ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2017, Vol. 91, No. 2, pp. 201–204. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.A. Shesterkina, E.V. Shuvalova, O.A. Kirichenko, A.A. Strelkova, V.D. Nissenbaum, G.I. Kapustin, L.M. Kustov, 2017, published in Zhurnal Fizicheskoi
Khimii, 2017, Vol. 91, No. 2, pp. 201–204.
NANOMATERIALS
AND ENVIRONMENT
Application of Silica-supported Fe–Cu Nanoparticles in the Selective
Hydrogenation of p-Dinitrobenzene to p-Phenylenediamine
a
a
a
a
A. A. Shesterkina *, E. V. Shuvalova , O. A. Kirichenko , A. A. Strelkova ,
a
a
a,b
V. D. Nissenbaum , G. I. Kapustin , and L. M. Kustov
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
a
b
Department of Chemistry, Moscow State University, Moscow, 119991 Russia
*
e-mail: anastasiia.strelkova@mail.ru
Received June 16, 2016
Abstract—Supported bimetallic Fe–Cu/SiO materials are synthesized, and their catalytic activity in
2
hydrogenation of dinitrobenzene to phenylenediamine at 145–180°С and 1.3 MPa hydrogen pressure
is studied for the first time. The best results (89% selectivity toward p-phenylenediamine at complete
conversion of p-dinitrobenzene) are obtained for the sample synthesized via co-deposition with subse-
quent calcination at 300°С. The sample contains 7% iron and 3% copper. The formation of separate
phases of metal oxides (for the catalysts prepared by impregnation) and mixed bimetallic oxide phases
(
in case of co-deposition procedure) in calcined samples is revealed via thermoprogrammed reduction
with hydrogen.
Keywords: Fe–Cu catalysts, dinitrobenzene hydration, phenylenediamine
DOI: 10.1134/S0036024417020285
INTRODUCTION
by solutions of metal salts (CIm) and by the co-depo-
sition of precursors of both metals onto the carrier
Aromatic amines obtained via the catalytic
reduction of corresponding nitrocompounds are
widely used in the synthesis of different compounds Vpor = 1.05 cm g ; D = 26 nm) was used as the
2
–1
using urea (CoD). KSKG silica gel (S = 108 m g ;
sp
3
–1
por
for fine organic synthesis and pharmaceutical
industry [1, 2]. Nickel-containing catalysts, as well
as catalysts based on platinum-group metals [3–8]
are the most commonly used for the selective
hydrogenation of dinitrobenzene (DNB) to phenyl-
enediamine (PhDA). The main drawback of these
catalysts is a high content of the active components
and their toxicity. The development and investiga-
tion of more effective and environmentally safe cat-
alytic systems remain important goals of modern
carrier. Copper nitrate, ammonium trioxalatoferrate
(
(
NH ) [Fe(C O ) ] · 3H O (98%, Acros Organics)
4 3 2 4 3 2
impregnation method) and iron (III) nitrate (co-
deposition method) were used as the initial com-
pounds. Once the metal precursors were supported,
the samples were dried at 60–110°С and then calcined
at 300°С. The calcined samples were reduced in a Н
2
flow at 300°С. We selected the temperatures on the
basis of thermal analysis and TPR-Н data for the
2
catalysis [9]. In particular, the catalysts containing samples. The synthesized materials were marked as
iron are of great interest, due to their relatively high xFeyCu–N–М, where х and у are the mass percent-
activity in hydrogenation reactions, abundance, low age of Fe and Cu, respectively; N is the method of syn-
cost, and low toxicity [10].
thesis; and M is the conditions of thermal treatment.
The goal of this work was to study the effects of The samples were characterized by TPR-Н
using the
2
the preparation procedure of the supported bimetal- technique described in [11].
lic Fe–Cu/SiO catalysts and the conditions of the
2
The catalytic hydrogenation was conducted in a
00 mL autoclave in the temperature range of 145–
thermal treatment on the catalytic activity and selec-
tivity of p-phenylenediamine formation from p-dini-
trobenzene.
1
1
80°C and initial hydrogen pressure of 1.3 MPa. The
autoclave was charged with 30 mL of 0.08 M DNB
solution in tetrahydrofuran and 0.2 g of catalyst.
Eicosan (0.100 g) was added as an internal standard.
EXPERIMENTAL
Supported bimetallic Fe–Cu catalysts were syn- The samples of the reaction mixture were analyzed by
thesized via the consecutive impregnation of a carrier gas-liquid chromatography.
201