ARTICLE

pubs.acs.org/IECR

Solvent Free Selective Oxidation of Styrene and Benzyl Alcohol to

Benzaldehyde over an Eco-Friendly and Reusable Catalyst,
Undecamolybdophosphate Supported onto Neutral Alumina
Anjali Patel* and Soyeb Pathan
Department of Chemistry, Faculty of Science, M. S. University of Baroda, Vadodara 390002, India
bS Supporting Information
ABSTRACT: Supported undecamolybdophosphate was synthesized and characterized by various physicochemical techniques and
successfully used for solvent free oxidation of styrene and of benzyl alcohol to benzaldehyde. Influence of the reaction parameters
(molar ratio of substrate to H2O2, amount of the catalyst, reaction time, and reaction temperature) were studied. The catalyst was
reused three times without any significant loss in the catalytic activity. FT-IR, XRD, and DRS of regenerated catalyst indicated that
the catalyst was undegraded and stable after the reaction. The novelty of the work lies in obtaining a single selective product,
benzaldehyde, as well as a high TON for the same, under mild conditions.

1. INTRODUCTION their structure,15
18 by removing one or more addenda atoms.

Benzaldehyde is a very valuable chemical that has widespread
applications in perfumery, dyestuff, and agro chemical industries.1
It is the second most important aromatic molecule (after vanillin)
used in the cosmetics and flavor industries. Generally it is obtained
by oxidation of styrene, benzyl alcohol, and toluene as well as
hydrolysis of benzyl chloride into benzaldehyde is one of the most
important transformations in organic synthesis.2
4 The oxidation
of styrene gives a variety of products such as carbonyl com-
pounds, epoxides, diols, and products (aldehydes) of oxidative
cleavage of C
C bond. Production of benzaldehyde is the first
step in oxidation of benzyl alcohol and further oxidation leads to
the production of benzoic acid with side reactions leading to
the other products like toluene, dibenzyl acetal, and benzyl
benzoate.5 Oxidation of toluene is usually carried out in organic
solvents which are environmentally undesirable and benzalde-
hyde produced from hydrolysis of benzyl chloride often contains
traces of chlorine impurities and copious waste is generated in
this process.6 These procedures suffer from a lack of selectivity,
use of organic solvents, toxicity of the reagents, and waste pro-
duction, which requires an environmentally benign alternative.
As a result selective and solvent free oxidation reactions in-
volving catalytic amount of the oxidizing agents or liquid phase
catalytic oxidation have come into prominence. In this con-
text, heteropolyacids/polyoxometalates (HPAs/POMs), espe-
cially 12-molybdophosphoricacid (PMo12) has been gaining
importance due to their redox properties.7
12 However, the
main drawback of PMo12 is its low thermal stability, which results
more or less in degradation of its Keggin structure under catalytic
conditions, resulting in a drop in catalytic performance. The
mentioned problem can be overcome by modifying their proper-
ties via supporting onto the supports. In our laboratory, during
our systematic research on supported POMs, we surprisingly
found that stability as well as catalytic performance of the PMo12
is improved by supporting it onto different supports.13,14
It is well-known that the redox properties of POMs, PMo12,
can be tuned at the atomic/molecular levels without affecting
These types of POMs are called lacunary phosphomolybdate and
lead to the development of active and selective catalysts. Keeping
this in mind, we have started working on lacunary phosphomo-
lybdate. Recently, we have reported the synthesis and character-
ization of undecamolybdophosphate (PMo11) supported onto
hydrous zirconia as well as its catalytic activity for solvent-free
oxidation of styrene.19
The obtained unique results for oxidation of styrene encour-
age us to carry out detailed studies on PMo11 supported onto
different support, in order to see the effect of support on thermal
as well as catalytic properties. It is known that support does not
play always merely a mechanical role but it can also modify the
catalytic properties of the POMs. It is well-known that basic
support cannot be used for supporting POMs, since it decom-
poses on the same. So, in the present study, as an extension of our
work, we have made use of neutral support, neutral alumina was
used as support.
In the present work, we report the synthesis and systematic
characterization of supported sodium salt of undecamolybdo-
phosphate as well as its use as catalyst for selective oxidation to
benzaldehyde from both routes; namely oxidation of styrene as
well as oxidation of benzyl alcohol. A series of catalysts containing
10
40% of Undecamolybdophosphate (PMo11) onto neutral
alumina (Al2O3), were synthesized. The synthesized catalyst was
characterized by various thermal, spectral, and surface techniques.
The catalytic activity was evaluated for the nonsolvent liquid
phase oxidation of styrene as well as benzyl alcohol with aqueous
30% H2O2. The conditions for maximum conversion as well as
selectivity for desired product was optimized by varying different
parameters such as the molar ratio of the substrate to H2O2,
amount of the catalyst, reaction time, and reaction temperature.
Received: September 9, 2011
Accepted: November 15, 2011
Revised: November 15, 2011
Published: November 15, 2011

r 2011 American Chemical Society 732 dx.doi.org/10.1021/ie2020608 | Ind. Eng. Chem. Res. 2012, 51, 732–740
Industrial & Engineering Chemistry Research
A catalytic property for recycled catalyst was also evaluated for
the oxidation of styrene and benzyl alcohol under optimized
condition.
2. EXPERIMENTAL SECTION
2.1. Materials. All of the chemicals used were of A. R. grade.
Sodium molybdate (Merck), Disodium hydrogen phosphate (Merck),
and neutral active Al2O3 (Activity I
II, according to Brockmann),
used as received. Nitric acid, acetone, dichloromethane and
styrene, benzyl alcohol were obtained from Merck and used as
received.
2.2. Synthesis of Undecamolybdophosphate (PMo11). Un-
decamolybdophosphate was synthesized by following the method
we reported earlier.19 Sodium molybdate dihydrate (0.22 mol,
5.32 g) and anhydrous disodium hydrogen phosphate (0.02 mol,
0.28 g) were dissolved in 50
70 mL of double-distilled water and
heated to 80
90 °C followed by the addition of concentrated
nitric acid in order to adjust the pH to 4.3. The volume was then
reduced to half by evaporation and the heteropolyanion was
separated by liquid
liquid extraction with 50
60 mL of acetone.
The extraction was repeated until the acetone extract showed
absence of NO3
ions (ferrous sulfate test). The extracted sodium
salt was dried in air. The obtained material was designated as
PMo11. Anal. Calcd. %: Na, 7.65; Mo, 50.12; P, 1.47; O, 39.52.
Found %: Na, 7.60; Mo, 49.99; P, 1.44; O, 39.92.
2.3. Synthesis of Catalyst. A series of catalysts containing
10
40% of PMo11 were synthesized by impregnating 1 g of Al2O3
with an aqueous solution of PMo11 (0.1
0.4 g/10
40 mL of
water) with stirring for 35 h and dried at 100 °C for 10 h. The
obtained materials were designated as 10% PMo11/Al2O3, 20%
PMo11/ Al2O3, 30% PMo11/Al2O3, 40% PMo11/Al2O3.
3. CHARACTERIZATION
The synthesized materials were characterized by FT-IR, TGA,
DRS, 31P MAS NMR, powder XRD, SEM, and BET surface area.
FTIR spectra of the samples were recorded as the KBr pellet on
the Perkin-Elmer instrument. The total weight loss was calcu-
lated by the TGA method on the Mettler Toledo Star SW 7.01 up
to 600 °C. The UV
vis-DR spectrum was recorded at ambient
temperature on Perkin-Elmer 35 LAMDA instrument using the
1 cm quartz cell. 31P MAS NMR spectra were recorded on a
Bruker Avance DSX—300 NMR spectrometer at 121.48 MHz
using a 7 mm rotor probe with 85% phosphoric acid as an
external standard. The spinning rate was 4
5 kHz. The powder
XRD pattern was obtained by using a Phillips Diffractometer
(Model PW—1830). The conditions used were Cu Kα radiation
(1.5417 A). Elemental analysis and SEM were carried out using
JSM 5610 LV combined with INCA instrument for EDX-SEM.
The BET specific surface area was calculated by using the
standard Bruanuer, Emmett, and Teller method on the basis of
the adsorption data. Adsorption
Desorption isotherms of sam-
ples were recorded on a micromeritics ASAP 2010 surface area
analyzer at
196 °C.
3.1. Catalytic Reaction. The oxidation reaction was carried out
in a borosilicate glass reactor equipped with a double walled
condenser. The desired catalyst, styrene, and H2O2 mixtures were
intensively stirred in the reactor at the set constant temperature for
the whole duration of reactions. The same reaction was carried out
by varying different parameters such as effect of % loading, molar
ratio of substrate to H2O2, amount of the catalyst, reaction time,
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and reaction temperature. A similar procedure was followed for
benzyl alcohol oxidation. After completion of the reaction, catalyst
was removed and the product was extracted with dichloro-
methane. The product was dried with magnesium sulfate and
analyzed on Gas Chromatograph using BP-5 capillary column.
Product was identified by comparison with the authentic samples
and finally by Gas Chromatography
Mass Spectroscopy (GC
MS).
3.2. Leaching Test. Any leaching of the active species from the
support makes the catalyst unattractive and hence it is necessary
to study the stability as well as leaching of PMo11 from the
support. Heteropoly acids can be quantitatively characterized by
the heteropoly blue color, which is observed when it reacted with
a mild reducing agent such as ascorbic acid. In the present study,
this method was used for determining the leaching of PMo11
from the support. Standard samples containing 1
5% of PMo11
in water were prepared. To 10 mL of the above samples, 1 mL of
10% ascorbic acid was added. The mixture was diluted to 25 mL.
The resultant solution was scanned at a λmax of 785 cm
1 for its
absorbance values. A standard calibration curve was obtained by
plotting values of absorbance against % concentration. One g of
supported catalyst with 10 mL water was refluxed for 18 h. Then
1 mL of the supernatant solution was treated with 10% ascorbic
acid. Development of blue color was not observed, indicating that
there was no leaching. The same procedure was repeated with
styrene and the filtrate of the reaction mixture after completion of
reaction in order to check the presence of any leached PMo11.
4. RESULTS AND DISCUSSION
4.1. Analytical Techniques. The absence of blue color
indicates no leaching of PMo11from Al2O3 into reaction medium,
i.e., aqueous supernatant, styrene, and filtrate.
The FT-IR spectra of PMo11 and 20% PMo11/ Al2O3 are
presented in Figure 1. The bands at 3500 cm
1, 1690 cm
1, and
1300 cm
1 are assigned to the O
H, H
O
H, and O
H
O
frequency, respectively, and 1048 and 999 cm
1, 935 and 906 cm
1,
and 855 cm
1 in parent PMo11 (Figure 1 b) attributed to
asymmetric stretching of P
O, Mo
Ot, and Mo
O
Mo respec-
tively. 20% PMo11/Al2O3 (Figure 1 c) shows bands at 1052 cm
1,
1010 cm
1 and 914 cm
1 (broad) correspond to asymmetric
stretching of P
O and Mo
O
Mo, respectively. A broad band of
Al2O3 covers the small Mo
Ot band (935 cm
1) in 20% PMo11/
Al2O3. The shifting and broadening of bands may be due to
interaction of terminal oxygen of PMo11 with Al2O3.
The TGA (Figure 2 a) of PMo11 shows the initial weight loss
observed of 16% up to 30
200 °C and 1.8% at 275 °C. This may
be due to the removal of adsorbed water molecules and crystal-
lization water molecules, respectively. DTA of PMo11 shows
(Figure 2a) endothermic peaks in the region 80
150 °C and
exothermic peak at 300 °C, due to the loss of adsorbed water and
water of crystallization, respectively. The endothermic peak
observed on DTA curve at 450 oC may be attributed to the
decomposition of PMo11.
The TGA of 20% PMo11/Al2O3 (Figure 2b) shows initial weight
loss up to 123 °C and then continues weight loss was observed in the
region 250
375 °C may be due to the removal of adsorbed water
molecules and crystallization water molecules, respectively. This
observation was further supported by DTA of 20% PMo11/Al2O3
(Figure 2b), which shows endothermic peaks at 80 °C, 140 °C
followed by a broad exothermic peak in the region 255
425 °C.
The DRS gives information about the nonreduced hetero-
polyanion due to charge transfer from oxygen to metal. The band
dx.doi.org/10.1021/ie2020608 |Ind. Eng. Chem. Res. 2012, 51, 732–740
Industrial & Engineering Chemistry Research
Figure 1. FT-IR of (a) Al2O3, (b) PMo11, and (c) 20% PMo11/Al2O3.
at 300 (λmax) is attributed to 0 f Mo charge transfer. The λmax of
20% PMo11/Al2O3 is same as that for PMo11. This confirms the
presence of the undegraded PMo11 on the surface of Al2O3. In
other words, the Keggin structure remains unaltered.
The 31P MAS NMR spectra of PMo11 (Figure S1a of the SI) and
20% PMo11/Al2O3 (Figure S1b of the SI) show a single peak at
1.64 ppm and
3.47 ppm respectively. In the present case, the ob-
served chemical shift, shielding, indicates the presence of a chemical
interaction between PMo11 and Al2O3, rather than simple adsorp-
tion. The broadening and shifting in the peak compare to PMo11 and
may be due to interaction of PMo11 and Al2O3. Also, a single peak
indicates no fragmentation of PMo11 species takes place after support.
Thus it can be concluded that PMo11 remains intact on to Al2O3.
XRD of PMo11 (Figure 3) shows sharp peaks indicating its
crystalline nature. XRD pattern of 20% PMo11/Al2O3 shows no
characteristic peaks of PMo11, indicating a very high dispersion of
PMo11 in a noncrystalline form on the surface of Al2O3.
This observation was further supported by scanning electron
microscopy (SEM). SEM of PMo11 shows its semicrystalline
nature. SEM of 20% PMo11/Al2O3 shows a uniform dispersion of
PMo11 in a noncrystalline form on the surface of the support.
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Figure 2. TGA thermograms for (a) PMo11 and (b) 20% PMo11/Al2O3.
The data for BET surface area measurements are shown in
Table 1. The larger surface area of the 20% PMo11/Al2O3 as
compared to that of the support was because of supporting of
PMo11 and it is as expected. With an increase in the percent
loading of PMo11, the surface area decreases. This may be due to
the blocking pores.
4.2. Catalytic Studies. A detail study was carried out on the
oxidation of styrene and benzaldehyde to optimize the condi-
tions. To ensure the catalytic activity, all reactions were carried
out without catalyst. It was found that no oxidation takes place.
4.2.1. Oxidation of Styrene Using Hydrogen Peroxide. The
reaction was carried out by varying the mole ratio of styrene to
H2O2 with 25 mg of the catalyst for 18 h at 80 °C. Generally,
styrene oxidation gives styrene oxide, benzaldehyde, and benzoic
acid (Scheme 1). However, in the present reaction conditions,
the major oxidation product obtained was benzaldehyde may be
because of (i) direct oxidative cleavage of CdC of styrene and
(ii) fast conversion of styrene oxide to benzaldehyde.
With a 1:3 molar ratio, the conversion of styrene was 95% and the
selectivity for benzaldehyde was 95%, While with 1:4 molar ratio, the
conversion was 96.6% with the same selectivity. Hence, further
optimization of the conditions was carried out with a 1:3 molar ratio.
The oxidation of styrene was carried out with H2O2 in a 1:3
molar ratio by using 25 mg of fresh catalysts for 18 h at 80 °C are
presented in Figure 4, which shows, as an increase in the
conversion with increase in the % loading of PMo11 from 10%
to 20%. Further, with increase in % loading from 20% to 40%,
decrease in conversion is found. This may be due to at higher %
loading, the particles may agglomerate on the surface, results in
dx.doi.org/10.1021/ie2020608 |Ind. Eng. Chem. Res. 2012, 51, 732–740
Industrial & Engineering Chemistry Research
Figure 3. Powder XRD and SEM of (a) PMo11 and (b) 20% PMo11/ Al2O3.
Table 1. Total Surface Area for Al2O3, 10% PMo11/ Al2O3,
20% PMo11/ Al2O3, 30% PMo11/ Al2O3 and
40% PMo11/ Al2O3
catalyst surface area (m2/g)
Al2O3 81.0
10% PMo11/ Al2O3 99.7
20% PMo11/ Al2O3 101.8
30% PMo11/ Al2O3 72.9
40% PMo11/ Al2O3 56.2
reduce accessbility to the active sites. Also, the decrease in %
conversion may be correlated with the values of surface area. As
seen in the Table 1, surface area for 30% PMo11/Al2O3 and 40%
PMo11/Al2O3 decreases as compare to 20% PMo11/Al2O3.
Hence, a decrease in % conversion of styrene is as expected.
Next, the loading of PMo11 on the support was fixed at 20%. A
detail study was carried out at 80 °C over 20% PMo11/ Al2O3.
The effect of temperature on the oxidation of styrene was
investigated at three different temperatures viz. 60, 80, and
100 °C, keeping the other parameters fixed: namely styrene
(10 mmol), 30% H2O2 (30 mmol), catalyst (25 mg), and
reaction time (18 h). The results are shown in Figure 5, which
reveals that 19.4, 95.0, and >99% conversion were found
corresponding to 60, 80, and 100 °C, respectively. At elevated
temperature (100 °C), >99% styrene conversion was found with
72% selectivity of benzaldehyde and 28% selectivity for benzoic
acid, i.e., decrease in selectivity for benzaldehyde was observed.
This is due to overoxidation of banzaldehyde to benzoic acid at
elevated temperature. Hence, further optimization of the condi-
tions was carried out with 80 °C temperature.
In order to determine the effect of H2O2 on the oxidation of
styrene to benzaldehyde, we studied six different styrene: H2O2
molar ratios (1:1, 1:2, 1:3, 1:4, 2:1, and 3:1) keeping other
parameter fixed: namely catalyst (25 mg), temperature (80 °C)
and reaction time (18 h). The results are shown in Figure 6.
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Styrene to H2O2 molar ratio of 1:1 and 1:2 resulted in 19.8 and
44.7% conversion, respectively, and when styrene to H2O2 molar
ratio was changed to 1:3, conversion increased to be nearly
95.0%, keeping all other conditions similar. However, conversion
was found to be almost the same at 96.6% when the styrene to
H2O2 molar ratio was further changed to 1:4. Therefore, 1:3
molar ratio of styrene to H2O2 was found to be the optimum in
terms of conversion of styrene.
The amount of catalyst has a significant effect on the oxidation
of styrene. Five different amounts of 20% PMo11/ Al2O3 viz., 10,
15, 20, 25, and 30 mg were used, keeping with all other reaction
parameters fixed: namely temperature (80 °C), namely styrene
(10 mmol), 30% H2O2 (30 mmol), and reaction time (18 h). The
results are shown in Figure 7, indicating 47.1, 78.9, 85.1, 95.0, and
95.1 conversion corresponding to 10, 15, 20, 25, and 30 mg
catalyst, respectively. Lower conversion of styrene into benzal-
dehyde with 10 to 20 mg catalyst may be due to fewer catalytic
sites. The maximum percentage conversion was observed with
25 mg catalyst but there was no remarkable difference in the
progress of reaction when 25 or 30 mg of catalyst was employed.
Therefore, 25 mg amount of catalyst was taken to be optimal.
The time dependence of catalytic solvent free oxidation
of styrene was studied by performing the reaction of styrene
(10 mmol) with 30% H2O2 (30 mmol) in the presence of 25 mg
of catalyst at 80 °C with constant stirring. The percentage of
conversion was monitored at different reaction times. It is seen
from Figure 8, that with increase in reaction time, the %
conversion also increases. Initial conversion of styrene increased
with the reaction time. This is due to the reason that more time is
required for the formation of reactive intermediate (substrate +
catalyst) which is finally converted into the products. It was seen
that 95% conversion was observed at 18 h; when the reaction was
allowed to continue for 24 h, no appreciable change in conver-
sion as well as selectivity was observed.
The optimum conditions for maximum % conversion of
styrene to benzaldehyde are the mole ratio of styrene to H2O2
as 1:3, with 25 mg of catalyst and 18 h reaction time at 80 °C.
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Industrial & Engineering Chemistry Research ARTICLE

Scheme 1. Oxidation of Styrene

Figure 4. Effect of % loading; % Conversion is based on styrene; time = Figure 6. Effect of mole ratio;% Conversion is based on styrene; time =
18 h; temperature = 80 °C; amount of catalyst = 25 mg, molar ratio of 18 h; temperature = 80 °C; amount of catalyst = 25 mg.
styrene to H2O2: 1:3.

Figure 7. Effect of amount of catalyst; % Conversion is based on

Figure 5. Effect of temperature; % Conversion is based on styrene; time = styrene; time = 18 h; temperature = 80 °C; molar ratio of styrene to
18 h; amount of catalyst = 25 mg, molar ratio of styrene to H2O2: 1:3. H2O2: 1:3.

4.2.2. Oxidation of Benzyl Alcohol Using Hydrogen Peroxide. benzoic acid (Scheme 2). However, benzaldehyde was character-
Generally, benzyl alcohol on oxidation gives benzaldehyde and ized as the major oxidation product in the present case. A detail
736 dx.doi.org/10.1021/ie2020608 |Ind. Eng. Chem. Res. 2012, 51, 732–740
Industrial & Engineering Chemistry Research ARTICLE

Figure 9. % Conversion is based on substrate (astyrene/bbenzyl

alcohol); amount of catalyst =25 mg; molar ratio of substrate to
H2O2: 1:3, temperature a80 °C, b90 °C.

Figure 8. Effect of reaction time; % conversion is based on styrene;

amount of catalyst = 25 mg; temperature = 80 °C; molar ratio of styrene Table 3. Oxidation of Styrene and Benzyl Alcohol with Fresh
to H2O2: 1:3. and Recycled Catalystsa
% selectivity
Scheme 2. Oxidation of Benzyl Alcohol catalyst cycle % conversion benzaldehyde TON

20% PMo11/ Al2O3 fresh 95b/22c 95b/91c 4960b/1125c

1 95b/21.6c 95b/90c 4944b/1115c
2 95b/21c 95b/91c 4933b/1115c
b c b c
3 94.4 /21 95 /91 4913b/1109c
a b c
% Conversion is based on substrate ( styrene/ benzyl alcohol);
amount of catalyst =25 mg; molar ratio of substrate to H2O2: 1:3, Time,
b
18 h, c24 h; temperature b80 °C, c 90 °C.

Table 2. Control Experiments for the Oxidation of Styrene

and Benzyl Alcohola

% selectivity
material % conversion benzaldehyde
b
Al2O3
c

b
PMo11 96 >99
c
21 93
a
% Conversion is based on substrate (bstyrene/cbenzyl alcohol);
Amount of PMo11, 4.2 mg, amount of Al2O3 21.8 mg; Substrate:
H2O2, 1: 3; Time, b18 h, c24 h; temperature b80 °C, c90 °C.

study, similar to oxidation of styrene, was carried out on the

oxidation of benzyl alcohol by varying different parameters such as
molar ratio of benzyl alcohol to H2O2, amount of the catalyst,
reaction time and reaction temperature to optimize the conditions
for maximum conversion and selectivity.
The optimum conditions for maximum % conversion of
benzyl alcohol (22%) with 90% selectivity of benzaldehyde are
the mole ratio of benzyl alcohol to H2O2 as 1:3, with 25 mg of
catalyst and 24 h reaction time at 90 °C.
The control experiments with Al2O3 and PMo11 were also
carried out under optimized conditions with styrene and H2O2 as
well as benzyl alcohol and H2O2. It can be seen from Table 2 that
Al2O3 is inactive toward the oxidation of styrene and oxidation of Figure 10. FT-IR frequency data for (a) fresh and (b) regenerated
benzyl alcohol indicating the catalytic activity is due to only catalyst.

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Industrial & Engineering Chemistry Research
PMo11. The same reaction was carried out by taking the active
amount of PMo11 (4.2 mg). It was found that the active catalyst
gives, 96% conversion of styrene with >99% selectivity of
benzaldehyde and 21% conversion of benzyl alcohol with 93%
selectivity of benzaldehyde. Almost the same obtained activity for
supported catalyst indicates that PMo11 is the real active species.
Thus, we are successful in supporting PMo11 onto Al2O3 without
any significant loss in activity and hence in overcoming the
traditional problems of homogeneous catalysis.
4.3. Heterogeneity Test. Heterogeneity test was carried out
for the oxidation of styrene and benzyl alcohol as examples. For
the rigorous proof of heterogeneity, a test20 was carried out by
filtering catalyst from the reaction mixture at 80 °C after 2 h
(for benzyl alcohol; 90 °C after 8 h) and the filtrate was allowed
to react up to 4 h (for benzyl alcohol; 10 h). The reaction mixture
of 2 h and the filtrate were analyzed by gas chromatography. No
change in the % conversion as well as % selectivity was found
indicating the present catalyst fall into category C,21 i.e., active
species does not leach and the observed catalysis is truly
heterogeneous in nature. The results are presented in Figure 9.
4.4. Recycling of the Catalyst. Oxidation of styrene as well as
oxidation of benzyl alcohol was carried out with the recycled
catalyst, under the optimized conditions. The catalyst was
removed from the reaction mixture after completion of the
reaction by simple filtration, washed with dichloromethane and
dried at 100 °C. The catalyst was recycled in order to test its
activity as well as stability. The obtained results are presented in
Table 3. As seen in the table, there was no appreciable change
observed in selectivity, however, little decrease in conversion was
Figure 11. Powder XRD of (a) 20% PMo11/Al2O3 and (b) R-20%
PMo11/Al2O3.
Table 4. Comparison of Oxidation of Styrene with Reported Catalysta
catalyst styrene (mmole) H2O2 (mmole)
b
20% PMo11/ Al2O3 10 30
c
(PPh4)4[PMo12O40] 3 3DMF 10 50
60
a
% Conversion is based on styrene; temperature b80 °C, c 65 °C; cco-catalyst NaHCO3.
Table 5. Comparison of Oxidation of Benzyl Alcohol with Reported Catalysta
catalyst benzyl alcohol (mmole) H2O2 (mmole) solvent
b
20% PMo11/ Al2O3 10 30
c
PMA/VAMO 20 60 toluene
a
% Conversion is based on bbenzyl alcohol; temperature b90 °C, c45 °C; cphase transfer agent CTABr.
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observed which shows that the catalysts are stable and can be
regenerated for repeated use.
4.5. Characterization of the Regenerated Catalyst. The
catalyst, 20% PMo11/ Al2O3, was regenerated in order to test its
stability. The regenerated catalyst (R-20% PMo11/Al2O3) was
characterized for FT-IR, XRD, and DRS in order to confirm the
retention of the catalyst structure, after the completion of the reaction.
The FT-IR data for the fresh as well as the regenerated catalysts are
represented in Figure 10. The characteristic FT-IR bands for PMo11
appear at 1048 and 999 cm
1, 935 and 906 cm
1, and 855 cm
1. No
appreciable shift in the FT-IR band position of the regenerated
catalyst compare to 20% PMo11/ Al2O3 indicates the retention of
Keggin type PMo11 onto Al2O3. The XRD pattern for the fresh as
well as the regenerated catalysts is shown in Figure 11. There is no
appreciable change in XRD spectra of fresh as well as regenerated
catalyst indicating the stability of PMo11 after regeneration. The
powder XRD of R-20% PMo11/ Al2O3 does not show any additional
peak indicating the PMo11species do not decompose after regenera-
tion and the Keggin unit remains intact on the surface of Al2O3.
The DRS gives information about the nonreduced hetero-
polyanion due to charge transfer from oxygen to metal. The λmax
of 20% PMo11/ Al2O3 and R-20% PMo11/ Al2O3 is same as that
for PMo11. This confirms the presence of the undegraded PMo11
species in catalysts. In other words, the Keggin structure remains
unaltered even after recycling of catalyst.
4.6. Comparison with Other Catalysts. Comparative data for
oxidation of styrene and benzyl alcohol over reported catalysts
and present catalyst is given in the Tables 4 and 5, respectively
(see Scheme 3).
A literature survey shows that, recently, Bhattacharyya et al. reported
oxidation of styrene catalyzed by (PPh4)4[PMo12O40] 3 3DMF
and NaHCO3 as cocatalyst.22 They have carried out oxidation
Scheme 3. Hypothetic Mechanism of the Catalytic Oxidation
solvent % conversion % selectivity TON ref.
95 95 4960
CH3CN 98 91 4950 22
% conversion % selectivity TOF TON ref.
22 91 47 1125
32 100 24 23
dx.doi.org/10.1021/ie2020608 |Ind. Eng. Chem. Res. 2012, 51, 732–740
Industrial & Engineering Chemistry Research
reaction using acetonitrile as a solvent and reported 98% conver-
sion and 91% selectivity of epoxide (Table 4) with TON of 4950.
In the present work, 20% PMo11/ Al2O3 gives 95% conver-
sion and 95% selectivity toward benzaldehyde (TON 4960),
an industrial important product.
Kumar et al. have carried out oxidation of benzyl alcohol
catalyzed by phosphomolybdic acid supported onto vanadium

aluminum mixed oxide (PMA/VAMO) using toluene as a solvent
with CTABr as phase transfer agent and 32% conversion is observed
with 100% selectivity of benzaldehyde (Table 5).23 While in the
present case, 20% PMo11/ Al2O3 gives 22% conversion with 91%
selectivity toward benzaldehyde under solvent free conditions
without phase transfer agent. Moreover, the present catalyst gives
double TOF (47 h1‑) for oxidation of benzyl alcohol as compare to
PMA/VAMO (24 h‑1). Thus, superiority of the catalyst lies in
obtaining higher selectivity of benzaldehyde in solvent free condi-
tions without using any phase transfer reagents.
4.7. Proposed Mechanism. The reaction mechanism of oxida-
tion of styrene or benzyl alcohol over supported PMo11/ZrO2 using
H2O2 as an oxidant is very similar to reported mechanism of the
catalytic oxidation of benzyl alcohol over [PW11O39]7‑.24 They
reported [PW11O39]7‑ react with H2O2 and the active species
[(PO4){WO(O2)2}4]3‑ is formed. This active species is responsible
for oxidation of substrate. In the present case, we are expecting similar
mechanism with [(PO4){MoO(O2)2}4]3‑ as an active species.
5. CONCLUSIONS
In conclusion, a heterogeneous catalyst comprising of undeca-
molybdophosphate and neutral alumina was proved to be success-
ful for solvent-free selective oxidation of styrene and benzyl alcohol
with H2O2 as an oxidant under mild reaction conditions. The
results are very unique and encouraging, as we were successful in
minimizing the waste products as the generated byproduct is water.
Superiority of the catalyst lies in obtaining higher selectivity of
benzaldehyde with 95% conversion of styrene with 4960 TON and
good conversion of benzyl alcohol with 1125 TON. In comparison
with the reported catalyst, the present catalyst is superior in terms of
higher TON/TOF under solvent free oxidation condition without
using any phase transfer reagents. FT-IR, XRD, and DRS of
regenerated catalyst showed that catalyst is stable under present
reaction conditions. Moreover, removal of the catalyst consists of
the single filtration and catalyst can be reused after a simple workup.
The present eco-friendly reusable catalyst is promising cleaner
alternative to the traditional liquid phase oxidation reactions
’ ASSOCIATED CONTENT
The DR Spectra and 31P MAS
bS Supporting Information.
NMR of PMo11 and 20% PMo11/Al2O3 as well as a detailed
study on Oxidation of Benzyl alcohol. This material is available
free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*Tel.: +91 265 2795552. Fax: +91 265 2795392. E-mail: aupatel_
chem@yahoo.com.
’ ACKNOWLEDGMENT
Mr. Soyeb Pathan is thankful to University Grants Commis-
sion (UGC-RFSMS), New Delhi for providing financial
739
ARTICLE
assistance. We are also thankful to Department of Science and
Technology (DST, No. SR/S5/GC-01/2009) for financing a
part of this work.
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