ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2015, Vol. 89, No. 5, pp. 766–770. © Pleiades Publishing, Ltd.

, 2015.

CHEMICAL KINETICS
AND CATALYSIS

Selective Hydrogenation of m-Chloronitrobenzene

to m-Chloroaniline over Polyvinylpyrrolidone-Stabilized Pt
and Pt/Sn Catalysts1
Feng Lia, Rui Maa, Hualin Songb, Hua Songa, and Dezhi Yua
a
Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry & Chemical Engineering,
Northeast Petroleum University, Daqing Heilongjing, 163318 China
b
Key Laboratory of Cancer Prevention and Treatment of Heilongjiang Province, Mudanjiang Medical University,
Mudanjiang Heilongjing, 157011 China
e-mail: lifeng@nepu.edu.cn
Received June 26, 2014

Abstract—A Pt–polyvinylpyrrolidone (PVP) catalyst was synthesized via chemical reduction of platinum ions
with hydrazine hydrate in a PVP/n-butanol/H2PtCl6 aqueous solution. Its catalytic activity was evaluated by
the liquid-phase hydrogenation of m-chloronitrobenzene (m-CNB) to m-chloroaniline (m-CAN) under mild
conditions (T = 303 K, p = 0.1 MPa). The as prepared catalyst exhibited higher activity and selectivity than
prepared via conventional ethanol reduction with the same platinum load. The catalytic performance of
PVP–Pt catalyst was remarkably improved by addition of 0.2 wt % Sn4+. The modification mechanism may
be related with the interaction of Sn4+ with nitro group of m-CNB and –NH2 in m-CAN.

Keywords: selective hydrogenation, m-chloronitrobenzene, Pt catalysts, Pt–Sn catalysts, catalysts modifica-

tion.
DOI: 10.1134/S003602441505012X

1. INTRODUCTION droxylamine, azo- and azoxy-dichlorobenzenes, and

Selective hydrogenation of chloronitrobenzenes
(CNBs) to the corresponding chloroanilines (CANs)
is an important reaction in synthesis of various fine
chemicals, such as dyes, corrosion inhibitors, pharma-
ceuticals, herbicides and insecticides [1]. The catalysts
for this process, such as platinum [2–5], palladium
[6], rhodium [7], nickel [8], ruthenium [9], and cop-
per chromite [10], are widely studied. Among hetero-
geneous and homogeneous catalysts, the Pt-based
catalysts with relatively low catalytic hydrodechlorina-
tion rates and high catalytic activities are particularly
attractive [3–5].
In recent years, polymer-stabilized noble-metal
catalysts and their use in heterogeneous catalysis have
received growing attention [11]. Polyvinylpyrrolidone
(PVP) as a water-soluble polymer works not only as
stabilizer of ultrafine particles but also as a functional-
izing material. Their special properties result in coop-
erative and multi-step catalysis [12].
Yu et al. [11] summarized the selective hydrogena-
tion of o-CNB to o-CAN over PVP–Pt catalysts, and
found that besides the desired o-CAN, many byprod-
ucts such as aniline, nitrobenzene, o-chlorophenylhy-
1 The article is published in the original.
chlorobenzene were also formed. To improve the cat-
alytic performance of homogeneous Pt-based cata-
lysts, the strategy of preparing multi- or bi-metallic
catalysts analogous to that in heterogeneous catalysis
shows a great potential. Han et al. [5] investigated the
catalytic performance of homogeneous Pt catalysts
and concluded that the presence of an electron-defi-
cient promoter can improve the selectivity towards
p-CAN. The selectivity of hydrogenation of o-CNB
over PVP–Pd/Pt bimetallic colloidal clusters was
reported to be higher than that over PVP–Pt and
PVP–Pd monometallic colloidal clusters (Yang et al.
[13]). Liu et al. [14] studied the selective hydrogena-
tion of o-CNB to o-CAN over a PVP-stabilized Pt/Ru
colloid with 99.0% selectivity at 100% conversion.
Besides Pt-based catalysts, the introduction of a sec-
ond metal ion into other noble-metal catalysts can
improve the catalytic performance. Li et al. [15, 16]
revealed that metal ions such as Fe3+, Co2+, Sn2+, or
some boron species could improve both the catalytic
activity and the selectivity of PVP-protected Ru col-
loid catalysts in the hydrogenation of CNB. The intro-
duction of Sn4+ into the reaction media at a Sn4+/Pd
molar ratio of 1 : 1 markedly improved the selectivity
to p-CAN (96.6%) with p-CNB conversion rate close
to 100% over a PVP–Pd/Al2O3 catalyst (Li et al. [17]).

766
 SELECTIVE HYDROGENATION OF m-CHLORONITROBENZENE
Therefore, it is reasonably expected that PVP-stabi-
lized bimetallic Pt-based catalysts may be effective for
the selective hydrogenation of CNB to CAN under
mild conditions.
In the present work, the PVP-stabilized platinum
(PVP–Pt) catalysts were prepared under mild condi-
tions in a PVP/n-butanol/H2PtCl6 aqueous solution
with hydrazine hydrate as a reducing agent, and the
effect of preparation conditions on the hydrogenation
of m-CNB to m-CAN was investigated. Besides, the
effect of Sn4+ on the hydrogenation of m-CNB over
PVP–Pt catalyst was studied and the underlying
mechanism was discussed.
2. EXPERIMENTAL
2.1. Preparation of Catalysts
The PVP/n-butanol/H2PtCl6 aqueous solution
was used as a microemulsion system. An aqueous solu-
tion of H2PtCl6 was added to the solution of PVP
(average molecular weight: 40000) and n-butanol and
stirred for 30 min. The mass ratios of H2PtCl6 solution
to n-butanol and PVP are 1 : 15 and 1 : 0.5, respec-
tively. Hydrazine hydrate (N2H4 : H2PtCl6 = 20 : 1,
molar ratio) was added to the obtained mixture and
stirred at 303 K for 20 min. During this step, the reac-
tion system gradually turned transparent dark brown.
The obtained catalyst with Pt loading of 1.0 wt % was
denoted as PVP–Pt. The PVP–Pt/Sn catalyst was
prepared with the similar method by adding Sn4+ to
the H2PtCl6 aqueous solution.
The PVP–n-butanol–H2PtCl6 aqueous solution
was refluxed in air for 3 h to obtain a dark brown liq-
uid, marked as PVP–Pt–BR.
For comparison, the PVP–Pt catalyst with Pt
loading of 1.0 wt % was also prepared by conventional
ethanol reduction method. An appropriate amount of
PVP was weighed, dissolved in H2PtCl6 solution, and
refluxed in ethanol solution in air for 3 h to obtain a
dark brown liquid, marked as PVP–Pt–ER.
2.2. Catalytic Reaction
Hydrogenation of m-CNB was preformed in a
50 mL 3-necked round-bottomed flask at 303 K and
0.1 MPa hydrogen pressure. For a typical reaction, the
vessel was flushed three times with high-purity hydro-
gen to replace air after addition of PVP–Pt catalyst
(containing 5 × 10–4 g Pt) and 5.0 mL of reactant solu-
tion (containing 2 × 10–3 mol m-CNB and 4 × 10–4 mol
NaOH in ethanol). The reaction mixture was stirred
vigorously for 30 min. The hydrogenation products
were analyzed on a Shimadzu GC–14C gas chromato-
graph equipped with a flame ionization detector
(FID) and a DB–Wax capillary column.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89
767
Table 1. Effects of mass ratio of H2PtCl6 solution to n-buta-
nol on hydrogenation of m-CNB over PVP–Pt catalystsa
ωb TOFc, s–1 Conversion, % Selectivity, %
1:8 0.174 53.4 98.6
1 : 10 0.208 63.9 97.9
1 : 12 0.222 68.2 99.5
1 : 15 0.257 78.9 98.3
1 : 18 0.128 39.4 99.1
1 : 20 0.087 26.9 99.3
a Reaction conditions: 5 × 10–4 g Pt; 2 × 10–3 mol m-CNB; T =
303 K; p = 0.1 MPa; reaction time 40 min.
b The mass ratio of H PtCl solution to n-butanol.
2 6
c m-CNB consumption (mol) per mole Pt per second, s–1.
3. RESULTS AND DISCUSSION
3.1. Effects of Mass Ratio of H2PtCl6 Solution
to n-Butanol
As is well known the catalyst performance depends
strongly on the preparation conditions, such as the
composition of the reaction system. In our study, the
PVP–Pt catalytic system was prepared from H2PtCl6
solution, n-butanol and PVP. Table 1 shows the effects
of mass ratio of H2PtCl6 solution to n-butanol on the
catalytic performance of PVP–Pt. Clearly, under the
same load of H2PtCl6, the catalytic performance was
gradually enhanced along with the increased dosage of
n-butanol, and was maximized at mass ratio of H2PtCl6
to n-butanol of 1 : 15, with turnover frequency (TOF)
up to 0.257 s–1, m-CNB conversion of 78.9%, and
m-CAN selectivity of 98.3%. However, with further
increased dosage of n-butanol, the catalytic perfor-
mance of PVP–Pt was gradually weakened.
3.2. Effect of Mass Ratio of H2PtCl6 Solution to PVP
In the PVP–Pt catalyst, PVP can stabilize the
resulting Pt particles. Moreover, as a non-ionic surfac-
tant, the addition of PVP can promote the intersolu-
bility between H2PtCl6 solution and n-butanol to form
a homogeneous microemulsion system. Table 2 shows
the effects of mass ratio of H2PtCl6 solution to PVP on
catalytic performance of PVP–Pt. Clearly, at the mass
ratio of 1 : 0.5, the catalytic performance was maxi-
mized, with TOF up to 0.287 s–1, m-CNB conversion
of 88.3%, and m-CAN selectivity of 98.9%. With fur-
ther increased dosage of PVP, however, the catalytic
performance of PVP–Pt was gradually weakened.
This is because with excessive PVP, which is a macro-
molecule, the resulting PVP–Pt colloid may agglom-
erate to form secondary particles, thus weakening the
catalytic performance.
No. 5 2015
768 FENG LI et al.

Table 2. Effects of mass ratio of H2PtCl6 solution to PVP 0.005–0.015 g mL –1. At the concentration of
on hydrogenation of m-CNB over PVP–Pt catalystsa 0.015 g mL–1, the catalytic activity was maximized
ωb TOF, s–1 Conversion, % Selectivity, % (0.325 s–1), and the conversion of m-CNB reached
100.0%. However, excessive hydrogenation occurred
1 : 0.2 0.179 55.2 98.9 and the selectivity towards m-CAN was decreased
1 : 0.3 0.257 78.9 98.3 from 99.5 to 96.4%, probably due to excessive hydro-
1 : 0.4 0.270 83.1 98.9 genation after complete conversion of m-CNB to
m-CAN.
1 : 0.5 0.287 88.3 98.9
We also compared the catalytic hydrogenation per-
1 : 0.6 0.196 60.3 97.8 formance of m-CNB over PVP–Pt, PVP–Pt–BR,
1 : 0.7 0.082 25.1 99.2 and PVP–Pt–ER catalysts, and the results are listed
a Reaction conditions are similar to Table 1. in Table 4. Clearly, PVP–Pt shows the highest cata-
b
The mass ratio of H2PtCl6 solution to PVP. lytic performance under normal pressure at 303 K.
The catalytic performance changes in the following
Table 3. Effect of H2PtCl6 solution concentration on order: PVP–Pt > PVP–Pt–ER > PVP–Pt–BR, and
hydrogenation of m-CNB over PVP–Pt catalystsa the selectivity towards m-CAN changes in the order:
H2PtCl6 · 6H2O, Conversion, Selectivity, PVP–Pt–BR > PVP–Pt > PVP–Pt–ER. Compared
–1 TOF, s–1 with the PVP–Pt–ER prepared via ethanol reduction,
g mL % %
the PVP–Pt prepared via proposed method displayed
0.005 0.168 51.6 99.5 a higher catalytic activity and selectivity.
0.010 0.315 96.8 98.3
0.015 0.325 100.0 96.4 3.4. Effect of Sn4+ Content
0.020 0.270 83.1 98.9 The addition of some metal cations can remarkably
0.030 0.126 38.6 99.3 enhance both activity and selectivity of the CNB
0.040 0.089 27.4 99.9 hydrogenation over polymer-stabilized platinum col-
a Reaction conditions are similar to Table 1. loid [11, 18]. Effect of Sn4+ addition to the PVP–Pt
catalyst was also investigated, and the results are
Table 4. Comparison of m-CNB hydrogenation over the shown in Table 5. Clearly, the catalytic activity was
PVP–Pt catalysts prepared by different methodsa improved remarkably with Sn4+ content increased
from 0 to 0.2 wt %. Compared with PVP–Pt catalyst,
Catalyst TOF, s–1 Conversion, % Selectivity, % the conversion of m-CNB over PVP–Pt/Sn with
PVP–Pt 0.325 100.0 96.4 0.2 wt % Sn increased from 83.4 to 98.6% and the
selectivity for m-CAN was improved from 97.5 to
PVP–Pt–BR 0.196 60.4 98.1
98.9%. Meanwhile the catalytic activity over PVP–Pt
PVP–Pt–ER 0.303 93.2 91.8 catalyst was enhanced from 0.362 to 0.427 s–1 by addi-
a Reaction conditions are similar to Table 1. tion of 0.2 wt % Sn. However, the catalytic activity was
weakened sharply when the Sn4+ content was higher
Table 5. Effect of Sn4+ content on hydrogenation of
m-CNB over PVP–Pt/Sn catalystsa than 0.2 wt %. Different from the conversion of
m-CNB, the selectivity to m-CAN was enhanced
Sn4+, wt % TOF, s–1 Conversion, % Selectivity, % slightly with increasing addition of Sn4+ into the
PVP‒Pt catalyst.
0 0.362 83.4 97.5
Coq et al. [18] investigated the selective hydrogena-
0.1 0.378 87.3 98.4 tion of p-CNB over bimetallic catalysts of PtM/Al2O3
0.2 0.427 98.6 98.9 (M = Sn, Pb, Ge, Al, Zn). For most of the bimetallic
0.3 0.405 93.3 98.5 formulations the activity was enhanced at low M/Pt
0.5 0.315 72.6 99.2 ratio, which was very likely promoted by an electron-
deficient M species.
1.0 0.160 36.8 98.7
a Reaction time 30 min, other conditions are similar to Table 1.
As it is well-known, the effect of metal cation on
the hydrogenation of halonitroaromatic compound is
extraordinarily complicated. The influence of PVP on
the catalytic properties of Pt colloids from steric or
3.3. Effect of H2PtCl6 Solution Concentration electronic aspects cannot be neglected although the
Table 3 shows the effects of H2PtCl6 solution con- interaction of Pt particles with PVP is weak [19]. How-
ever, the coordination effect of –NH2 in m-CAN with
centration on catalytic performance of PVP–Pt. The Pt particles was much stronger than that of PVP,
catalytic performance was enhanced with the increase which may damage the protective layer of PVP around
of H2PtCl6 solution concentration in the range of Pt particles, thus promoting the agglomeration of Pt

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 89 No. 5 2015

 SELECTIVE HYDROGENATION OF m-CHLORONITROBENZENE
Modification mechanism of Sn4+ to the PVP–Pt catalyst.
particles. Compared with the PVP–Pt catalyst, the
Sn4+ introduced into the PVP–Pt/Sn catalyst coordi-
nated with –NH2 in m-CAN, which weakened the
coordination of –NH2 with Pt particles and enhanced
the protective effect of PVP on Pt particles, thus slow-
ing clown the aggregation of Pt particles. The
improved dispersion of Pt particles in the reaction sys-
tem led to higher activity.
In addition to the coordination between Sn4+ and
‒NH2, the electron-deficient Sn4+ (hard Lewis acid)
preferentially to attracted oxygen (hard Lewis base) in
–NO2 rather than chlorine, which enhanced the
polarity of N=O bond, thereby promoting activated
dihydrogen or hydride on the surface of Pt to attack
the O and N in N=O [17, 20]. However, if the Sn4+
content was too high, the excessive Sn4+ would be
absorbed on the surface to largely occupy the active
centers of catalyst, thus inhibiting the catalytic activity.
The coordination of –NO2 in m-CNB with Sn4+ also
enhanced the electron-withdrawing ability of –NO2
group and induced the lone electron pair on chlorine
transferring to phenyl ring, thus weakening the polar-
ity of C–Cl. The strengthening of C–Cl bond makes
the dehalogenation of m-CNB becomes more difficult.
The proposed mechanism is illustrated in the figure.
4. CONCLUSIONS
We successfully prepared PVP–Pt catalyst in a
PVP–n-butanol–H2PtCl6 aqueous solution using
hydrazine hydrate as a reducing agent. The catalytic
activity and selectivity in hydrogenation of m-CNB to
m-CAN over PVP–Pt are higher than PVP–Pt–ER
prepared via ethanol reduction with the same plati-
num load. The hydrogenation of m-CNB over
PVP‒Pt catalyst was obviously promoted with the
addition of Sn4+. The catalyst with Sn4+ content of
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
769
0.2 wt % exhibited the highest activity. The interaction
of Sn4+ with –NO2 in m-CNB and –NH2 in m-CAN
may explain the improved hydrogenation catalytic
performance of Sn4+ improved PVP–Pt catalyst.
ACKNOWLEDGMENTS
The authors acknowledge the financial supports
from the National Natural Science Foundation of
China (21276048), the Education Department of Hei-
longjiang Province (12541060).
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