Catalytic properties of nanostructured Pd–Ag catalysts in the liquid-phase hydrogenation of terminal and internal alkynes

Article abstract of DOI:10.1134/S0023158416060124

A comparative catalytic study of Pd–Ag bimetallic catalysts and the commercial Lindlar catalyst (Pd–Pb/CaCO₃) has been carried out in the hydrogenation of phenylacetylene (PA) and diphenylacetylene (DPA). The Pd–Ag catalysts have been prepared using the heterobimetallic complex PdAg₂(OAc)₄(HOAc)₄ supported on MgAl₂O₄ and aluminas (α-Al₂O₃ and γ-Al₂O₃). Physicochemical studies have demonstrated that the reduction of supported Pd–Ag complex with hydrogen results in homogeneous Pd–Ag nanoparticles. Equal in selectivity to the Lindlar catalyst, the Pd–Ag catalysts are more active in DPA hydrogenation. The synthesized Pd–Ag catalysts are active and selective in PA hydrogenation as well, but the unfavorable ratio of the rates of the first and second stages of the process makes it difficult to kinetically control the reaction. The most promising results have been obtained for the Pd–Ag₂/α-Al₂O₃ catalyst. Although this catalyst is less active, it is very selective and allows efficient kinetic control of the process to be carried out owing to the fact that, with this catalyst, the rate of hydrogenation of the resulting styrene is much lower than the rate of hydrogenation of the initial PA.

Full text of DOI:10.1134/S0023158416060124

ISSN 0023-1584, Kinetics and Catalysis, 2016, Vol. 57, No. 6, pp. 853–858. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.V. Rassolov, P.V. Markov, G.O. Bragina, G.N. Baeva, I.S. Mashkovskii, I.A. Yakushev, M.N. Vargaftik, A.Yu. Stakheev, 2016, published in Kinetika
i Kataliz, 2016, Vol. 57, No. 6, pp. 857–864.
Catalytic Properties of Nanostructured Pd–Ag Catalysts
in the Liquid-Phase Hydrogenation of Terminal and Internal Alkynes
A. V. Rassolova, P. V. Markova, G. O. Braginaa, G. N. Baevaa, I. S. Mashkovskiia, I. A. Yakushevb,
M. N. Vargaftikb, and A. Yu. Stakheeva, *
aZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
bKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119991 Russia
*e-mail: st@ioc.ac.ru
Received June 8, 2016
Abstract⎯A comparative catalytic study of Pd–Ag bimetallic catalysts and the commercial Lindlar catalyst
(Pd–Pb/CaCO3) has been carried out in the hydrogenation of phenylacetylene (PA) and diphenylacetylene
(DPA). The Pd–Ag catalysts have been prepared using the heterobimetallic complex PdAg2(OAc)4(HOAc)4
supported on MgAl2O4 and aluminas (α-Al2O3 and γ-Al2O3). Physicochemical studies have demonstrated
that the reduction of supported Pd–Ag complex with hydrogen results in homogeneous Pd–Ag nanoparti-
cles. Equal in selectivity to the Lindlar catalyst, the Pd–Ag catalysts are more active in DPA hydrogenation.
The synthesized Pd–Ag catalysts are active and selective in PA hydrogenation as well, but the unfavorable
ratio of the rates of the first and second stages of the process makes it difficult to kinetically control the reac-
tion. The most promising results have been obtained for the Pd–Ag2/α-Al2O3 catalyst. Although this catalyst
is less active, it is very selective and allows efficient kinetic control of the process to be carried out owing to
the fact that, with this catalyst, the rate of hydrogenation of the resulting styrene is much lower than the rate
of hydrogenation of the initial PA.
Keywords: Pd–Ag, liquid-phase hydrogenation, bimetallic catalysts, nanoparticles, terminal alkynes, internal
alkynes, catalyst structure, selectivity, phenylacetylene, diphenylacetylene
DOI: 10.1134/S0023158416060124
INTRODUCTION
Phenylacetylene (PA) was chosen to be the model
compound for the reason that one of the important
applications of the selective hydrogenation of terminal
alkynes is PA removal from styrene. Styrene is a valu-
able monomer used in the commercial-scale manu-
facturing of polystyrene, styrene–butadiene rubbers
The selective catalytic hydrogenation of the С≡С
bond to С=С in terminal and internal alkynes is
widely used in both the chemical industry and labora-
tory practice. In industry, selective hydrogenation is
used on a large-scale to remove alkynes from olefins, and latexes, unsaturated polyesters, and other prod-
ucts. The most common method of obtaining styrene
is the catalytic dehydrogenation of ethylbenzene,
which yields, along with the target olefin monomer,
PA as a by-product, whose concentration in crude sty-
rene is ca. 2–3% [3, 4]. Even small amounts of this
alkyne poisons the Ziegler–Natta catalyst during its
operation and markedly spoil the quality of the result-
ing polymers; for this reason, the concentration of
acetylenic impurities in styrene to be used in polymer-
ization should be reduced to the maximum acceptable
level (~10 ppm) [3, 5].
In industry, the selective removal of PA from sty-
rene is carried out using highly active catalysts based
on noble metals, primarily palladium. However, these
catalysts are insufficiently selective at high PA conver-
sions. One of the most efficient ways of enhancing the
С≡С bond hydrogenation selectivity is by promoting
Pd catalysts with another metal [6–8]. In recent years,
which are raw materials for polymer production.
These processes are also of great importance for fine
organic synthesis, providing means to obtain cis- and
trans-alkynes which are necessary for the synthesis of
physiologically active compounds, drugs, and food
additives.
The selective hydrogenation of terminal alkynes is a
particularly complicated problem. Because of the steric
accessibility of their С≡С bond, terminal alkynes are
more reactive than internal alkynes and the rate of their
hydrogenation is more difficult to control. As a conse-
quence, they undergo undesired further hydrogenation
to alkanes even in the presence of the commercial Lind-
lar catalyst [1, 2]. In view of this fact, the main purpose
of this study was to develop a catalyst that would show
favorable catalytic properties in the hydrogenation of
terminal alkynes.
853

854
RASSOLOV et al.
there has been increasing interest in bimetallic com- stantially enhances the catalyst selectivity in the liq-
positions as promising catalysts for fine organic syn- uid-phase hydrogenation of various alkynes [20, 21].
theses [9]. This is due to the progress in the synthesis
of nanostructured materials and advances in physico-
chemical methods of characterizing these materials,
including in situ analytical techniques [10].
Here, we report the data on the properties of
nanostructured Pd–Ag catalysts in the selective
hydrogenation of substituted alkynes. The catalysts
were prepared by depositing the bimetallic acetate
complex PdAg2(OAc)4(HOAc)4 onto different types
of supports. The selectivity of the Pd–Ag catalysts
was studied in the hydrogenation of PA (model com-
pound) and diphenylacetylene (DPA), an internal
alkyne that is structurally similar to PA. To carry out
a detailed analysis of the catalytic properties the cat-
alyst selectivity was determined at low, medium, and
high alkyne conversions. Synthesized samples were
comprehensively characterized using a complex of
physicochemical methods, which revealed the for-
mation of bimetallic nanoparticles in the catalyst
structure [22].
The addition of Group IB elements to palladium
considerably enhances the selectivity of the catalyst in
the hydrogenation of the С≡С bond. Great attention
has been focused on Pd–Ag compositions as very
promising С≡С bond hydrogenation catalysts [11]
employed in the gas-phase hydrogenation of impurity
acetylene in pyrolysis ethylene, a process necessary to
prevent poisoning of polymerization catalysts [12–14].
In recent years, there have been a number of stud-
ies confirming the efficiency of Pd–Ag catalysts in
gas- and liquid-phase PA hydrogenation. Karakha-
nov et al. [15] discovered that the target product
selectivity for a wide variety of substituted terminal
and internal alkynes, including PA, can be increased
by using Pd–Ag hybrid catalysts supported on sur-
face-immobilized dendrimers. Nikolaev et al. [16]
demonstrated that the introduction of Ag into the
Pd/Al2O3 system by coprecipitation enhances the on-
stream stability of the catalyst in liquid-phase PA
hydrogenation. Authors observed an increase in the
styrene formation rate and suppression of oligomeri-
zation and ethylbenzene formation. The advantages
offered by Pd–Ag bimetallic catalysts for cascade
reactions and one-pot syntheses were demonstrated
by Chen et al. [17], who investigated catalysts sup-
ported on metal-organic frameworks (MOFs),
promising next-generation nanoporous materials.
EXPERIMENTAL
Catalyst Preparation
Pd–Ag catalysts were prepared by incipient-wet-
ness impregnation. The supports were γ-Al2O3 (Sasol,
SBET = 56 m2/g), α-Al2O3 (Alfa Aesar, SBET = 8 m2/g),
and MgAl2O4 (Sasol, SBET = 40 m2/g). The supports
were impregnated with
a
solution of the
PdAg2(OAc)4(HOAc)4 complex in dilute acetic acid
(pH 2.8) and air-dried at room temperature. Without
being calcined, the dry catalysts were activated by
reduction with a flowing 5 vol % Н2/Ar mixture
(550°C, 1 h). It was demonstrated earlier that these
conditions ensure the formation of compositionally
identical bimetallic particles [23]. The resulting cata-
lysts contained 2 wt % Pd and 4 wt % Ag.
It should be noted that the properties of bimetallic
catalysts depend significantly on the degree of bime-
tallic nanoparticles homogeneity. During the prepara-
tion, it is necessary to prevent the formation of mono-
metallic Pd particles, which are typically more active
but much less selective in the hydrogenation reaction.
Even if the quantity of the resulting monometallic par-
ticles is relatively small, the selectivity of the catalyst
may decrease considerably. In the ideal case, the com-
position of each nanoparticle must correspond to the
proportions of the components in the catalyst as a
whole; however, it is difficult to attain this high degree
of homogeneity. From this standpoint, conventional
catalyst preparation methods are not always accept-
able and generally do not allow the formation of
monometallic Pd nanoparticles to be avoided [18]. An
efficient way of preparing bimetallic catalysts is by
using heterobimetallic Pd(II) acetate complexes with
The reference catalyst was the commercial Lindlar
catalyst (Aldrich).
Liquid-Phase Hydrogenation
The reaction was carried out using a catalytic setup
that included an autoclave-type reactor, a magnetic
stirrer, an electronic pressure sensor, and gas dosage
and reaction mixture sampling systems [24]. The sub-
strates were DPA (98%) and PA (98%) purchased from
Aldrich. The solvent was n-hexane (98%, Merck).
Measurements were taken at 25°C and an initial hydro-
gen pressure of 10 bar. Control over the kinetics of the
process was detailed in an earlier paper [21].
The reaction mixture was analyzed by Gas Chroma-
divalent and/or trivalent 3d and 4f modifying metals. A tography Mass Spectrometry (GC–MS) using a Mae-
unique feature of these compounds is that the metal stro-2 chromatograph (Interlab, Russia) fitted with an
atoms therein are strongly bonded to one another by HP5-MS column (5% phenyldimethylsiloxane, length
acetate bridges within all stages of catalyst preparation, of 30 m, inner diameter of 0.25 mm, stationary phase
making it possible to obtain highly organized homoge- film thickness of 0.25 μm). The carrier gas was helium,
neous, bimetallic nanoparticles in the final catalyst and the sample was ionized by electron impact at an
[19]. We demonstrated earlier that this approach sub- electron energy of 70 eV. The spectra were processed
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CATALYTIC PROPERTIES OF NANOSTRUCTURED
855
using the MSD ChemStation software [25] and the
(а)
NIST 14 mass spectral library [26].
–1 –1
mol H (mol alkene)–1
AH , mol H (mol alkene)
,
2
2
2
The catalytic activity of the synthesized catalysts
was estimated in terms of catalyst turnover frequency
(TOF) at the first (TOF1) and second (TOF2) stages of
hydrogenation from the reaction rates at these stages
(r1 and r2, respectively). Their values were determined
from the slope of the rectilinear segments of hydrogen
uptake versus reaction time curves at H2/alkyne =
0.2–0.6 for the first stage and 1.1–1.5 for the second
stage as the ratio of the Н2 uptake rate to the catalyst
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
weight (mmol H2 min–1 (mg Cat)–1).
Lindlar catalyst
For the bimetallic catalysts, the number of surface
Pd atoms is difficult to determine by electron micros-
copy because part of the surface may be occupied by
atoms of the second metal. For this reason, TOF was
calculated at the ratio of the number of converted sub-
strate molecules (consumed Н2 molecules) to the total
number of Pd atoms in the catalyst.
Pd–Ag2/γ-Al2O3 (56)
Pd–Ag2/MgAl2O4
Pd–Ag2/α-Al2O3
0
20
40
60
80
100 120 140
τ, min
The target alkene selectivity (S=) was calculated
from GC–MS data for the reaction mixture via the
formula
(b)
–1
–1
–1
AH , mol H (mol alkene)
mol H (mol alkene)
,
2
2
2
2.0
1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
S= = n= (n= + n−),
where n= and n– are the mole fractions of the resulting
alkene and alkane, respectively.
The efficiency of kinetic control of the process was
estimated by comparing ratios of alkyne to alkene
hydrogenation rates, r1/r2 [27].
Lindlar catalyst
Pd–Ag2/γ-Al2O3 (56)
Pd–Ag2/MgAl2O4
Pd–Ag2/α-Al2O3
RESULTS AND DISCUSSION
Diphenylacetylene Hydrogenation
Figure 1a illustrates the hydrogen uptake kinetics in
DPA hydrogenation. The hydrogenation rates at the
first and second stages of the process and the TOF val-
ues calculated from these data are listed in the table.
0
20 40 60 80 100 120 140 160
τ, min
The highest DPA hydrogenation activity is shown by
the Pd–Ag2/γ-Al2O3 (56) catalyst (TOF1 = 2.56 s–1),
which is 10 times higher than for the commercial Lind-
lar catalyst. The Pd–Ag2/MgAl2O4 sample is also more
Fig. 1. Hydrogen uptake as a function of reaction time for
the liquid-phase hydrogenation of (a) diphenylacetylene
and (b) phenylacetylene over Pd-containing catalysts.
–1
= 10 bar, Т = 25°C, [С ] = 0.160 mol L , m
=
P
H2
≡
Cat
active than the commercial catalyst (TOF1 = 0.99 s–1).
A considerably lower activity in selective DPA hydroge-
nation is displayed by the Pd–Ag2/α-Al2O3 (8) sample
2.5–10 mg (see the table), n-hexane as a solvent.
(TOF1 = 0.096 s–1). Apparently, this is due to the fact prevent undesired hydrogenation of the target product.
The efficiency of kinetic control can be characterized
by the ratio of the hydrogenation rates at the first and
second stages of the process, r1/r2 [27]. For the Lindlar
catalyst, this ratio in our experiments was 8.36.
that the bimetallic particles in this catalyst are the
biggest in comparison with the other samples in this
study [22].
An important advantage of the Lindlar catalyst is
that its hydrogenation rate decreases sharply on transi-
tion to the second hydrogenation stage giving the bend
on the hydrogen uptake curve. This makes it possible to
kinetically control the process, to terminate the reac-
tion after the consumption of 1 equiv. of Н2, when
alkyne-to-alkene hydrogenation is complete, and to
An analysis of our experimental data suggests that
the kinetic parameters observed with the Pd–Ag cata-
lysts are similar to those of the Lindlar catalyst. For all
catalysts studied, the kinetic curve shows an bend after
the consumption of 1 equiv. of Н2, which is the evi-
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856
RASSOLOV et al.
Kinetic characteristics of liquid-phase diphenylacetylene and phenylacetylene hydrogenation catalysts
r1 × 103* r2 × 103*
TOF1** TOF2**
r1/r2
Substrate
Catalyst
Lindlar catalyst
m, mg
2.5
2.5
10.0
2.5
5.0
2.5
5.0
2.5
6.99
11.11
1.09
28.37
9.06
5.04
0.84
8.23
0.84
1.66
0.06
3.44
4.34
8.09
0.10
0.25
0.99
0.096
2.52
0.32
0.45
0.08
0.73
0.03
0.15
8.36
6.71
17.76
8.26
2.08
0.62
8.46
0.55
2%Pd–4%Ag2/MgAl2O4
2%Pd–4%Ag2/α-Al2O3
2%Pd–4%Ag2/Al2O3 (56)
Lindlar catalyst
0.005
0.30
0.15
2%Pd–4%Ag2/MgAl2O4
2%Pd–4%Ag2/α-Al2O3
2%Pd–4%Ag2/Al2O3 (56)
0.72
0.009
1.34
CH3
15.07
–1
–1
* mmol Н min (mg Cat)
.
2
–1
** s
.
dence that the reaction slows down on transferring
from the first reaction stage to the second one.
Indeed, the PA and DPA hydrogenation processes
differ considerably in kinetic characteristics. The
kinetic curves of PA hydrogenation show no charac-
teristic bend at an Н2 uptake of 1 equiv (which is
observed in DPA hydrogenation, arising from the
slowdown of the process at its second stage). More-
over, there is a noticeable acceleration of hydrogena-
tion transferring to the second stage. The TOF2 value
For the Pd–Ag2/γ-Al2O3 (56) catalyst, the rate
ratio r1/r2 (~8.3) is the same as for the Lindlar catalyst.
The activity of the Pd–Ag catalyst is 10 times higher
than the activity of the Lindlar catalyst. For Pd–
Ag2/MgAl2O4, r1/r2 is somewhat smaller than for the
commercial catalyst (6.71 against 8.36), but the kinetic
curve still has a characteristic bend at a hydrogen
uptake of 1 equiv.
The most pronounced slowdown of hydrogenation
at the second stage is observed for the Pd–Ag2/α-
Al2O3 catalyst, with r1/r2 = 17.8, which is two times
larger than the same parameter for the Lindlar cata-
lyst. This provides the most favorable conditions for
kinetic control of the process.
Although the, Pd–Ag catalysts differ in terms of
reaction kinetics, they show similar selectivities at low
conversions (~97% at a DPA conversion of ~35%),
irrespective of the support nature. The selectivity of
the Lindlar catalyst in this conversion range is slightly
higher (~98.5%). However, at high conversions
(>80%), which are most interesting in practice, all of the
catalysts, including the Lindlar’s, demonstrate almost
equal selectivities of ~95–97%. A slightly lower selectiv-
ity (~91%) is observed for the Pd–Ag2/γ-Al2O3 (56)
sample.
is 0.15 s–1 for the Lindlar catalyst, 0.72 s–1 for Pd–
Ag2/MgAl2O4, and 1.34 s–1 for Pd–Ag2/γ-Al2O3 (56).
The hydrogenation rate ratio r1/r2 decreases from 2.08
to 0.55 in the following order: Lindlar > (Pd–
Ag2/MgAl2O4) > Pd–Ag2/γ-Al2O3 (56) (see the table).
In spite of the increase in the total hydrogenation
rate of the intermediate olefin, an analysis of “styrene
selectivity vs. PA conversion” profile did not reveal
any adverse effect of the latter parameter on the selec-
tivity of the process. At low conversions, the olefin
selectivity for all of the catalysts, including the com-
mercial one, is ~95%. A slight decrease in the selectiv-
ity (to 92–93%) takes place as the PA conversion
increases to 90% (Fig. 2).
This fact can be explained by the following. The
selective hydrogenation of alkynes proceeds via the
mechanism suggested by Bond [28], assuming that
selectivity is controlled by two factors, one kinetic and
the other thermodynamic [29, 30]. When the rate of the
resulting styrene desorption is low (Scheme, pathway I),
the overall selectivity of the process is determined by the
ratio of the rate constants for pathways I and III. In this
Phenylacetylene Hydrogenation
As was mentioned above, selective hydrogenation case, an increase in the rate of hydrogenation via path-
is difficult to carry out for terminal alkynes because of way III would inevitably diminish the styrene selectiv-
the steric accessibility of the triple carbon–carbon ity, but in fact this does not take place. The catalysts
bond and the high reactivity of the alkyne and the studied show a high selectivity within all PA conversion
resulting olefin. In contrast to internal alkynes, the tri- range. At PA conversions of >85%, the average selectiv-
ple bond in terminal alkynes does not undergo internal ity is ~92–94%. These data suggest that the rate of sty-
isomerization and directly hydrogenated to yield an rene desorption from the catalysts (pathway II) is
intermediate alkene, which then turns rapidly into an much higher than the rate of styrene hydrogenation
alkane [1, 2].
(pathway III), preventing the reaction via pathways III
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CATALYTIC PROPERTIES OF NANOSTRUCTURED
857
(а)
(b)
S=
S=
1.00
1.00
0.95
0.90
0.85
0.80
0.95
0.90
Lindlar catalyst
Lindlar catalyst
Pd–Ag2/γ-Al2O3 (56)
Pd–Ag2/MgAl2O4
Pd–Ag2/α-Al2O3
0.85
0.80
Pd–Ag2/γ-Al2O3 (56)
Pd–Ag2/MgAl2O4
Pd–Ag2/α-Al2O3
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
XDPA
XPA
Fig. 2. Olefin selectivity (S ) as a function of alkyne conversion (X) for monometallic and bimetallic catalysts in the selective
=
hydrogenation of terminal and internal alkynes: (a) diphenylacetylene and (b) phenylacetylene.
= 10 bar, T = 25°С, [С ] =
≡
P
H2
–1
0.160 mol L , m = 2.5–10 mg (see the table), n-hexane as a solvent.
Cat
and IV. In this case, the selectivity of the process is con- alkene desorption into the solution, and the further
trolled by the competitive adsorption of the initial PA hydrogenation of the alkene occurs via its readsorption
and the resulting styrene and determined by the ther- on active sites. The initial PA blocks the catalyst surface,
modynamic factor, according to Bond’s classification ensuring a high olefin selectivity until the complete
[28]. Thus, the dominant pathway of the process is conversion of the substrate.
solution
solution
IV
II
+2H
+2H
III
I
ads.
ads.
ads.
Scheme.
However, an increase in the rate of the second stage a high selectivity comparable with that of the other
of hydrogenation relative to the rate of the first stage samples of the series studied, including the Lindlar
catalyst, and its kinetic characteristics allow effective
kinetic control over the hydrogenation of both internal
and terminal alkynes.
causes serious difficulties in kinetic control of the pro-
cess, because the reaction is difficult to terminate at
the first hydrogenation stage. In view of this fact, the
data obtained for Pd–Ag2/α-Al2O3 are of particular
interest. This catalyst, unlike Pd–Ag2/MgAl2O4 and
Pd–Ag2/γ-Al2O3, ensures a significant decrease in the
hydrogenation rate once the reaction transfers from its
first stage to its second stage, and the rate ratio for the
Pd–Ag2/α-Al2O3 catalyst, r1/r2 ~ 8.46, is larger than
the same value for the Lindlar catalyst (r1/r2 ~ 2.08). An
obvious advantage of Pd–Ag2/α-Al2O3 is that it shows
Thus, our study demonstrated that, in DPA and PA
hydrogenation, all of the synthesized Pd–Ag catalysts
exhibit a high selectivity close to the selectivity of the
Lindlar catalyst. It should be especially mentioned
that this high selectivity was attained at a Pd content
(2 wt % Pd) that is lower than that of the Lindlar cata-
lyst (5 wt % Pd). This makes the Pd–Ag system attrac-
tive for industrial and laboratory practices. The best
KINETICS AND CATALYSIS Vol. 57 No. 6 2016

858
RASSOLOV et al.
14. Studt, F., Abild-Pedersen, F., Bligaard, T., Sørensen, R.Z.,
Hviid Christensen, C., and Nørskov, J. K., Science, 2008,
vol. 320, p. 1320.
15. Karakhanov, E.A., Maximov, A.L., Zolotukhina, A.V.,
Yatmanova, N., and Rosenberg, E., Appl. Organomet.
Chem., 2015, vol. 29, p. 777.
performance in PA hydrogenation is shown by the
Pd–Ag2/α-Al2O3 catalyst. With this catalyst, the
hydrogenation process slows down considerably at its
second stage, so the kinetic characteristics of the cata-
lyst enable one to effectively control the hydrogena-
tion of both internal and terminal alkynes.
16. Nikolaev, S.A. and Krotova, I.N., Pet. Chem., 2013,
vol. 53, no. 6, p. 394.
ACKNOWLEDGMENTS
The authors are grateful to the International Analyt-
ical Center of the Zelinsky Institute of Organic Chem-
17. Chen, Yu-Z., Zhou, Yu-X., Wang, H., Lu, J., Uchida, T.,
Xu, Q., Yu, S.-H., and Jiang, H.-L., ACS Catal., 2015,
vol. 5, p. 2062.
istry for providing the opportunity to make GC-MS 18. Wang, Z., Yang, L., Zhang, R., Li, L., Cheng, Z., and
Zhou, Z., Catal. Today, 2016, vol. 264, p. 37.
analyses. This work was supported by the Russian
Foundation for Basic Research (grant nos. 15-03-07652
and 16-29-10788).
19. Kozitsyna, N.Yu., Nefedov, S.E., Dobrokhotova, Zh.V.,
Ikorskii, V.N., Stolyarov, I.P., Vargaftik, M.N., and
Moiseev, I.I., Nanotechnol. Russ., 2008, vol. 3, nos. 3–4,
p. 166.
20. Mashkovsky, I.S., Baeva, G.N., Stakheev, A.Yu., Var-
gaftik, M.N., Kozitsyna, N.Yu., and Moiseev, I.I.,
Mendeleev Commun., 2014, vol. 24, no. 6, p. 355.
21. Markov, P.V., Bragina, G.O., Baeva, G.N.,
Tkachenko, O.P., Mashkovskii, I.S., Yakushev, I.A.,
Kozitsyna, N.Yu., Vargaftik, M.N., and Sta-
kheev, A.Yu., Kinet. Catal., 2015, vol. 56, p. 591.
22. Rassolov, A.V., Markov, P.V., Bragina, G.O.,
Baeva, G.N., Krivoruchenko, D.S., Mashkovskii, I.S.,
Yakushev, I.A., Vargaftik, M.N., and Stakheev, A.Yu.,
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KINETICS AND CATALYSIS
Vol. 57
No. 6
2016