Applied Catalysis A: General 499 (2015) 227–231

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Selective transfer hydrogenation of phenol to cyclohexanone on

supported palladium catalyst using potassium formate as hydrogen
source under open atmosphere
Rajendra D. Patil, Yoel Sasson ∗
Casali Institute of Applied Chemistry, The Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel

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

Article history: A selective, effective and sustainable catalytic transfer hydrogenation of phenol to cyclohexanone on sup-
Received 7 February 2015 ported palladium using potassium formate as benign hydrogen source at atmospheric pressure and mild
Received in revised form 27 March 2015 reaction conditions has demonstrated. A reaction temperature, catalyst (Pd/C), solvent (water) quantity
Accepted 8 April 2015
and type of hydrogen source are found to be most influencing factors for effective phenol conversion.
Available online 20 April 2015
Hydrogen donor potassium formate playing important dual role; as hydrogen source and as additive
to enhance the cyclohexanone selectivity. The catalyst Pd/C has successfully recovered through filtra-
Keywords:
tion and reused up to few batches without considerable loss of phenol conversion and cyclohexanone
Transfer hydrogenation
Heterogeneous catalysis
selectivity.
Cyclohexanone © 2015 Elsevier B.V. All rights reserved.
Phenol
Open atmosphere

1. Introduction as necessity of special facilities for H2 generation, storage, and

Hydrogenation of phenol to cyclohexanone has been subject of
contineous interest and it is widely studied [1]. Cyclohexanone is
known as one of the key chemicals in the synthesis of caprolactam
and adipic acid, which are the main ingredients for the preparation
of Nylon 6, Nylon 66 and polyamide resin [2].
Traditionally, phenol hydrogenation has been carried out in
gas phase, with supported Pd or Pt catalysts as efficient systems
for this reaction [3–6]. However, high temperatures are normally
required for this process (150–300 ◦ C), and the generation of car-
bonaceous deposits (CO) in the course of the reaction leads to
deactivation of the catalyst [7]. The effect of various reaction
parameters (solvents, temperature, support nature) in the phe-
nol hydrogenation on palladium/carbon (Pd/C) has been studied in
the literature [8–10]. More recently, mild (below or at 100 ◦ C tem-
perature) liquid-phase phenol hydrogenation protocols have been
continuously studied under variable molecular hydrogen pressure
using heterogeneous supported palladium catalysts [11,12]. The
selective phenol hydrogenation to cyclohexanone using palladium
catalysts was also reported [13,14]. However, hydrogen (H2 ) is
potentially dangerous, expensive and has some limitations such
∗ Corresponding author. Tel.: +972 265 845 30; fax: +972 265 296 26.
E-mail address: ysasson@huji.ac.il (Y. Sasson).
transportation [1].
Alternative to molecular H2 ; in situ hydrogen generated through
aqueous phase reforming (APR) of methanol on supported palla-
dium catalysts (Pd/Al2 O3 , Pd-La1 /-Al2 O3 ) has been utilized for the
hydrogenation of phenol [15,16]. Formic acid (HCOOH) is another
in situ hydrogen source reported for catalytic phenol hydrogena-
tion using Pd/C [17]. Sodium formate (HCOONa) has been also
utilized as in situ hydrogen source for the catalytic phenol hydro-
genation using Pd/C [18], Pd-PANI/CNF [19] and RuCl2 (PPh3 )3 [20].
However these phenol hydrogenation protocols (using methanol
or ethanol, formic acid and sodium formate) [15–20] also has
few shortcomings. To illustrate, the hydrogenation of phenol with
hydrogen generated from the APR of methanol or ethanol was car-
ried out in stainless steel reactor at very high temperature (217 ◦ C),
3.5 MPa argon pressure and uses bimetallic catalyst (Pd-La1 /-Al2 O3 )
[15,16]. The phenol hydrogenation using formic acid on Pd/C was
carried out in pressure reactor under specific 3 bar N2 pressure and
specific N2 pressure (3 bar) found necessary to achieve high phe-
nol conversion [17]. Further similar phenol hydrogenation using
formic acid performed under open atmosphere (without N2 pres-
sure) resulted into incomplete reaction (60% conversion) and reach
to plateau; which further never lead to completion even with excess
amount of reagent (3–10 eqv.) [17]. Authors assumed that some of
the hydrogen has evolved out under open atmosphere which was
responsible for incomplete phenol hydrogenation [17].

http://dx.doi.org/10.1016/j.apcata.2015.04.009
0926-860X/© 2015 Elsevier B.V. All rights reserved.
228 R.D. Patil, Y. Sasson / Applied Catalysis A: General 499 (2015) 227–231
Scheme 1. Phenol conversion to cyclohexanone using Pd/C catalyst under aqueous
conditions and open atmosphere.
The phenol hydrogenation using sodium formate as hydrogen
donor on Pd/C in closed reaction tube under microwave irradiation
at 80 ◦ C revealed complete phenol conversion and high cyclohex-
anone selectivity [18]. However when phenol hydrogenation was
carried out using conventional heating (instead of microwave) at
80 ◦ C; low conversion was observed (1%) even after few hours (5 h)
[18]. Therefore microwave effect found to be specific and neces-
sary for effective phenol hydrogenation. The phenol hydrogenation
using sodium formate on Pd-PANI/CNF as catalyst shows high
conversion consistently as in closed conditions as well as at atmo-
spheric pressure [19]. However polymer (PANI) grafting on Pd/CNF
is necessary because phenol hydrogenation using only Pd/CNF
shows relatively low conversion (72%) and reduced cyclohexanone
selectivity (81%). Therefore pre-requisite complex synthesis of sup-
porting material PANI/CNF using polymerization of corresponding
aniline in carbon nanofibers (CNF) suspension involves additional
synthesis steps, economical cost and hazardous chemicals [19].
In order to make industrially important phenol hydrogenation to
cyclohexanone as chemist friendly or sustainable chemical trans-
formation; it is necessary to minimize above shortcomings.
Recently our research group has demonstrated that water acti-
vated through reducing metals (Zn, Mg) act as green and alternative
hydrogen source for sustainable catalytic transfer hydrogenation
(CTH) of organic molecules [21,22]. We have revisited the catalytic
transfer hydrogenation of phenol using potassium formate as a
benign H2 source and Pd/C as heterogeneous catalyst under aque-
ous conditions and open atmosphere (atmospheric pressure). In
this context, we report herein one pot, selective phenol hydrogena-
tion to cyclohexanone under open atmosphere without the need of
specific equipments (autoclave or microwave etc.), closed condi-
tions or specific pressure conditions and specific catalyst synthesis
(Scheme 1). Potassium formate as hydrogen source in an organic
transformation has been well known in the literature [23]; however
the phenol hydrogenation using potassium formate as hydrogen
source has been not studied in the past.
2. Experimental
2.1. General
Chemicals were purchased from commercial firms (Aldrich) and
used without further purification. Reactions were performed in a
round bottom flask. GC analyses were performed using Focus GC
from Thermo Electron Corporation, equipped with low polarity ZB-
5 column. The NMR (1 H and 13 C) spectra were recorded in CDCl3 and
D2 O with Bruker DRX-400 instrument in CDCl3 . The Transmission
Electron Microscope (TEM) studies of Pd/C catalyst were done in
a Tecnai F20 G2 instrument (FEI). The palladium (Pd) content of
product was determined by an Inductively Coupled Plasma-Mass
Spectrometry (ICP-MS) Spectrometer (Agilent 7500 cx).
2.2. Experimental procedure for gram scale phenol
hydrogenation to cyclohexanone:
In a typical reaction, phenol (2 g, 21.3 mmol), 0.9 g of 10 wt.%
Pd/C (0.43 mmol), potassium formate (7.15 g, 85 mmol) and de-
ionized water (20 mL) were introduced into 100 mL round bottom
flask. Reaction mixture was subjected to heating at 90 ◦ C for 6 h
with continuous stirring. At the end of reaction, the reaction flask
was allowed to come at room temperature. The product cyclohex-
anone was extracted with diethylether [(25 + 25 + 10) mL] followed
by drying with sodium sulphate, filtration using Whatman paper
and analyzed by GC. The GC analysis shows >99% of phenol con-
version to cyclohexanone. The residue after solvent (diethylether)
evaporation affords the desired cyclohexanone product (Isolated
yield = 94%) as colorless liquid. The product cyclohexanone was
confirmed through standard injection to GC and 1 H NMR.
2.3. Recovery and reuse of Pd/C catalyst
After the aqueous–organic reaction work up, catalyst Pd/C dis-
persed in aqueous phase was filtered through Whatman filter
paper. The catalyst Pd/C remains as residue on the filter paper
washed with diethyl ether (5 mL), dried in the air and reused as
such for further recycling experiments under the similar optimized
reaction condition (Table 4, entry 2).
3. Results and discussion
In order to optimize reaction condition for higher phenol
conversion and excellent selectivity of desired cyclohexanone
various experimental parameters were explored. Initially we
have optimized reaction time for phenol hydrogenation while
other reaction parameters [phenol (2.1 mmol), potassium for-
mate (4 eqv.), 10 wt.% Pd/C (2 mol%), water (10 mL) and 100 ◦ C
temperature] were kept constants (Table 1). Since reaction
mixture containing water, organic substrate and products is non-
homogenous; it has difficult task to monitor the reaction kinetics
(reaction rate with time) in a single reaction. Therefore we have
carried out separate reactions for different time period to optimize
reaction time (Table 1). The phenol hydrogenation showed 85%
conversion after 5 h with excellent selectivity (Table 1, entry 1).
After 6 h, excellent phenol conversion and cyclohexanone selectiv-
ity (>99%) was observed and it was found as optimize reaction time
for phenol hydrogenation under given conditions (Table 1, entry
2). A reduction of reaction time less than 6 h, provided incomplete
conversion (85% in 5 h) while excess time (14 h) allows conversion
of desired cyclohexanone to cyclohexanol and thereby decreases
cyclohexanone selectivity (Table 1, entries 3 and 4). It is challeng-
ing task in phenol hydrogenation to achieve high cyclohexanone
selectivity especially at high conversion [24,25]. In the present sys-
tem, we were successful to achieve excellent phenol conversion and
cyclohexanone selectivity simultaneously under simple and mild
reaction conditions (Table 1, entry 2).
Subsequently, we turned our attention to examine the effects
of the other reaction parameters on the present reaction outcome.
Reactions at 80 ◦ C or above it were provided complete phenol con-
version and excellent cyclohexanone selectivity without any other
external driving force such as external pressure (Table 2, entries
1–4). When the temperature decreased at or below 70 ◦ C, phenol
conversion starts slightly decreasing (Table 2, entry 5). At 60 ◦ C,
Table 1
Optimization of reaction time for phenol hydrogenation.a
Entry Time (h) Conv. (%) C O/C OH (%) Select. (%) C O
1 5 85 85/0 >99
2 6 >99 99/0 >99
3 7 >99 95/05 95
4 14 >99 75/25 75
a
Reaction conditions: substrate (2.1 mmol); potassium formate = 4 eqv.; 10 wt.%
Pd/C, 2 mol%; water (10 mL), 100 ◦ C (oil bath). GC yield. Selectivity is cyclohexanone
to cyclohexanol. C O is cyclohexanone and C OH is cyclohexanol.
 R.D. Patil, Y. Sasson / Applied Catalysis A: General 499 (2015) 227–231 229

Table 2 of potassium formate there is large decrease of cyclohexanone

Temperature optimization for phenol hydrogenationa
selectivity (Table 4, entries 4 and 5). The present results obtained
Entry Temp. (◦ C) Conv. (%) C–O/C–OH(%) Select. (%)C O for cyclohexanone selectivity are inconsistent with those obtained
1 110 >99 99/0 >99 using Pd-PANI/CNF where selectivity remains unchanged irrespec-
2 100 >99 99/0 >99 tive of the amount of reagent (HCOONa) [19]. A stoichiometric
3 90 >99 99/0 >99 amount of 2.1 eqv. of reagent is sufficient to convert most of phenol
4 80 99 98/1 >99 (92%) to products but with less cyclohexanone selectivity (Table 4,
5 70 94 91/3 97
entry 5). Here it should be noted that potassium formate playing
6 60 52 52/0 >99
7 60b 87 87/0 >99 important dual role, as hydrogen source and as additive to increase
8 50 19 19/0 >99 the reaction selectivity toward cyclohexanone.
a
Reaction conditions: substrate (2.1 mmol); potassium formate = 4 eqv.; 10 wt.% We have chosen water as solvent over previously reported
Pd/C, 2 mol%; water (10 mL), 6 h. organic solvents; supercritical carbon dioxide (scCO2 ), ionic liq-
b
16 h reaction time. GC yield. uids for phenol hydrogenation (water also reported) [1]. Use of
water as solvent has obvious advantages in the present work
Table 3 such as; (i) it has a high capacity to dissolve H2 [26], (ii) eas-
Palladium catalyst optimization for phenol hydrogenation.a ily available, environmentally innocuous and relatively cheap; (iii)
Entry Pd (mol%) Conv. (%) C O/C OH(%) Select. (%)C O phenol is completely water soluble while product cyclohexanone
is slightly soluble at higher temperature (above 66 ◦ C) [27], thus
1 2.5 >99 99/0 >99
2 2 >99 99/0 >99
facilitates the easy separation of product from the aqueous phase;
3 1 56 56/0 >99 (iv) increases hydrophilicity of carbon support which favors cyclo-
4 1b 80 80/0 >99 hexanone selectivity [8–10].
5 0.5 37 37/0 >99 We have tested reactions using various amounts of water as
a
Reaction conditions: substrate (2.1 mmol); potassium formate = 4 eqv.; water well as in absence of water (Table 5). A relatively low amount of
(10 mL), 90 ◦ C, 6 h. water (Table 5, entries 4 and 5) or complete absence of water (neat)
b
16 h reaction time. GC yield. (Table 5, entry 6) resulted into large decrease of phenol conversion
and therefore optimum amount of water or above it is necessary
phenol conversion notably decreased to 52% (Table 2, entry 6). Even for effective phenol conversion (Table 5, entries 1–3). From this
longer reaction time (16 h) at 60 ◦ C could not help to reach complete water effect study, it is convenient to conclude that the present phe-
phenol conversion (Table 2, entry 7). Lercher et al. studied temper- nol hydrogenation taking place “in-water” instead of interface of
ature effect on the chemical state and structure of the palladium water i.e. “On water”. Optimum amount of water (2.5 mL) or above
in the relative phenol hydrogenation and implicate the change in it (5–10 mL) helps to dissolve substrate and reagents, increases
chemical behavior of palladium catalyst with change of reaction hydrophilicity of support and consequently necessary collision of
temperature [9]. During the present work also, shift of temperature all the reactive species in liquid phase took place for effective phe-
from 60 ◦ C to optimum temperature (80–90 ◦ C) could be responsi- nol hydrogenation.
ble for chemical change at the surface of Pd/C and increased activity After optimizing various reaction parameters for catalytic phe-
of other reactive species (substrate and reagent) also. Such chem- nol hydrogenation such as; time (6 h), temperature (90 ◦ C), amount
ical reactivity enhancement with increase of temperature in the of palladium catalyst (2 mol%), amount of potassium formate
phenol hydrogenation is in line with literature [18,19]. (3.5 eqv.) and water (2.5–10 mL); we have tested different hydro-
Next we have optimized palladium catalyst (Pd/C); 2 mol% of gen sources under optimized conditions (Table 6). We found that
palladium catalyst with respective to phenol (substrate) was found potassium formate is best of choice as hydrogen source to obtain
enough to get the excellent conversion and selectivity (Table 3, excellent phenol conversion and selectivity (Table 6, entry 1). Like
entry 2). The phenol conversion decreases considerably from 99% potassium formate, sodium formate given comparable results in
to 37% with decrease of palladium catalyst from 2 mol% to 0.5 mol% terms of conversion and selectivity (Table 6, entry 2). The higher
respectively (Table 3, entry 5). Still cyclohexanone selectivity has activity of potassium formate and sodium formate can be attributed
remains constant and was high throughout for all phenol conver- to their counter cations (K+ , Na+ ). It was proposed that such cations
sions irrespective of amount of palladium catalyst. (K+ , Na+ ) interact with oxygen atom of phenolate thereby the
The hydrogen donor potassium formate is another important desorption rate of cyclohexanone and catalytic activity of phenol
aspect to highlight its effect in details during the present opti- hydrogenation are improved [28,29]. Ammonium formate found
mization study (Table 4). The use of potassium formate from 4 less active as hydrogen source in the present phenol hydrogenation
equivalents to 3 equivalents given comparable results in terms of (Table 6, entry 3). Notably reaction using formic acid as hydrogen
conversion and selectivity (Table 4, entries 1–3). At 2.5 equivalents source diminishes phenol conversion (Table 6, entry 4). The phenol
of potassium formate, there is slight decrease of phenol conver- hydrogenation using continuous bubbling of molecular hydrogen
sion and cyclohexanone selectivity. However below 2.5 equivalent given complete conversion but with less cyclohexanone selectivity
(Table 6, entry 5). Additive like formic acid to potassium formate
Table 4
Potassium formate (reagent) optimization for phenol hydrogenation.a Table 5
Water (solvent) effect on phenol hydrogenation.a
Entry Potassium formate (eqv.) Conv. (%) C O/C OH(%) Select. (%)C O
Entry Water (mL) Conv. (%) C O/C OH(%) Select. (%)C O
1 4 >99 99/0 >99
2 3.5 >99 99/0 >99 1 10 >99 99/0 >99
3 3 98 98/0 >99 2 5 >99 99/0 >99
4 2.5 95 69/25 73 3 2.5 >99 99/0 >99
5 2.1 92 52/40 57 4 1 93 93/0 >99
6 1 39 39/0 >99 5 0.5 67 67/0 >99
7 0 5 5/0 >99 6 0 (neat) 31 31/0 >99
a a
Reaction conditions: substrate (2.1 mmol); 10 wt.% Pd/C, 2 mol%; water (10 mL), Reaction conditions: substrate (2.1 mmol); 10 wt.% Pd/C, 2 mol%; potassium for-
90 ◦ C, 6 h. GC yield. mate = 3.5 eqv., 90 ◦ C, 6 h. GC yield.
230 R.D. Patil, Y. Sasson / Applied Catalysis A: General 499 (2015) 227–231

Table 6 pathway it could have given mixture of cyclohexanone and cyclo-

Effect of various hydrogen sources for phenol hydrogenation.a
hexanol as products from phenol. However under force conditions
Entry Hydrogen Conv. (%) C O/C OH (%) Select. (%) C O of longer reaction time (16 h) some of the cyclohexanone converted
source to cyclohexanol in the present work. The controlled experiments
(3.5 eqv.)
using external molecular hydrogen for phenol hydrogenation is
1 Potassium >99 99/0 >99 non-selective giving mixture of cyclohexanone as well as cyclohex-
formate anol (Table 6, entry 5). This also illustrates that phenol conversion
2 Sodium 94 94/0 >99
to cyclohexanone follows transfer hydrogenation pathway under
formate
3 Ammonium 51 51/0 >99 the present reaction conditions.
formate A remarkable effect of excess potassium formate on cyclohex-
4 Formic acid 19 19/0 >99 anone selectivity was observed whereby the competing undesired
5 H2 b 100 78/22 57
cyclohexanol formation was inhibited, allowing an efficient and
6 Potassium 71 48/23 68
formate:formic selective transfer hydrogenation of phenol to cyclohexanone. At the
acidc first assumption it seems that potassium formate (1.5 eqv. excess)
a increases the basicity of support and fascinates moderate phe-
Reaction conditions: substrate (2.1 mmol); 10 wt.% Pd/C, 2 mol%; water (10 mL),
90 ◦ C, 6 h. nol adsorption on support thereby increases reaction activity and
b
Contineous H2 bubbling. cyclohexanone selectivity which is in line with literature obser-
c
9:1 ratio of potassium formate:formic acid used. GC yield. vations [30,31]. Further the product cyclohexanone might weakly
adsorbed on the reactive sites of the catalyst under given conditions
decreases both phenol conversion as well as cyclohexanone selec- and not much available for further hydrogenation to cyclohexanol.
tivity (Table 6, entry 6). Therefore reduction rate of phenol to cyclohexanone is much higher
Different reaction mechanisms have been proposed for catalytic compare to rate of reduction of cyclohexanone to cyclohexanol at
phenol hydrogenation [1]. The widely accepted mechanism is that, higher potassium formate concentration (3.5 eqv.) within optimum
phenol strongly adsorbed on the catalyst support via the oxygen reaction time period. This could be possible reason for high cyclo-
atom of the hydroxyl group and can adopt two different modes hexanone selectivity. On the contrary, at relatively lower potassium
[30,31]. Phenol absorbed on the acidic sites in a coplanar form formate concentration (below 2.5 eqv. of KF); relative reduction
[31], favors the formation of cyclohexanol. On the contrary, phe- rate of two reactions (phenol to cyclohexanone and cyclohexanone
nol can be chemisorbed on the basic sites in a nonplanar form, to cyclohexanol) are not sufficiently differing from each other and
favors the formation of cyclohexanone [32]. In general, a high phe- therefore reaction is non-selective. Also excess potassium formate
nol adsorption capacity [33] on the support promotes high catalytic might be act as reducing agent for some of the oxidized palladium
activity and selectivity to cyclohexanone. By comparison, a weak during the course of the reaction to convert back into palladium (0)
interaction between cyclohexanone and the support [25] favors and thereby increasing the catalyst efficiency.
cyclohexanone desorption and prevent its over-hydrogenation. The TEM analysis was carried out on Pd/C catalyst before and
We propose probable mechanism which involves direct transfer after its use in the reaction to study a change in palladium size
hydrogenation of phenol using potassium formate on Pd/C rather under the given reaction conditions. No significant change in the
than hydrogen production and then hydrogenation of phenol. palladium size (∼3–5 nm) before and after its (Pd/C) use in the reac-
The present catalytic phenol hydrogenation with stoichiometric tion was observed as analyzed from the TEM images (Fig. 1). The
amount of potassium formate as hydrogen donor under open atmo- leaching of palladium (Pd) into products was determined by ICP-MS
sphere shows excellent phenol conversion and selectivity (Table 4, analysis. A negligible amount of Pd was found in the product (1.4 ␮g
entry 5). This fact indicates that phenol hydrogenation follows the of palladium per 1 g of product) by ICP-MS analysis. These facts
direct one step concerted transfer hydrogenation pathway without (TEM and ICP-MS analysis) also support that Pd/C catalyst is stable
loss of H-atoms. Because if reaction could have proceed through and could be reusable under the present reaction conditions. The
free in situ molecular hydrogen; then one can very expect loss of catalyst palladium supported on carbon has successfully recovered
free hydrogen under present open atmosphere condition which through filtration and reused up to four batches without consider-
consequently provided less phenol conversion. Also the selective able loss of phenol conversion and cyclohexanone selectivity (>99%,
formation of cyclohexanone and absence of cyclohexanol under >99%, 98% and 94% phenol conversion observed for first and three
present optimized reaction conditions is more likely to be the consecutive recycle experiments respectively; and selectivity was
case of transfer hydrogenation because if it was the free hydrogen >99% in all the cases).

Fig. 1. TEM image of (A) Pd/C catalyst before the reaction; (B) Pd/C after the reaction.
 R.D. Patil, Y. Sasson / Applied Catalysis A: General 499 (2015) 227–231
4. Conclusions
In conclusion, we have demonstrated effective method for the
selective catalytic phenol hydrogenation using potassium formate
as benign hydrogen source and Pd/C as heterogeneous catalyst
under mild conditions in an open atmosphere. The high conver-
sion of phenol was much dependant on temperature, amount of
water (solvent), amount of palladium catalyst, while cyclohex-
anone selectivity largely depend on the amount of potassium
formate and reaction time. A remarkable effect of excess potas-
sium formate was observed whereby the competing undesired
cyclohexanol formation was inhibited, allowing an efficient and
selective transfer hydrogenation of phenol to cyclohexanone to be
demonstrated. The catalyst Pd/C is recoverable up to large extent
and fully reusable for few recycles without any pre-treatment and
without considerable decrease of phenol conversion and cyclohex-
anone selectivity. Unlike literature methods, present method for
phenol hydrogenation to cyclohexanone is free from specific equip-
ments (microwave or autoclave etc.), closed conditions or specific
pressure conditions, catalyst deactivation and specific catalyst
synthesis.
Acknowledgments
We are thankful to Hani Gnayem and Elad Meller of our lab for
their help during the present work.
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