Polymer-modified supported palladium catalysts for the hydrogenation of acetylene compounds

Article abstract of DOI:10.1134/S0023158416030174

Palladium catalysts supported on zinc oxide modified with polyethylene glycol or pectin were synthesized and investigated in the hydrogenation of acetylene compounds. It was established that the polymercontaining catalysts reduce acetylene hyrbons to olefins with high activity, selectivity, and stability. The composition and structure of the obtained composites were studied by elemental analysis, transmission electron microscopy, and XPS spectroscopy. It was found that the nanosized particles of palladium uniformly immobilized on the surface of zinc oxide were formed in the course of the synthesis of a supported polymer/oxide complex.

Full text of DOI:10.1134/S0023158416030174

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2016, Vol. 57, No. 3, pp. 360–367. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.K. Zharmagambetova, K.S. Seitkalieva, E.T. Talgatov, A.S. Auezkhanova, G.I. Dzhardimalieva, A.D. Pomogailo, 2016, published in Kinetika i Kataliz,
2016, Vol. 57, No. 3, pp. 362–369.
PolymerꢀModified Supported Palladium Catalysts
1
for the Hydrogenation of Acetylene Compounds
a,
a
a
a
A. K. Zharmagambetova *, K. S. Seitkalieva , E. T. Talgatov , A. S. Auezkhanova ,
b,
b, †
G. I. Dzhardimalieva **, and A. D. Pomogailo
a
Sokol’skii Institute of Organic Catalysis and Electrochemistry, Academy of Sciences of Kazakhstan,
Almaty, 050010 Kazakhstan
b
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia
*
eꢀmail: zhalima@mail.ru; **dzhardim@icp.ac.ru
Received July 5, 2015
Abstract—Palladium catalysts supported on zinc oxide modified with polyethylene glycol or pectin were synꢀ
thesized and investigated in the hydrogenation of acetylene compounds. It was established that the polymerꢀ
containing catalysts reduce acetylene hyrbons to olefins with high activity, selectivity, and stability. The comꢀ
position and structure of the obtained composites were studied by elemental analysis, transmission electron
microscopy, and XPS spectroscopy. It was found that the nanosized particles of palladium uniformly immoꢀ
bilized on the surface of zinc oxide were formed in the course of the synthesis of a supported polymer/oxide
complex.
Keywords: catalysis, hydrogenation, acetylene compounds, polymerꢀmodified catalysts
DOI: 10.1134/S0023158416030174
†
INTRODUCTION
this is not the case at least because this reaction is nonꢀ
competitive with homopolymerization in solution folꢀ
lowed by the covalent immobilization of grafted polyꢀ
mer chains. Nevertheless, adsorption polymerization
methods and even the adsorption of polymers in the
pores and on the surface of mineral supports are most
promising for catalytic systems on mixed supports as
the simplest in preparation.
In this work, we used waterꢀsoluble polymers of
both synthetic and natural origin (polyethylene glycol
and pectin) adsorbed on zinc oxide, on which pallaꢀ
dium complexes were immobilized, for the preparaꢀ
tion of catalysts on mixed supports. These polymers
contained considerable amounts of functional groups
In spite of the comparatively shortꢀterm history of
the development of the polymerꢀimmobilized cataꢀ
lysts [1–4], their potential capabilities and disadvanꢀ
tages currently became clear. Among the disadvanꢀ
tages of polymer supports is their low surface area (as
a rule, it rarely reaches tens of square meters per
gram). A solution was found in the development of
mixedꢀtype carriers: polymers with functional groups
were applied as a ligand layer, which is capable of
chemically binding catalytic metal complexes, to traꢀ
ditional mineral carriers (metal oxides or activated
soot) with high specific surface areas [5]. These sysꢀ
tems combine the advantages of traditional homogeꢀ
neous and heterogeneous catalysts: the retention of a
polymer coil as a homogeneous microreactor and the
easy separation and repeated use of a catalyst. In the
general case, polymers can be bound to a powdered
mineral support at any of the stages of its formation [6,
(
OH, COOH, CHO, NH2, etc.). Because of this, on
the one hand, they were adsorbed on an inorganic supꢀ
port and, on the other hand, they retained palladium
complexes to form polymer–metal compounds of difꢀ
ferent composition and structure with them [10–13].
7]. For example, it is believed that the freeꢀradical
polymerization of acrylonitrile, vinylpyrrolidone, and
vinylcarbazole initiated by benzoyl peroxide in the
presence of SiO2 occurs with the formation of grafted
chains on its surface. It is reasonable to assume that
EXPERIMENTAL
Chemicals
n
ꢀHexꢀ2ꢀyne and phenylacetylene of chemically
pure grade were purified by distillation, and the purity
was monitored by chromatography. Ethanol (reagent
†
Deceased.
1
Communication no. 77 from the series Reactivity of MetalꢀConꢀ grade), PdCl2 (reagent grade), HCl (reagent grade,
=
ρ
taining Monomers. For communication no. 76, see Izv. Akad.
Nauk, Ser. Khim., 2016, no. 1, p. 139 [Russ. Chem. Bull., 2016,
vol. 65, no. 1].
3
1
.19 g/cm ), KOH (reagent grade), polyethylene glyꢀ
col ((PEG); weightꢀaverage molecular weight (Mw),
360

POLYMERꢀMODIFIED SUPPORTED PALLADIUM CATALYSTS
361
0
reag
6
1
000; SigmaꢀAldrich), and beet pectin ((BP), Mw
=
where
S
is selectivity, %;
n
is the initial molar amount
5000; uronide component content, 90.3%; the of the reagent; ntp and nreag are the molar amounts of the
degree of esterification, 23.7%) were used without target product and the reagent, respectively, at the point
additional purification. Zinc oxide (chemically pure) in time when the selectivity was calculated;
with a specific surface area of 4.4 m /g was used as an stoichiometric coefficients of substances in the reaction
β
are the
i
2
inorganic support.
equations, which are equal to unity in this case (for the
hydrogenation of alkynes into alkenes).
Conversion was calculated via the formula
Preparation of the 1%Pd/ZnO Catalyst
A 0.02 M solution of K PdCl (5 mL) was added
dropwise to a suspension of zinc oxide (1 g) in water
5 mL) under continuous stirring for 2 h. The resulting
0
reag
2
4
m
− mreag
α =
×100%,
(2)
0
m
(
reag
catalyst was kept in the mother liquor for 12–15 h;
thereafter, it was washed with water and dried in air.
0
reag
where
α
is conversion, %;
m
and mreag are the initial
The completeness of palladium immobilization was and current masses of the reagent, respectively.
controlled by photoelectric colorimetry based on a
difference between the concentrations of palladium
ions in the mother liquor before and after the sorption
of the metal ions.
The stability of catalysts was evaluated by carrying
out the sequential cycles of substrate (2.23 mmol)
hydrogenation on the same sample (0.01 g):
TON = 2370
n,
(3)
where TON is the turnover number; 2370 is the turnꢀ
Preparation of the 1%Pd–Polymer/ZnO Catalyst
over number per cycle; and is the number of cycles
n
The PEG and BP amounts for the preparation of carried out.
the catalyst were taken in terms of one transition metal
Error in parallel experiments was no greater than 5%.
atom per monomer unit. A 5ꢀmL portion of a 0.02 M
solution of PEG (0.0042 g in 5 mL of water) or BP
(
0.0188 g in 5 mL of water) was added dropwise to a
Analysis of Catalysts
suspension of zinc oxide (1 g) in water (5 mL) at room
temperature with continuous stirring for 2 h; then,
5
The analysis of catalysts by Xꢀray photoelectron
spectroscopy (XPS) was carried out on a Kratos Axis
Ultra DLD photoelectron spectrometer (Kratos Anaꢀ
mL of a 0.02 M solution of K PdCl was added for
2 4
3
h. The resulting catalyst was kept in the mother
lytical LTD, United Kingdom). The area of analysis
liquor for 12–15 h; thereafter, it was washed with water
until a negative reaction for chloride ions and dried in
air. The completeness of palladium immobilization
was controlled by photoelectric colorimetry.
2
for each sample was 220
×
220
µ
m , and the depth of
an analyzed layer was 1–2 nm. The radiation source
was a monochromated Al line (1486.6 eV). The
K
α
energy resolution of the instrument was 0.5 eV (for the
Ag d5/2 line of silver). For the minimization of chargꢀ
3
Hydrogenation of nꢀHexꢀ2ꢀyne and Phenylacetylene
ing processes on the sample surface, the powder was
pressed in indium foil, and the spectra were measured
under identical conditions with the use of a neutralizer
and calibrated based on the C1s line of aliphatic comꢀ
pounds (284.8 eV).
Hydrogenation was performed in a thermostatiꢀ
cally controlled longꢀnecked glass flask reactor in an
ethanol solution (25 mL) at an atmospheric pressure
of hydrogen and a temperature of 40°С with intenꢀ
A Vario Micro cube elemental analyzer (Elementar
Analysensysteme GmbH, Germany) was used in the
organic microanalysis of the samples. The carbon
content of the samples (CHNS/O) was determined by
sive stirring (600–700 rockings per minute). The catꢀ
alyst (0.01 g) was preliminarily treated with hydrogen
directly in the reactor for 30 min with intensive stirꢀ
ring; then, 2.23 mmol (0.09 mol/L) of a substrate was
introduced. The substrate amount was taken based
on the uptake of 100 mL of hydrogen. The rate of
reaction was calculated from the hydrogen uptake per
unit time.
a method of combustion at 1150°С in the presence of
pure oxygen with the subsequent reduction of oxides
and separation on a chromatographic column with a
thermal conductivity detector.
The palladium content of the mother liquors before
The selectivity of the action of catalysts was evaluꢀ
ated as the fraction of the target product in the reacꢀ
tion products at a specified degree of conversion:
and after the precipitation of K PdCl4 was calculated
2
from photoelectric colorimetry data, which were
obtained on a Jenway 6300 spectrophotometer (Jenꢀ
way, United Kingdom) based on calibration curves
ntp ×β
reag
S =
×100%,
(1)
0
(n
− nreag)βtp
constructed at the wavelength = 421 nm.
λ
reag
KINETICS AND CATALYSIS Vol. 57
No. 3 2016

3
62
Table 1. Carbon and palladium contents of the 1%Pd–polymer/ZnO catalysts
Element concentration, wt %
ZHARMAGAMBETOVA et al.
Sample
Cexpt/calcd
Pdexpt/calcd
Pd–PEG/ZnO
Pd–BP/ZnO
0.17/0.23
0.57/0.67
1.12/1.00
0.96/1.00
The palladium content of the samples of catalysts
was determined on an XꢀArtM energyꢀdispersive
Xꢀray fluorescence spectrometer (Komita, Russia).
RESULTS AND DISCUSSION
The advantages of waterꢀsoluble polymers include
their biodegradability, nontoxicity [14], and the possiꢀ
bility of synthesizing nanocatalysts in aqueous soluꢀ
tions, which is consistent with the principles of green
chemistry [15]. In particular, polyethylene glycols are
The electronꢀmicroscopic studies were performed
on a JEMꢀ2100 transmission electron microscope
(
Jeol, Japan) with an accelerating voltage of 100 kV.
The specific surface areas ( BET
S
) of zinc oxide and resistant to oxidation and the action of acids and
bases; they possess moderate thermal stability, good
solvating characteristics, and complexꢀforming propꢀ
erties with respect to many metals [16].
a polymerꢀhybrid nanocomposite were measured by
the lowꢀtemperature adsorption of nitrogen on an
Autosorbꢀ1 instrument (Quantachrome, the United
States).
Synthesis of 1%Pd–Polymer/ZnO Catalysts
Chromatographic Analysis of the Reaction Products
of the Hydrogenation of Unsaturated Compounds
According to the photoelectric colorimetry data,
8–99% of the introduced palladium amount was preꢀ
9
cipitated on zinc oxide modified with BP and PEG.
Palladium was also adsorbed quantitatively (to 96%) on
ZnO without treatment by a polymer. Thus, in both of
the catalysts, the palladium concentration of 1.0 wt %
on a total catalyst component basis was close to calcuꢀ
lated data.
The analysis was carried out on a Khromos GKhꢀ
000 chromatograph (Khromos, Russia) with a flameꢀ
ionization detector in the isothermal regime using a
BP21 (FFAP) capillary column with a polar phase
1
(
PEG modified by nitroterephthalate) 50 m in length
and 0.32 mm in inside diameter. The column temperꢀ
ature was 90 , and the injector temperature was
00
sample volume was 0.2
°С
The results of the Xꢀray fluorescence elemental
2
°С; helium served as the carrier gas; the injected analysis of 1%Pd–polymer/ZnO catalysts confirm the
µ
L. The liquid reaction mixꢀ data obtained by photoelectric colorimetry. The carbon
tures were sampled two or three times in the course of content determined by organic microanalysis is consisꢀ
an experiment.
tent with the calculated values and indicative of the
immobilization of polymers on zinc oxide (Table 1).
The lines of zinc, oxygen, carbon, palladium, and
chlorine were detected in the survey XPS spectrum of
the 1%Pd–PEG/ZnO catalyst (Fig. 1). An analogous
pattern was also observed in the XPS spectrum of
Zn 2
p
1
6000
2000
1
%Pd–BP/ZnO.
1
O 1
Zn LMM a
Zn LMM b
Pd 3
s
According to the XPS data, palladium in 1%Pd–
2+
PEG/ZnO occurred in an oxidized state (Pd ) with a
d5/2 binding energy of ~337.4 eV (Fig. 2a). It is likely
8
000
000
0
3
O
KLL
p
that a shift toward smaller energies was caused by the
interaction of palladium with the modified support
matrix and by the formation of a Pd–O bond [17, 18].
In the spectrum of the catalyst modified with pectin,
peaks characteristic of both the oxidized (336.8 eV)
and reduced (335.4 eV) forms of palladium were
detected (Fig. 2b). Probably, the presence of pallaꢀ
dium metal in the initial sample of 1%Pd–BP/ZnO
was caused by its partial reduction with the functional
groups of pectin in the presence of a basic oxide [19].
C 1
s
Zn 3
Zn 3
Cl 2
p
4
s
s
1000
800
600
400
Binding energy, eV
200
0
Fig. 1. Survey XPS spectrum of 1%Pd–PEG/ZnO.
KINETICS AND CATALYSIS Vol. 57
No. 3 2016

POLYMERꢀMODIFIED SUPPORTED PALLADIUM CATALYSTS
a) 3000
363
(
4000
3000
2000
1000
2
000
000
1
0
3
48 346 344 342 340 338 336 334 332 330
Binding energy, eV
0
3
48 346 344 342 340 338 336 334 332 330
Binding energy, eV
Fig. 3. The Pd3
d
XPS spectrum of the reduced sample of
1
%Pd–PEG/ZnO.
(b)
2000
1500
1000
and pore volumes for Pd–PEG/ZnO or ZnO were 7.9
3
and 0.035 or 4.4 and 0.025 cm /g, respectively.
Catalytic Properties of 1%Pd–Polymer/ZnO
in the Hydrogenation of Phenylacetylene
The polymerꢀmodified catalysts manifested high
activity in the reaction of phenylacetylene hydrogenaꢀ
tion. Thus, under comparable conditions, the maxiꢀ
mum rate of reaction on the polymerꢀmodified cataꢀ
lysts was twice as high as that on a polymerꢀfree analog
(
Fig. 5).
The rate of hydrogenation of phenylacetylene in
the presence of 1%Pd/ZnO increased in the first three
3
48 346 344 342 340 338 336 334 332 330
Binding energy, eV
Fig. 2. The Pd3
PEG/ZnO and (b) 1%Pd–BP/ZnO.
d XPS spectra of the samples of (a) 1%Pd–
minutes and then slowly decreased after reaching 4.0
1
×
–6
0
mol/s (Fig. 5, curve
1). The maximum yield of
styrene (65.7%) is observed after 16 min; in this case,
After the treatment of catalysts with hydrogen in a the ethylbenzene content was 28.0% (Fig. 6a).
reactor at 40 , palladium was completely reduced to
a zerovalent state. The Pd d5/2 XPS spectrum (Fig. 3)
°
С
The hydrogenation of phenylacetylene in the presꢀ
3
–6
ence of 1%Pd–PEG/ZnO (8.8
×
10 mol/s) and
exhibited a peak corresponding to the binding energy
of palladium in the zerovalent state (~335.2 eV) [20,
1]. Polymer modification significantly affected the
particle size of palladium and the distribution of the
particles on the support. According to the transmisꢀ
–6
1
%Pd–BP/ZnO (8.1
×
10 mol/s) occurred at a high
rate: in both cases, it sharply increased with passing
through a maximum and then decreased (Fig. 5,
2
curves
2 and 3). According to the data of the chroꢀ
matographic analysis of the test samples taken in the
sion electron microscopy (TEM) data, the supporting course of hydrogenation, styrene accumulated on
of a palladium compound onto materials preliminarily 1%Pd–PEG/ZnO in the initial period; then, it was
treated with PEG or BP led to an increase in the disꢀ reduced to ethylbenzene (Fig. 6b). The composition
persity of palladium. Thus, the metal particle sizes of of the reaction mixture similarly changed in the
Pd/ZnO prepared without a polymer were 30–35 nm hydrogenation of phenylacetylene on 1%Pd–
(
particles of size >40 nm were also detected), whereas BP/ZnO. The concentrations of styrene in the presꢀ
the particle sizes of palladium in the polymerꢀmodiꢀ ence of the pectinꢀcontaining and PEGꢀmodified catꢀ
alysts reached optimum values (74.5 and 72.2%,
respectively) after 7 and 6 min, respectively.
fied catalysts decreased to 2–4 nm. The sufficiently
uniform distribution of an active phase over the oxide
surface treated with a polymer has engaged our attenꢀ
tion (Fig. 4). Note that the catalysts obtained were
The complete conversion of phenylacetylene into
ethylbenzene through the formation of styrene as an
characterized by a comparatively developed surface intermediate product was observed on all of the catalysts
area and a porous structure. Thus, the values of SBET (Fig. 6). The curves of hydrogen uptake confirm the
KINETICS AND CATALYSIS Vol. 57
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364
ZHARMAGAMBETOVA et al.
50 nm
10 nm
10 nm
(а)
(b)
(c)
Fig. 4. Micrographs of the samples of (a) 1%Pd/ZnO, (b) 1%Pd–PEG/ZnO, and (c) 1%Pd–BP/ZnO reduced with hydrogen in
a reactor at 40°C and atmospheric pressure.
chromatographic analysis data: the volume of absorbed tures with ratios of 3 : 1, 1 : 1, and 1 : 3 between the
hydrogen on all of the catalysts was 100 mL (Fig. 7). components. We found that the rate of reaction
The styrene formation selectivity (Sst) for 1%Pd– decreased with the olefin content of the substrate,
whereas Sst remained almost constant (Table 3). By
PEG/ZnO and 1%Pd–BP/ZnO was 88.7 and 86.7%,
respectively. The 1%Pd/ZnO catalyst exhibited lower this is meant that the hydrogenation of phenylacetyꢀ
selectivity. Both of the polymerꢀcontaining catalytic lene occurs consecutively through the stage of the forꢀ
systems were sufficiently stable (TON = 11850– mation of styrene.
1
4220), as compared with the unmodified palladium
Thus, based on the conducted investigations, we
found that the modification of a palladium catalyst
catalyst (Table 2).
The styrene formation selectivity and the activity of with polymers considerably increased its activity and
the polymerꢀmodified catalysts in the course of three selectivity. The activity and stability increased by a facꢀ
repeated cycles decreased insignificantly (Fig. 8). tor of 2, and Sst increased by 16–18% in comparison
Thus, in the hydrogenation of phenylacetylene in the with that of the unmodified catalyst (Table 2).
presence of 1%Pd–BP/ZnO, the values of Sst in the
first and third cycles were 86.7 and 83.4%, respectively
Catalytic Properties of 1%Pd–Polymer/ZnO
(
Fig. 9).
For the determination of the possibility of reducing
phenylacetylene in the presence of styrene, we carried
in the Hydrogenation of nꢀHexꢀ2ꢀyne
All of the catalysts developed exhibited high activꢀ
out experiments on the hydrogenation of their mixꢀ ity in the stereoselective hydrogenation reaction of
ꢀhexꢀ2ꢀyne. The rates of the reaction sharply
increased in the first minutes to (6.2–7.8)
n
×
⎯
6
1
0
8
6
4
2
10 mol/s and then, after passing through a maxiꢀ
2
–6
mum, decreased to (1–2) 10 mol/s (Fig. 10).
An analysis of changes in the composition of the
reaction mixture in the course of the hydrogenation of
×
3
n
ꢀhexꢀ2ꢀyne showed that, in all cases, the process
occurred selectively with respect to cisꢀ2ꢀhexene. At a
substrate conversion higher than 97%, the concentraꢀ
tion of cisꢀolefin reached a maximum value (85–
1
8
9%); in this case, the fraction of hexane did not
exceed 3%. Upon the continuation of the reaction,
hexane and thermodynamically more stable transꢀ2ꢀ
hexene were accumulated in the products (Fig. 11).
Thus, the hydrogenation reaction of nꢀhexꢀ2ꢀyne
in the presence of all of the catalytic systems occurs at
high rates with a high cisꢀhexene selectivity. The modꢀ
ification of a catalyst with a macroligand affects its staꢀ
bility, which is higher than the stability of the unmodꢀ
ified palladium catalyst (Table 4). Consequently, the
role of the macroligand in these systems is reduced to
a stabilizing function and its ability to the formation of
the lowꢀdimensional nanoparticles of an active phase
0
10
20
Time, min
30
40
Fig. 5. Changes in the rate of phenylacetylene hydrogenaꢀ
tion in the presence of ( ) 1%Pd/ZnO, ( ) 1%Pd–
PEG/ZnO, and ( ) 1%Pd–BP/ZnO. Conditions: catalyst
sample weight, 0.01 g; temperature, 40°C; H pressure,
1
2
3
2
0
.1 MPa; solvent, ethanol (25 mL); and initial phenylacetꢀ
ylene amount, 2.23 mmol.
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POLYMERꢀMODIFIED SUPPORTED PALLADIUM CATALYSTS
365
(а)
100
80
100
1
3
2
80
60
40
20
3
2
1
60
40
20
0
10
20
Time, min
30
40
0
10
20
Time, min
30
40
Fig. 7. Hydrogen uptake curves for the hydrogenation of
phenylacetylene in the presence of ( ) 1%Pd/ZnO,
) 1%Pd–PEG/ZnO, and ( ) 1%Pd–BP/ZnO. Condiꢀ
1
(b)
(
2
3
100
tions: catalyst sample weight, 0.01 g; temperature, 40°C;
1
3
H pressure, 0.1 MPa; solvent, ethanol (25 mL); and initial
2
phenylacetylene amount, 2.23 mmol.
8
6
4
2
0
0
0
0
2
8
6
4
2
2
3
1
0
10
20
30
Time, min
0
1
2
3
Cycle number
4
5
6
Fig. 6. Changes in the composition of reaction mixtures in
the course of phenylacetylene hydrogenation in the presꢀ
ence of (a) 1%Pd/ZnO and (b) 1%Pd–PEG/ZnO:
Fig. 8. Hydrogenation of the sequential portions of phenyꢀ
lacetylene in the presence of ( ) 1%Pd/ZnO, ( ) 1%Pd–
PEG/ZnO, and ( ) 1%Pd–BP/ZnO. Initial substrate
amount, 2.23 mmol; catalyst sample weight, 0.01 g; solꢀ
1
2
(
1
) phenylacetylene, (
Conditions: catalyst sample weight, 0.01 g; temperature,
0°C; H pressure, 0.1 MPa; solvent, ethanol (25 mL);
2
) styrene, and (
3
) ethylbenzene.
3
4
vent, ethanol (25 mL); temperature, 40°C; and H presꢀ
2
2
and initial phenylacetylene amount, 2.23 mmol.
sure, 0.1 MPa.
and the prevention of their aggregation in the course of that the results obtained can be valuable to petroleum
a catalytic process. As a result, the activity and selecꢀ chemistry for the removal of acetylene impurities in
tivity of the catalysts in the hydrogenation reactions of the synthesis of vinylꢀtype monomers from petroleum
acetylene compounds considerably increases. Note raw material, (for example, acetylene compounds
Table 2. Results of the hydrogenation of phenylacetylene (2.23 mmol) on palladium catalysts (0.01 g) in ethanol (25 mL)
at 40
°
C and 0.1 MPa
Maximum rate of reacꢀ
tion (Wmax × 10 , mol/s)
Catalysts
Sst, %
Conversion, %
Stability (TON)
–6
1
1
1
%Pd/ZnO
4.0
8.8
8.1
70.1
88.7
86.7
93.7
81.4
85.9
7110
14 220
11850
%Pd–PEG/ZnO
%Pd–BP/ZnO
KINETICS AND CATALYSIS Vol. 57
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366
ZHARMAGAMBETOVA et al.
100
(а)
100
1
3
1
2
2
80
60
40
20
80
60
40
20
4
3
0
20
40
Time, min
60
80
0
10
20
30
Time, min
40
50
60
Fig. 9. Changes in the composition of the reaction mixture
in the course of phenylacetylene hydrogenation in the
presence of 1%Pd–BP/ZnO in the third cycle: (
lacetylene, ( ) styrene, and ( ) ethylbenzene. Conditions:
catalyst sample weight, 0.01 g; temperature, 40°C; H2
pressure, 0.1 MPa; solvent, ethanol (25 mL); and initial
phenylacetylene amount, 2.23 mmol.
(b)
1) phenyꢀ
1
2
3
100
80
2
6
4
2
0
0
0
8
6
4
2
3
3
2
1
4
0
10
20
30
Time, min
40
50
60
0
10
20
Time, min
30
40
Fig. 11. Changes in the composition of the reaction mixꢀ
ture in the course of ꢀhexꢀ2ꢀyne hydrogenation in the
presence of (a) 1%Pd/ZnO and (b) 1%Pd–PEG/ZnO:
ꢀhexꢀ2ꢀyne, ( cisꢀ2ꢀhexene, ( transꢀ2ꢀhexene,
and ( ) hexane. Conditions: catalyst sample weight, 0.01 g;
temperature, 40°C; H pressure, 0.1 MPa; solvent, ethanol
Fig. 10. Changes in the rate of
n
ꢀhexꢀ2ꢀyne hydrogenation
n
in the course of reaction in the presence of (
1) 1%Pd/ZnO,
(2
) 1%Pd–PEG/ZnO, and ( ) 1%Pd–BP/ZnO. Condiꢀ
3
(
1)
n
2)
3)
tions: catalyst sample weight, 0.01 g; temperature, 40°C; H2
pressure, 0.1 MPa; solvent, ethanol (25 mL); and initial
phenylacetylene amount, 2.23 mmol.
4
2
(25 mL); and initial nꢀhexꢀ2ꢀyne amount, 2.23 mmol.
Table 3. Results of the hydrogenation of phenylacetylene–styrene mixtures on the 1%Pd–BP/ZnO catalyst (0.01 g) in ethꢀ
anol (25 mL) at 40 C and 0.1 MPa
°
Phenylacetylene : styrene ratio Maximum rate of reaction
Sst, %
Conversion, %
–6
in the substrate
(Wmax
×
10 , mol/s)
3
1
1
: 1
: 1
: 3
7.8
7.6
3.9
87.3
88.9
90.1
88.2
93.8
97.4
KINETICS AND CATALYSIS Vol. 57
No. 3 2016

POLYMERꢀMODIFIED SUPPORTED PALLADIUM CATALYSTS
367
Table 4. Results of the hydrogenation of ꢀhexꢀ2ꢀyne (2.23 mmol) on palladium catalysts (0.01 g) in ethanol (25 mL) at
n
40
°
C and 0.1 MPa
Maximum rate
of reaction
cisꢀ2ꢀHexene selectiviꢀ
Catalysts
Conversion, %
Stability (TON)
ty, %
–6
(
Wmax
×
10 , mol/s)
1
1
1
%Pd/ZnO
6.2
7.0
7.8
86.1
90.5
89.5
98.8
97.2
99.5
9480
16590
33180
%Pd–PEG/ZnO
%Pd–BP/ZnO
from ethylene, propylene, etc., which inhibit their catꢀ
alytic polymerization).
8. Ivanchev, S.S. and Dmitrenko, A.V., in Kompleksnye
metalloorganicheskie katalizatory polimerizatsii olefinov
(Organometallic Complex Catalysts for Olefin Polymerꢀ
ization), vol. X: Sintez i svoistva polimerizatsionnoꢀnapolꢀ
nennykh poliolefinov (Synthesis and Properties of Polyꢀ
merizationꢀFilled Polyolefins), D’yachkovskii, F.S., Ed.,
Chernogolovka, Moscow oblast: Inst. Khimicheskoi
Fiziki, 1986, p. 183.
. Kritskaya, D.A. and Ponomarev, A.N., Vysokomol. Soeꢀ
din., Ser. B: Khim. Polim., 1975, vol. 17, p. 67.
0. Tal’roze, R.V., Shandryuk, G.A., Merekalov, A.S.,
Shatalova, A.M., and Otmakhova, O.A., Polym. Sci.,
Ser. B: Polym. Chem., 2009, vol. 51, nos. 3–4, p. 57.
1. Bu, F.X., Hu, M., Xu, L., Meng, Q., Mao, G.Y.,
Jiang, D.M., and Jiang, J.S., Chem. Commun., 2014,
vol. 62, p. 8543.
ACKNOWLEDGMENTS
We are grateful to Senior Researcher S.G. Protaꢀ
sova and Leading Researcher A.M. Ionov (Institute of
Solid State Physics, Russian Academy of Sciences,
Chernogolovka) for performing XPS analysis. This
work was supported by the Committee of Science of
the Ministry of Education and Science of the Republic
of Kazakhstan and, in part, by the Russian Foundation
for Basic Research (project no. 14ꢀ03ꢀ00675).
9
1
1
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Translated by V. Makhlyarchuk
KINETICS AND CATALYSIS Vol. 57
No. 3 2016