Carbon Oxide Hydrogenation over GdBO3 (B = Fe, Mn, Co) Complex Oxides: Effect of Carbon Dioxide on Product Composition

Article abstract of DOI:10.1134/S0965544120050114

Abstract: The catalytic properties of GdFeO₃, GdСоO₃, and GdMnO₃ perovskite-type complex oxides in carbon oxide hydrogenation are studied. A correlation between the composition and catalytic properties of the oxide is found. It is shown that carbon monoxide conversion increases in the following order: GdFeO₃ < GdMnO₃ ≤ GdСоO₃; carbon dioxide conversion increases in the reverse order. Differences in the catalytic characteristics of GdFeO₃, GdMnO₃, and GdCoO₃ are attributed to different forms of chemisorbed CO, CO₂, and H₂ and the hydrogen mobility across the catalyst surface. The introduction of carbon dioxide into the reaction mixture suppresses the formation of olefins and causes an increase in methane yield. In the catalytic process, GdCoO₃ is partially decomposed into Gd₂O₃, Co, and Gd₂O₂CO₃. It is assumed that carbon oxides are adsorbed by Gd³⁺ ions (A site), while transition metal ions (B site) are responsible for the formation of atomic hydrogen. It is presumed that carbon sites formed on the surface differ in catalytic activity: some of them are responsible for the formation of unsaturated hydrocarbons, and the others are responsible for the formation of paraffins.

Full text of DOI:10.1134/S0965544120050114

ISSN 0965-5441, Petroleum Chemistry, 2020, Vol. 60, No. 5, pp. 571–576. © Pleiades Publishing, Ltd., 2020.
Russian Text © The Author(s), 2020, published in Nanogeterogennyi Kataliz, 2020, Vol. 5, No. 1, pp. 17–23.
Carbon Oxide Hydrogenation over GdBO3 (B = Fe, Mn, Co)
Complex Oxides: Effect of Carbon Dioxide on Product Composition
T. F. Sheshkoa, *, A. A. Sharaevaa, **, O. K. Powella, Yu. M. Serova, I. V. Chislovab,
L. V. Yafarovab, A. V. Korolevab, and I. A. Zverevab
aPeoples’ Friendship University of Russia, Moscow, 117198 Russia
bSt. Petersburg State University, St. Petersburg, 198504 Russia
*e-mail: sheshko-tf@rudn.ru
**e-mail: alminasharaeva@gmail.com
Received July 22, 2019; revised November 17, 2019; accepted January 9, 2020
Abstract—The catalytic properties of GdFeO3, GdСоO3, and GdMnO3 perovskite-type complex oxides in
carbon oxide hydrogenation are studied. A correlation between the composition and catalytic properties of
the oxide is found. It is shown that carbon monoxide conversion increases in the following order: GdFeO3 <
GdMnO3 ≤ GdСоO3; carbon dioxide conversion increases in the reverse order. Differences in the catalytic
characteristics of GdFeO3, GdMnO3, and GdCoO3 are attributed to different forms of chemisorbed CO,
CO2, and H2 and the hydrogen mobility across the catalyst surface. The introduction of carbon dioxide into
the reaction mixture suppresses the formation of olefins and causes an increase in methane yield. In the cat-
alytic process, GdCoO3 is partially decomposed into Gd2O3, Co, and Gd2O2CO3. It is assumed that carbon
oxides are adsorbed by Gd3+ ions (A site), while transition metal ions (B site) are responsible for the forma-
tion of atomic hydrogen. It is presumed that carbon sites formed on the surface differ in catalytic activity:
some of them are responsible for the formation of unsaturated hydrocarbons, and the others are responsible
for the formation of paraffins.
Keywords: hydrogenation, carbon monoxide, carbon dioxide, perovskite
DOI: 10.1134/S0965544120050114
Fischer–Tropsch synthesis is a catalytic process to tronic conductivity and a high stability, are used as
convert synthesis gas to a broad range of hydrocar- catalysts for various processes, in particular, carbon
bons, the most important of which are light olefins oxide hydrogenation [11–13]. A variation in the cat-
(ethylene, propylene, and butylene) used for various ionic composition at A and B sites provides the forma-
chemical industries. A promising process for light ole- tion of systems with a controlled yield and selectivity
fin production is a modified Fischer–Tropsch synthe- for target synthesis products [14–17].
sis involving CO2 [1–5]. Selectivity for particular
products depends on the composition of the reaction
mixture and the ratio of carbon oxides in it. For exam-
ple, the authors of [6, 7] state that CO2 behaves as an
inert component; however, the introduction of CO2
into the reaction mixture shifts the product distribu-
This study is focused on the catalytic activity of
complex oxides GdBO3 (B = Fe, Co, Mn) in carbon
oxide hydrogenation and the determination of the
effect of CO2 on the reaction product distribution and
the olefin/paraffin ratio.
=
=
tion toward
[8].
C2 –C4
EXPERIMENTAL
Conventional carbon oxide hydrogenation cata-
lysts are systems based on iron and cobalt [9, 10]; how-
ever, their main disadvantage is that they are prone to
poisoning and coking. In addition, in the presence of
conventional catalysts, the range of the resulting prod-
ucts is extremely broad. Therefore, the control of
selectivity remains one of the most important and
complex problems in the field of scientific research.
Perovskite-type complex oxides ABO3 (A is an alkali
Complex oxides GdBO3 (B = Fe, Co, Mn) were
synthesized by the sol–gel (citrate) method described
in [18].
The phase composition of the catalysts was deter-
mined by X-ray powder diffraction analysis (Rigaku
MiniFlex II instrument). The surface morphology of
the samples was studied by scanning electron micros-
copy on Zeiss EVO®40 and Carl Zeiss Supra 40VP
or rare-earth metal cation, B is a transition metal cat- microscopes. Data on specific surface area were calcu-
ion), which exhibit a mixed oxygen-ionic and elec- lated by the Brunauer–Emmett–Teller (BET) method
571

572
SHESHKO et al.
As evidenced by scanning electron microscopy, all
the samples have a porous structure. The particle mor-
phologies are slightly different: the GdFeO3 sample
consists of agglomerated elongated particles with a
diameter of 30–60 nm and a length of about 200 nm,
whereas GdCoO3 and GdMnO3 consist of spherical
particles with a diameter of about 100 and 200 nm,
respectively.
1
30
30
30
35
35
35
40
40
45
45
45
50
50
50
55
55
55
60
20
20
20
25
25
25
2
60
X-ray photoelectron spectroscopy showed that, in
all the studied compounds, gadolinium is in the 3+
state; the Gd 4d energy is ~143.5 eV1. In the GdFeO3
compound, the Fe 2p3/2 binding energy is 710.9 eV;
this value suggests that iron is in the 3+ state [20, 21].
The XPS results show that the main Co 2p3/2 peak is
broad and consists of a peak at 779.89 eV and a satellite
peak at 789.5 eV; this finding is consistent with the
published data for Co3O4 [20, 21] and indicates the
presence of cobalt atoms in the heterovalent state (+3
and +2). According to the published data1, the 2p3/2
peak localized at an energy of 641.48 eV indicates the
presence of manganese in heterovalent states of 2+
and 3+.
3
40
2θ, deg
60
Fig. 1. X-ray diffraction patterns of complex oxides:
(1) GdFeO , (2) GdCoO , and (3) GdMnO .
3
3
3
from nitrogen adsorption isotherms (Quantachrome
Nova 4200e instrument). The oxidation state of iron,
cobalt, and manganese was determined by X-ray pho-
toelectron spectroscopy (XPS). The XPS measure-
ments were conducted on a Thermo Fisher Scientific
Escalab 250Xi instrument (AlKα, λ = 0.1541 nm).
In the case of carbon monoxide hydrogenation at a
CO : H2 ratio of 1 : 2 in the presence of GdFeO3,
GdMnO3, and GdCoO3, the CO conversion was 50–
70%, respectively (Fig. 2). The lowest CO conversion
(about 55%) was observed for gadolinium ferrite. Up
to a temperature of 673 K, gadolinium manganite
exhibited the highest activity in carbon monoxide
conversion. At temperatures above 623 K, an abrupt
increase in the CO conversion was observed in the case
of using gadolinium cobaltite as a catalyst: in the tem-
perature range of 648–673 K, the carbon monoxide
conversion achieved almost 90%; in addition, the for-
mation of CO2 was observed; in the presence of gado-
linium cobaltite, the amount of carbon dioxide
increased with increasing temperature and signifi-
cantly exceeded the amount of CO2 formed in the
presence of manganite and ferrite (Fig. 2).
The catalytic activity in carbon monoxide hydroge-
nation was tested in a U-shaped flow quartz reactor
with a fixed catalyst bed composed of a 0.1-g weighed
portion of the catalyst diluted with silica. The reactor
was placed in a temperature-controlled furnace; tem-
perature was measured/controlled using a K-type
thermocouple placed into the center of the catalyst
bed without direct contact. The process temperature
was increased from 523 to 708 K. Carbon oxide hydro-
genation was run at atmospheric pressure and a gas
mixture flow rate of 1.5 L/h (CO + CO2/H2 = 1/2). In
all tests, the samples without prereduction were used.
Analysis of the reaction mixture above the catalyst sur-
face was conducted on a Kristall 5000.2 gas chromato-
graph equipped with a stainless steel column filled
with the Porapak Q sorbent and thermal conductivity
and flame ionization detectors.
Carbon monoxide undergoes both molecular
adsorption to form linear and bridge species and disso-
ciative adsorption; СО2 can be formed owing to the
Reaction product formation rate (specific catalytic
activity) R (mol/(h g)) was determined from the con- interaction of СОads with either perovskite surface oxy-
stancy of chromatographic peaks. Carbon oxide con-
versions (Xi, %), product formation rates (Ri,
mmol/(h g)), and olefin selectivity (Si, %) were calcu-
lated by the equations given in [19].
gen (OS) or oxygen released during the dissociative
adsorption of carbon monoxide: СОads + ОS → СО2
[22]. Higher carbon monoxide conversions in the
presence of GdMnO3 can be attributed to different
heats of adsorption of CO and H2 on the metal surface
and the difference in these values. According to [23],
the difference in the surface adsorption energies of CO
and H2 decreases in the following order: Mn > Fe >
RESULTS AND DISCUSSION
According to X-ray diffraction analysis, the syn-
thesized GdBO3 oxides (B = Fe, Co, Mn) are single-
phase materials and do not contain impurity phases
(Fig. 1); the diffraction peaks are consistent with the
PDF2 database: #01-070-9906 (GdFeO3), #00-025-
1057 (GdCoO3), and #01-070-9190 (GdMnO3).
1
J.F. Moulder, W.F. Stickle, P.E. Sobol, and K.D. Bomben,
Handbook of X-ray Photoelectron Spectroscopy: A Reference
Book of Standard Spectra for Identification and Interpretation
of XPS Data (Physical Electronics Division, PerkinElmer,
1992).
PETROLEUM CHEMISTRY
Vol. 60
No. 5
2020

CARBON OXIDE HYDROGENATION OVER GdBO3 (B = Fe, Mn, Co)
573
Co; these energies are not extremely high; therefore,
the energy barrier to the reaction of adsorbed CO and
H2 will be small. The Me–CO binding energy
increases in the same order: Mn < Fe < Co. These val-
ues correlate well with the observed CO conversions.
1
2
3
4
5
6
100
80
60
40
20
0
10
8
6
4
In the case of cohydrogenation of CO and CO2 at a
mixture : hydrogen ratio of 1 : 2, the carbon monoxide
conversions in the presence of GdMnO3 and GdCoO3
were comparable with the values obtained in the
hydrogenation of pure CO (Fig. 3). At the same time,
in the presence of GdFeO3, a significant decrease in
X(CO) was observed; it can be attributed to the
desorption of carbon monoxide formed during the
dissociative adsorption of carbon dioxide at lower
temperatures. With respect to CO2 conversions, an
opposite tendency was observed: the lowest values
(<50%) were obtained in the case of using GdCoO3 as
a catalyst, and the highest values (80–100%) were
observed in the presence of GdFeO3. However, at
temperatures above 648 K, the X(CO2) conversions
began to decrease. This process was particularly pro-
nounced in the presence of gadolinium ferrite; this
fact can be apparently attributed to a more intense
occurrence of the Boudouard reaction to form active
carbon: 2СО → СО2 + С.
The introduction of carbon dioxide into the reac-
tion mixture in amounts not exceeding 11% (CO :
CO2 = 2 : 1) hardly affected the CO conversion in the
reaction over GdFeO3 (Fig. 4). However, an increase
in the CO2 content to an amount equimolar with that
of CO led to a significant decrease in the CO conver-
sion. At a temperature of 648 K, it was as low as 20%.
A decrease in CO conversions with an increase in the
СО2 content in the feed mixture can be associated with
the desorption of carbon monoxide formed during the
dissociative adsorption of carbon dioxide at initial
reaction temperatures. A further increase in tempera-
ture (catalytic region) leads to an increase in the car-
bon dioxide content in the mixture, which is most
probably attributed to the further chemisorption of
both CO and CO2 on active surface sites released
during catalysis. However, it is not improbable that
Boudouard and Bosch side reactions can occur:
2СО → С + СО2 and СО2 + 2Н2 → С + 2Н2О,
respectively.
2
0
550
600
650
700
750
500
T, K
Fig. 2. Temperature dependences of CO conversions and
СО content in the case of the reaction at a СО : Н ratio
2
2
of 1 : 2 in the presence of (1, 4) GdFeO , (2, 5) GdCoO ,
3
3
and (3, 6) GdMnO .
3
1
2
3
4
5
6
100
80
60
40
20
0
100
80
60
40
20
0
348 398 448 498 548 598 648 698
298
T, K
Fig. 3. Temperature dependences of CO and CO conver-
2
sions in the reaction at ratios of (CO : CO = 1 : 1) : H =
2
2
1 : 2 in the presence of (1, 4) GdFeO , (2, 5) GdCoO , and
3
3
(3, 6) GdMnO .
3
100
80
60
40
20
1 2 3
At the same time, for a mixture with excess CO2
(22%, CO : CO2 = 1 : 2), an increase in CO conver-
sions was observed; the conversions achieved 80%,
which is higher than the values obtained in the hydro-
genation of pure carbon monoxide. The data on the
reaction in the presence of GdFeO3 and excess carbon
dioxide in the reaction mixture indicate an intensifica-
tion of dissociative chemisorption СО2 → CO + O and
the possible occurrence of carbon monoxide dispro-
portionation to form active carbon: 2СО → СО2 + С;
it is these factors that lead to a significant increase in
carbon monoxide conversions. The authors of [24]
0
5
10
15
20
25
Carbon dioxide content, %
Fig. 4. Dependence of CO conversions on the СО content
2
in the reaction mixture of carbon oxides in the presence of
(1) GdFeO , (2) GdCoO , and (3) GdMnO .
3
3
3
PETROLEUM CHEMISTRY Vol. 60 No. 5 2020

574
1.0
SHESHKO et al.
50
(a)
(b)
1
0.8
0.6
0.4
0.2
40
2
30
3
20
10
0
5
10
15
20
25
0
5
10
15
20
25
30
35
Carbon dioxide content, %
Carbon dioxide content, %
Fig. 5. Dependence of (a) the olefin/paraffin ratio at 648 K and (b) olefin selectivity on the CO content in the reaction mixture:
2
(1) GdFeO , (2) GdCoO , and (3) GdMnO .
3
3
3
believe that two active phases—Fe0/Fe carbides and
ganese surface, the formation of CHx radicals and
iron oxides (Fe3O4)—are simultaneously present on their subsequent recombination to olefins are
observed.
On the other hand, the catalyst activity and selec-
the iron surface. The carbide phase is active in the dis-
sociation of CO and the formation of hydrocarbons,
while the oxide phase adsorbs CO by the associative
mechanism.
Unlike GdFeO3, in the case of GdMnO3 and
GdCoO3, the presence of CO2 had hardly any effect
on CO conversion: regardless of the CO2 content, car-
bon monoxide conversions were comparable to those
obtained in the hydrogenation of pure CO (Fig. 4).
In either case—the hydrogenation of pure CO and
the cohydrogenation of CO and CO2—the reaction
products were C1–C6 hydrocarbons, among which
methane, ethylene, and propylene were dominant. A
variation in the CO/CO2 ratio in the reaction mixture
led to a change in the quantitative ratio of hydrogena-
tion products. An increase in the carbon dioxide con-
tent suppressed the formation of unsaturated hydro-
carbons and caused a decrease in the olefin/paraffin
ratio (Fig. 5).
tivity in this synthesis are also determined by the
mechanism of CO and CO2 adsorption the magnitude
of which exceeds the adsorption of hydrogen by an
order of magnitude; in addition, CO can be adsorbed
on both metal and oxide components of the catalyst
[28, 29]. The adsorption by the dissociative mecha-
nism increases in the following order: Co, Fe, Mn; the
Me–CO binding energy decreases and, as noted
above, the difference in the adsorption energy of CO
and H2 on the catalyst surface increases in the same
order.
To determine the energy barrier to the reaction
path, the experimental data were reduced to the linear
coordinates of the Arrhenius equation (Table 1). For
all the studied catalysts, the introduction of CO2 into
the reaction mixture leads to a decrease in the appar-
ent activation energies for methane formation.
For GdFeO3 and GdCoO3, at an equimolar ratio of
CO and CO2 in the feed reaction mixture, the effective
activation energies for methane formation and the
pre-exponential factor logarithms are almost identical
to the values obtained in the hydrogenation of pure
carbon monoxide. For GdMnO3, the introduction of
CO2 into the reaction mixture leads to a significant
decrease in Еа(СН4); i.e., an increase in the fraction of
paraffins in the hydrogenation products is apparently
attributed to the energy factor. In this case, for all the
catalysts, the pre-exponential factor logarithm with
respect to ethylene, which indirectly characterizes the
number of active surface sites, decreases.
Catalyst systems based on lanthanides can form
carbonate complexes with carbon oxides [30–33]. The
formation of a metal phase and the presence of
Gd2O2CO3 play an important role for the hydrogena-
tion reaction, because it was found that the resulting
Gd2O3 is an active site for the adsorption of CO and
CO2 in this process. Earlier, in studying the adsorption
It should be noted that, in the case of using
GdMnO3 as a catalyst, at an equimolar content of CO
and CO2 in the reaction mixture, an anomalous
increase in olefin selectivity was observed.
The ratio between saturated and unsaturated
hydrocarbons in hydrogenation products is mostly
determined by the amount of atomic hydrogen capa-
ble of migrating from some active surface sites to other
and by the structure of these sites [25, 26]. Differences
in the catalytic activity of the samples can be associ-
ated with different rates of hydrogen diffusion across
the catalyst surface (the spillover effect). Hydrogen is
known to undergo mostly molecular adsorption on the
manganese surface and dissociative adsorption in the
atomic form on the surface of iron and cobalt [27].
The high rates of formation of paraffins (in particular,
methane) in the presence of GdFeO3 and GdCoO3
(Table 1) are apparently attributed to both a larger
amount of atomic hydrogen on the surface and its
higher diffusion rate across the surface. On the man-
PETROLEUM CHEMISTRY
Vol. 60
No. 5
2020

CARBON OXIDE HYDROGENATION OVER GdBO3 (B = Fe, Mn, Co)
575
Table 1. Comparative characteristics of the studied samples in carbon oxide hydrogenation reactions at T = 648–708 K
Kinetic parameters of the formation processes
СН4
С2H4
Methane
formation rate,
mmol/(h g)
Mixture
composition
Olefin
selectivity, %
pre-exponential
pre-exponential
activation
activation
factor of the rate
constant, lnK0
factor of the rate
constant, lnK0
energy, kJ/mol
energy, kJ/mol
GdFeO3
СО
2.54
1.26
27
7
70
68
5.70
5.39
65
60
3.49
2.65
СО + СО2 = 1 : 1
GdCoO3
50
54
СО
37.42
27.34
65
3
5.32
5.40
65
28
3.49
–2.54
СО + СО2 = 1 : 1
GdMnO3
136
43
СО
0.51
4.29
35
33
23.48
14.75
45
60
6.15
2.60
СО + СО2 = 1 : 1
FUNDING
of carbon oxides on GdFeO3 and Fe2O3 [34], the exis-
tence of two molecular forms of carbon monoxide
adsorption on the perovskite surface was revealed. It
was shown that carbon dioxide undergoes molecular
adsorption to form carbonate–carboxylate complexes
and dissociative adsorption with recombination
during desorption in CO2. It can be assumed that the
formation of carbonate complexes occurs on Gd3+
ions (A site), whereas transition metal ions (B site) are
responsible for the formation of atomic hydrogen.
This work was supported by the Russian Foundation for
Basic Research (project no. 17-03-00647). The publication
has been prepared with the support of the RUDN Univer-
sity Program 5-100.
CONFLICT OF INTEREST
The authors declare that there is no conflict of interest
regarding the publication of this manuscript.
ADDITIONAL INFORMATION
Thus, our results suggest the following: if the intro-
duction of CO2 into the reaction mixture contributes
to an increase in saturated hydrocarbon yields and
causes the suppression of olefin formation reactions,
then the carbon sites formed on the surface during the
process most probably differ in catalytic activity: some
of the sites, which are assumed to arise from the disso-
ciative adsorption of CO, are responsible for the for-
mation of unsaturated hydrocarbons, while the other
sites, which possibly arise from the interaction of CO2
with catalytic surface sites in accordance with the
mechanism proposed in [35], are responsible for the
formation of paraffins.
T.F. Sheshko, ORCID: https://orcid.org/0000-0003-
4176-4085
A.A. Sharaeva, ORCID: https://orcid.org/0000-0001-
6465-7368
O.K. Powell, ORCID: https://orcid.org/0000-0001-
8186-2195
Yu.M. Serov, ORCID: https://orcid.org/0000-0003-
0634-3314
I.V. Chislova, ORCID: http://orcid.org/0000-0001-
5212-5014
L.V. Yafarova, ORCID: http://orcid.org/0000-0001-
7572-2209
A.V. Koroleva, ORCID: https://orcid.org/0000-0002-
5899-0436
I.A. Zvereva, ORCID: http://orcid.org/0000-0002-
6898-3897
ACKNOWLEDGMENTS
The physicochemical studies were conducted using the
equipment of the Thermogravimetric and Calorimetric
Research Center, the Center for X-ray Diffraction Studies,
the Center for Physical Methods of Surface Investigation,
and the Interdisciplinary Resource Center for Nanotech-
nology of the St. Petersburg State University Research Park.
REFERENCES
1. M. Martinelli, C. G. Visconti, L. Lietti, P. Forzatti,
C. Bassano, and P. Deiana, Catal. Today 228, 77
(2014).
https://doi.org/10.1016/j.cattod.2013.11.018
PETROLEUM CHEMISTRY Vol. 60 No. 5 2020

576
SHESHKO et al.
2. M. Mikkelsen, M. Jorgensen, and F. C. Krebs, Energy 19. A. A. Sharaeva, T. F. Sheshko, T. A. Kryuchkova,
Environ. Sci. 3 (1), 43 (2010).
https://doi.org/10.1039/b912904a
L. V. Yafarova, and I. A. Zvereva, Bulg. Chem. Com-
mun. 51, 143 (2019).
3. J. Wang, Z. You, Q. Zhang, W. Deng, and Y. Wang,
20. K. Zhao, L. Li, A. Zheng, Z. Huang, F. He, Y. Shen,
G. Wei, and Z. Zhao, Appl. Energy 197, 393 (2017).
https://doi.org/10.1016/j.apenergy.2017.04.049
21. K. Zhao, Y. Shen, Z. Huang, F. He, G. Wei, and
A. Zheng, J. Energy Chem. 26 (3), 501 (2017).
https://doi.org/10.1016/j.jechem.2016.11.016
Catal. Today 215, 186 (2013).
https://doi.org/10.1016/j.cattod.2013.03.031
4. S. Saeidi, N. A. S. Amin, and M. R. Rahimpour, J. CO2
Util. 5, 66 (2014).
https://doi.org/10.1016/j.jcou.2013.12.005
5. S. Kiatphuengporn, M. Chareonpanich, and J. Limtr-
22. A. L. Lapidus and A. Yu. Krylova, Ross. Khim. Zh. 44
akul, Chem. Eng. J. 240, 527 (2014).
(1), 43 (2000).
https://doi.org/10.1016/j.cej.2013.10.090
23. P. C. Keith, Oil Gas J. 45, 102 (1946).
6. C. G. Visconti, L. Lietti, E. Tonconi, P. Forzatti,
R. Zennaro, and E. Finocchio, Appl. Catal., A 355, 61
(2009).
24. M. A. Vannice, J. Catal. 50, 228 (1977).
https://doi.org/10.1016/0021-9517(77)90031-8
https://doi.org/10.1016/j.apcata.2008.11.027
25. V. A. Matyshak, V. N. Korchak, T. N. Burdeinaya,
V. F. Tret’yakov, A. G. Zakirova, A. S. Lermontov, and
V. V. Lunin, Kinet. Catal. 49 (3), 434 (2008).
7. Y. Yao, X. Liu, D. Hildebrandt, and D. Glasser, Appl.
Catal., A 433–434, 58 (2012).
https://doi.org/10.1134/S0023158408030154
https://doi.org/10.1016/j.apcata.2012.04.041
26. V. A. Matyshak, I. T. Ismailov, V. F. Tret’yakov, and
O. N. Sil’chenkova, in Proceedings of the Russian Con-
gress on Catalysis (Moscow, 2011), Vol. II, p. 61 [in Rus-
sian].
8. P. Sirikulbodeea, T. Ratanaa, T. Sornchamnic,
M. Phongaksorna, and S. Tungkamania, Energy Pro-
cedia 138, 998 (2017).
https://doi.org/10.1016/j.egypro.2017.10.112
9. D. J. Duvenhage and N. J. Coville, Appl. Catal., A 289, 27. N. M. Popova, L. V. Babenkova, and G. A. Savel’eva,
231 (2005).
Adsorption and Interaction of the Simplest Gases with
VIII Group Metals (Nauka, Alma-Ata, 1979), pp. 83–
97 [in Russian].
https://doi.org/10.1016/j.apcata.2005.05.008
10. M. Arsalanfar, A. A. Mirzaei, H. R. Bozorgzadeh,
A. Samimi, and R. Ghobadi, J. Ind. Eng. Chem. 20,
1313 (2014).
28. G. Blyholder, J. Phys. Chem. 79 (7), 756 (1975).
https://doi.org/10.1021/j100574a018
https://doi.org/10.1016/j.jiec.2013.07.011
29. Y. Iwasawa, R. Mason, M. Textor, and G. A. Samorjai,
11. T.-W. Kim, F. Kleitz, J. W. Jun, H.-J. Chae, and
C.-U. Kim, J. Ind. Eng. Chem. 51, 196 (2017).
https://doi.org/10.1016/j.jiec.2017.02.032
Chem. Phys. Lett. 44 (3), 468 (1976).
https://doi.org/10.1016/0009-2614(76)80706-3
30. G. Valderrama, A. Kiennemann, and M. R. Goldwass-
12. N. Escalona, S. Fuentealba, and G. Pecchi, Appl.
er, Catal. Today 133–135, 142 (2008).
Catal., A 381, 253 (2010).
https://doi.org/10.1016/j.cattod.2007.12.069
https://doi.org/10.1016/j.apcata.2010.04.022
31. D. Pakhare and J. Spivey, Chem. Soc. Rev. 43 (22),
13. M. Ao, G. H. Pham, V. Sage, and V. Pareek, J. Mol.
7813 (2014).
Catal. A: Chem. 416, 96 (2016).
https://doi.org/10.1039/c3cs60395d
https://doi.org/10.1016/j.molcata.2016.02.020
32. K. Nagaoka, K. Takanabe, and K.-I. Aika, Appl.
14. F. Li, H. Zhao, N. Zhao, and F. Xiao, Int. J. Hydrogen
Catal., A 268 (1–2), 1 510 158 (2004).
Energy 42, 20640 (2017).
https://doi.org/10.1016/j.apcata.2004.03.029
https://doi.org/10.1016/j.ijhydene.2017.06.200
33. O. U. Osazuwa and C. K. Cheng, J. Cleaner Prod. 148,
15. Z. Song, X. Shi, H. Ning, G. Liu, H. Zhong, and
202 (2017).
Y. Liu, Appl. Surf. Sci. 405, 1 (2017).
https://doi.org/10.1016/j.jclepro.2017.01.177
https://doi.org/10.1016/j.apsusc.2017.02.003
34. T. F. Sheshko, Yu. M. Serov, T. A. Kryuchkova,
I. A. Khairullina, I. V. Chislova, and I. A. Zvereva,
Russ. J. Phys. Chem. A 90 (6), 1137 (2016).
16. L. Bedel, A. C. Roger, C. Estournes, and A. Kien-
nemann, Catal. Today 85, 207 (2003).
https://doi.org/10.1016/S0920-5861(03)00388-2
https://doi.org/10.1134/S0036024416060236
17. N. Thao Tien and L. T. Son, J. Sci.: Adv. Mater. Devic-
35. H. Iwahara, T. Esaka, H. Uchida, and N. Maeda, Solid
es 1, 337 (2016).
State Ionics 3–4, 359 (1981).
https://doi.org/10.1016/j.jsamd.2016.07.011
https://doi.org/10.1016/0167-2738(81)90113-2
18. I. V. Chislova, A. A. Matveeva, A. V. Volkova, and
I. A. Zvereva, Glass Phys. Chem. 37 (6), 653 (2011).
https://doi.org/10.1134/S1087659611060071
Translated by M. Timoshinina
PETROLEUM CHEMISTRY
Vol. 60
No. 5
2020