerization: Preparation, characterization and catalytic
behavior study. Catal. Lett., 2008, 125, 340-347.
[81] Hernandez-Enriquez, J. M.; Lajas, L. A. C.; Alamilla, R. G.; Mares, A.
C.; Robles, G. S.; Armenta, J. L. R.; Serrano, L. A. G. Synthesis and
characterization physicochimique de zircone promue avec de l'acide
tungstophosphorique et de l'acide borique et utilisée comme catalyseur
d'isomérisation du n-pentane. Afinidad, 2008, 534, 129-136.
[82] Miyaji, A.; Echizen, T.; Nagata, K.; Yoshinaga, Y.; Okuhara, T.
Selective hydroisomerization of n-pentane to isopentane over highly
dispersed Pd-H4SiW12O40/SiO2. J. Mol. Catal. A. Chem., 2003, 201, 145-
153.
[83] Oulmekki, A.; Lefebvre, F., n-hexane cracking over heteropolyacids.
Part 1. Treatment of data and temperature dependence of the catalytic
activity of H3PW12O40. React. Kinet. Catal. Lett., 1992, 48, 593-600.
[84] Oulmekki, A.; Lefebvre, F. n-hexane cracking over heteropolyacids. Part
2. Catalytic activity and thermal stability of H4SiW12O40, H6P2W18O62
and H6P2W21O71(H2O)3. React. Kinet. Catal. Lett., 1992, 48, 601-606.
[85] Oulmekki, A.; Lefebvre, F. n-hexane cracking over heteropolyacids. Part
3. Silica supported heteropolyacids. React. Kinet. Catal. Lett., 1992, 48,
607-612.
[86] Kuang, W.; Rives, A.; Fournier, M.; Hubaut, R. Solid-state NMR studies
and reactivity of silica-supported 12-tungstophosphoric acid. NATO Sci.
Series II, 2002, 76, 565-569.
[87] Kuang, W.; Rives, A.; Fournier, M.; Hubaut, R. Structure and reactivity
of silica-supported 12-tungstophosphoric acid. Appl. Catal. A. Gen.,
2003, 250, 221-229.
Frédéric Lefebvre
[88] Jalil, P. A.; Al-Daous, M. A.; Al-Arfaj, A.-R. A.; Al-Amer, A. M.;
Beltramini, J.; Barri, S. A. I. Characterization of tungstophosphoric acid
supported on MCM-41 mesoporous silica using n-hexane cracking,
benzene adsorption, and X-ray diffraction. Appl. Catal. A. Gen., 2001,
207, 159-171.
[89] Jalil, P. A.; Tabet, N.; Faiz, M.; Hamdan, N. M.; Hussain, Z. Surface
investigation on thermal stability of tungstophosphoric acid supported on
MCM-41 using synchrotron radiation. Appl. Catal. A. Gen., 2004, 257,
1-6.
[90] Jalil, P. A.; Faiz, M.; Tabet, N.; Hamdan, N. M.; Hussain, Z. A study of
the stability of tungstophosphoric acid, H3PW12O40, using synchrotron
XPS, XANES, hexane cracking, XRD and IR spectroscopy. J. Catal.
2003, 217, 292-297.
[91] Pinto, T.; Dufaud, V.; Lefebvre, F. Isomerization of n-hexane on
heteropolyacids supported on SBA-15. 1. Monofunctional impregnated
catalysts. Appl. Catal. A: Gen., 2014, 483, 103-109.
[92] Pinto, T.; Szeto, K.; Oueslati, N.; Essayem, N.; Dufaud, V.; Lefebvre, F.
Comparison of the acidity of heteropolyacids encapsulated in or
impregnated on SBA-15. Oil Gas Sci. Technol., 2016, 71, 25-37.
[93] Chakhari, S.; Younes, M. K.; Rives, A.; Ghorbel, A. Effect of the doping
agent nature on the charateristic and catalytic properties of aerogel
zirconia catalysts doped with sulfate groups or heteropolytungstic acid.
Mat. Res. Bull., 2015, 72, 35-42.
[94] Essayem, N.; Taarit, Y. B.; Gayraud, P. Y.; Sapaly, G.; Naccache, C.
Heteropolyacid catalysts for hydroisomerization of n-hexane: Effects of
alkali salt modification. J. Catal., 2001, 204, 157-162.
[95] Travers, C.; Essayem, N.; Delage, M.; Quelen, S. Heteropolyanions
based catalysts for paraffins isomerization. Catal. Today, 2001, 65, 355-
361.
[96] Liu, Y.; Koyano, G.; Misono, M. Hydroisomerization of n-hexane and n-
heptane over platinum-promoted Cs2.5H0.5PW12O40 (Cs2.5) studied
in comparison with several other solid acids. Topics Catal., 2000, 11/12,
239-246.
[97] Kuang, W.; Rives, A.; Fournier, M.; Hubaut, R. Silica-supported
heteropoly acids promoted by Pt/Al2O3 for the isomerization of n-
hexane. Catal. Lett., 2002, 79, 133-135.
[98] Kuang, W.; Rives, A.; Tayeb, B. O. B.; Fournier, M.; Hubaut, R.
Isomerization of n-hexane over silica-supported heteropoly acids
promoted by the reduced Ce-Ni oxides. J. Colloid Interf. Sci., 2002, 248,
123-129.
[99] Hubaut, R.; Tayeb, B.O.B.; Kuang, W.; Rives, A.; Fournier, M.
Mechanichal mixtures of Me (Ni, Pd) Ce oxides and silica-supported
heteropolyacids: Role and optimal concentration of each active species in
n-hexane isomerization. Kinet. Catal., 2006, 47, 20-24.
[100] Gherib, A.; Aouissi, A.; Rives, A.; Fournier, M.; Hubaut, R. Isomeriz-
ation of n-hexane over silica-supported heteropolyoxometallates
promoted by Pt-Ce oxides. Chin. J. Catal., 2007, 28, 1041-1046.
[101] Chen, L. F.; Norena, L. E.; Wang, J. A.; Zhou, X. L.; Navarrete, J.;
Hernandez, I.; Montoya, A.; Romo, P. P.; Sala, P.; Pergher, S. C. A study
of n-hexane hydroisomerization catalyzed with the Pt/H3PW12O40/Zr-
MCM-41 catalysts. Catal. Today, 2008, 133-135, 331-338.
[102] Pinto, T.; Arquillière, P.; Niccolai, G. P.; Lefebvre, F.; Dufaud, V. The
comparison of two classes of bifunctional SBA-15 supported platinum-
heyeropolyacid catalysts for the isomerization of n-hexane. New J.
Chem., 2015, 39, 5300-5308.
[103] Ivanov, A.V.; Vasina, T. V.; Nissenbaum, V. D.; Kustov, L. M.;
Timofeeva, M. N.; Houzvicka, J. I. Isomerization of n-hexane on the Pt-
promoted Keggin and Dawson tungstophosphoric heteropoly acids
supported on zirconia. Appl. Catal. A. Gen., 2004, 259, 65-72.
[104] Macht, J.; Carr, R. T.; Iglesia, E. Consequences of Acid Strength for
Isomerization and Elimination Catalysis on Solid Acids. J. Am. Chem.
Soc., 2009, 131 (18), 6554-6565.
[105] Aouissi, A. Transformation of n-heptane by Bronsted acidic sites over
12-tungstosilicic acid. Asian J. Chem., 2010, 22, 4924-4930.
[106] Aouissi, A.; Al-Dhayan, D.; Al-Othman, Z. A.; Lokbaichi, A. Hetero-
polyanions catalysts for n-heptane conversion: Effect of the counter
cation and the addenda atoms. Asian J. Chem., 2012, 24, 3899-3904.
[107] Miyaji, A.; Okuhara, T. Skeletal isomerization of n-heptane and hydroi-
somerization of benzene over bifunctional heteropoly compounds. Catal.
Today, 2003, 81, 43-49.
[108] Sugii, T.; Ohnishi, R.; Zhang, J.; Miyaji, A.; Kamiya, Y.; Okuhara, T.
Acidity-attenuated heteropolyacid catalysts: Acidity measurement using
benzonitrile-TPD and catalytic performance in the skeletal isomerization
of n-heptane. Catal. Today, 2006, 116, 179-183.
[109] Miyaji, A.; Ohnishi, R.; Okuhara, T. Skeletal isomerization of n-heptane
over Pd-H4SiW12O40 supported on SiO2: comparative study with typical
bifunctional catalysts. Appl. Catal. A: Gen., 2004, 262, 143-148.
Acid Catalysis by Heteropolyacids: Transformations of Alkanes
[110] Liu, D.; Quek, X.-Y.; Hu, S.; Li, L.; Lim, H. M.; Yang, Y. Mesostruc-
tured TUD-1 supported molybdophosphoric acid (HPMo/ TUD-1)
catalysts for n-heptane hydroisomerization. Catal. Today, 2009, 147S,
S51-S57.
[111] Yang, X.; Wang, J. A.; Chen, L.; Sebastian, S. P. R.; Robledo, A. M.
Heteropolyacid grafted Pt/Si-MCM-41 catalyst for C7 skeletal
isomerization. Catal. Commun., 2012, 28, 202-206.
[112] Wang, J.A.; Chen, L.F.; Norena, L.E. Al-MCM-41 and Pt/H3PW12O40/
Al-MCM-41: structure, characterization and catalytic properties. Proc.
4th Int. FEZA Conf., 2008, 174, 1259-1262.
[113] Wang, J.A.; Chen, L.F.; Norena, L.E.; Navarrete, J. Spectroscopic study
and catalytic evaluation of mesostructured Al-MCM-41 and Pt/H3PW12
O40/Al-MCM-41 catalysts. Appl. Catal. A. Gen., 2009, 357, 223-235.
[114] Yang, X. K.; Chen, L. F.; Wang, J. A.; Norena, L. E.; Navaro, O. Study
of the Keggin structure and catalytic properties of Pt-promoted
heteropoly compound/Al-MCM-41 hybrid catalysts. Catal. Today, 2009,
148, 160-168.
[115] Wang, J. A.; Zhou, X. L.; Chen, L. F.; Norena, L. E.; Yu, G. X.; Li, C. L.
Hydroisomerization of n-heptane on the Pt/H3PW12O40/Zr-MCM-41
catalysts. J. Mol. Catal. A. Chem., 2009, 299, 68-76.
[116] Wang, J. A.; Chen, L. F.; Norena, L. E.; Navarrete, J.; Llanos, M. E.;
Contreras, J. L.; Navaro, O. Mesoporous structure, surface acidity and
catalytic properties of Pt/Zr-MCM-41 catalysts promoted with 12-
tungstophosphoric acid. Microp. Mesop. Mater., 2008, 112, 61-76.
[117] Wang, Y.; Cui, Y.; Suo, Y.; Zhang, W. Influence of cerium on structure
and catalytic performance of n-heptane hydroisomerization of Ni-
HPW/MCM-48. J. Rare Earths, 2015, 33, 46-54.
[118] Devassy, B. M.; Halligudi, S. B.; Elangovan, S. P.; Ernst, S.; Hartmann,
M.; Lefebvre, F. Zirconia supported phosphotungstic acid as an efficient
catalyst for resorcinol tert-butylation and n-heptane hydroisomerization.
J. Mol. Catal. A. Chem., 2004, 221, 113-119.
[119] Wang, J.; Lin, Z.; Han, S.-Y.; Eum, M.; Lee, C. W. 12-
tungstophosphoric acid supported on dealuminated USY as a catalyst for
hydroisomerization of n-heptane. J. Ind. Eng. Chem., 2003, 9, 281-286.
[120] Wei, R.; Gu, Y.; Wang, J. Hydroisomerization of n-heptane over
bimetal-bearing H3PW12O40 catalysts supported on dealuminated USY
zeolite. Sci. China B, 2008, 51, 120-127.
[121] Gu, Y.; Wei, R.; Ren, X.; Wang, J. Cs salts of 12-tungstophosphoric acid
supported on dealuminated USY as catalysts for hydroisomerization of
n-heptane. Catal. Lett., 2007, 113, 41-45.
[122] Wang, J.; Jiang, D.; Baeg, J. O.; Lee, C. W. Hydroisomerization of n-
heptane over modified USY-supported H3PW12O40 catalysts: Effect of
hydrotreatment for USY. J. Ind. Eng. Chem., 2004, 10, 454-459.
[123] Wei, R.; Wang, J.; Xiao, G. Hydroisomerization of n-heptane over Cr
promoted Pt-bearing H3PW12O40 catalysts supported on dealuminated
USY zeolite. Catal. Lett., 2009, 127, 360-367.
[124] Yori, J.C.; Grau, J.M.; Benitez, V.M.; Sepulveda, J. Hydroisomerization-
cracking of n-octane on heteropolyacid H3PW12O40 supported on ZrO2,
Current Catalysis, 2017, Vol. 6, No. 2 89
SiO2 and carbon. Effect of Pt incorporation on catalyst performance.
Appl. Catal. A. Gen., 2005, 286, 71-78.
[125] Chen, L.; Wang, X.; Guo, H.; Guo, X.; Wang, Y.; Liu, H.; Li, G.
Hydroconversion of n-octane over nanoscale HZSM-5 zeolites promoted
by 12-molybdophosphoric acid and Ni. Catal. Commun., 2007, 8, 416-
423.
[126] Yin, C. L.; Zhao, R. Y.; Liu, C. G. Hydrotreating of cracked naphtha
over Ni/HZSM-5 catalyst. Energ Fuels, 2003, 17, 1356-1359.
[127] Gagea, B. C.; Lorgouilloux, Y.; Altintas, Y.; Jacobs, P. A.; Martens, J. A.
Bifunctional conversion of n-decane over HPW heteropoly acid
incorporated into SBA-15 during synthesis. J. Catal., 2009, 265, 99-108.
[128] Qiu, B.; Yi, X.; Lin, L.; Fang, W.; Wan, H. The hydrocracking of n-
decane over bifunctional Ni-H3PW12O40/SiO2 catalysts. Catal. Today,
2008, 131, 464-471.
[129] Sheng, J.; Qiu, B.; Jin, H.; Yi, X.; Fang, W. Alumina supported
H3PW12O40 and Ni catalysts for hydrocracking of n-decane. Asian J.
Chem., 2010, 22, 4439-4449.
[130] Jin, H.; Guo, D.; Sun, X.; Sun, S.; Liu, J.; Zhu, H.; Yang, G.; Yi, X.;
Fang, W. Direct synthesis, characterization and catalytic performance of
non-sulfided Ni-CsxH3-xPW12O40/SiO2 catalysts for hydrocracking of n-
decane. Fuel, 2013, 112, 134-139.
[131] Jin, H.; Yi, X.; Sun, S.; Liu, J.; Yang, G.; Zhu, H.; Fang, W.
Hydrocracking of n-decane over non-sulfided Ni-CsxH3-xPW12O40/Al2O3
catalysts. Fuel Process. Technol., 2012, 97, 52-59.
[132] Jin, H.; Yi, X.; Sun, X.; Qiu, B.; Fang, W.; Weng, W.; Wan, H. Influence
of H4SiW12O40 loading on hydrocracking activity of non-sulfide Ni-
H4SiW12O40/SiO2 catalysts. Fuel, 2010, 89, 1953-1960.
[133] Jalil, P. A. Investigations on polyethylene degradation into fuel oil over
tungstophosphoric acid supported on MCM-41 mesoporous silica. J.
Anal. Appl. Pyrol., 2002, 65, 185-195.
[134] Hernandez, A.; Norena, L.; Chen, L.; Wang, J.-A.; Aguilar, J. Refinery
oil fraction fuels obtained from polyethylene catalytic cracking
employing heteropolyacid-MCM-41 materials. Adv. Mater. Res., 2010,
132, 236-245.
[135] Lee, J.; Hwang, S.; Park, D. R.; Seo, J. G.; Youn, M. H.; Jung, J. C.; Lee,
S.-B.; Chung, J. S.; Song, I. K. Production of middle distillate through
hydrocracking of paraffin wax over Pd0.15CsxH2.7-xPW12O40 catalysts:
Effect of cesium content and surface acidity. Korean J. Chem. Eng.,
2010, 27, 807-811.
[136] Eom, H. J.; Lee, D. W.; Kim, S.; Chung, S. H.; Hur, Y. G.; Lee, K. Y.
Hydrocracking of extra-heavy oil using Cs-exchanged phosphotungstic
acid (CsxH3-xPW12O40, x = 1 - 3) catalysts. Fuel, 2014, 126, 263-270.
[137] Wang, C.; Liu, C.; Hu, Y.; Bu, X.; Zhao, T.; Chou, K.; Li, Q. Highly
efficient polyoxometalate-based catalysts for clean-gasoline synthesis. J.
Mater. Chem. A, 2015, 3, 21424-21427.