Carbon Monoxide Hydrogenation over Gd(Fe/Mn)O3 Perovskite-Type Catalysts

Article abstract of DOI:10.1134/S0965544119120107

Abstract: Catalytic properties of GdFeO₃ and GdMnO₃ perovskite-type oxides in CO hydrogenation processes is conducted. Complex oxides Gd(Fe/Mn)O₃ are synthesized by the sol–gel technology and characterized by X-ray diffraction, temperature-programmed reduction, and scanning electron microscopy. It is found that the iron-containing catalyst has fairly high catalytic characteristics; therefore, it provides lower temperatures of carbon monoxide hydrogenation. The presence of manganese in the catalyst leads to an increase in light olefin selectivity compared with the sample containing iron at the B-site. It is assumed that gadolinium cations are responsible for dissociative chemisorption, while iron and manganese cations are responsible for the formation of atomic hydrogen. The two catalysts exhibit resistance to carbon deposition.

Full text of DOI:10.1134/S0965544119120107

ISSN 0965-5441, Petroleum Chemistry, 2019, Vol. 59, No. 12, pp. 1307–1313. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Nanogeterogennyi Kataliz, 2019, Vol. 4, No. 2, pp. 118–124.
Carbon Monoxide Hydrogenation
over Gd(Fe/Mn)O3 Perovskite-Type Catalysts
T. F. Sheshkoa, *, E. B. Markovaa, A. A. Sharaevaa, T. A. Kryuchkovaa, I. A. Zverevab,
I. V. Chislovab, and L. V. Yafarovab
aPeoples’ Friendship University of Russia, Moscow, 117198 Russia
bSt. Petersburg State University, St. Petersburg, 198504 Russia
*e-mail: sheshko-tf@rudn.ru
Received January 8, 2019; revised July 10, 2019; accepted August 9, 2019
Abstract—Catalytic properties of GdFeO3 and GdMnO3 perovskite-type oxides in CO hydrogenation pro-
cesses is conducted. Complex oxides Gd(Fe/Mn)O3 are synthesized by the sol–gel technology and charac-
terized by X-ray diffraction, temperature-programmed reduction, and scanning electron microscopy. It is
found that the iron-containing catalyst has fairly high catalytic characteristics; therefore, it provides lower
temperatures of carbon monoxide hydrogenation. The presence of manganese in the catalyst leads to an
increase in light olefin selectivity compared with the sample containing iron at the B-site. It is assumed that
gadolinium cations are responsible for dissociative chemisorption, while iron and manganese cations are
responsible for the formation of atomic hydrogen. The two catalysts exhibit resistance to carbon deposition.
Keywords: perovskites, hydrogenation, carbon monoxide, olefins, perovskite-type complex oxides, ferrites
DOI: 10.1134/S0965544119120107
Perovskite-type complex oxides with a general for- structure. A variation in the Co/Fe ratio and the La
mula of ABO3 (A is an alkaline, alkaline-earth, or content in LaCoxFe(1 – x)O3 [4] also led to a change in
rare-earth element; B is a transition metal) are used as the crystal structure type (rhombic, orthorhombic,
catalysts for various organic synthesis processes. cubic), which affected the formation of metal phases
Owing to the structural stability of these oxides and on the catalyst surface due to reduction and, as a con-
the possibility of varying the cationic composition sequence, influenced the C2–C4 olefin selectivity. The
over a wide range, these materials can be adapted to a
number of processes for the selective synthesis of reac-
tion products. The high thermal stability and oxygen
and ion conductivity make perovskites ideal candi-
dates for use as catalysts for high-temperature reac-
tions [1]. It was shown [2] that the substitution of met-
als at the A- and B-sites of the complex oxide structure
can provide the reaction selectivity for the target prod-
uct.
The activity of La(1 – y)Co0.4Fe0.6O3–δ perovskites in
carbon monoxide hydrogenation increased with a
decrease in the lanthanum fraction in the systems [3];
the highest selectivity for C2–C4 olefins was exhibited
by a La(1 – y)Co0.4Fe0.6O3–δ catalyst, where y = 0.4, due
to the formation of a Fe–Co metal alloy on the surface
owing to the partial reduction of the complex oxide
under the action of the reaction medium. The authors
of [1] found that the substitution of strontium for lan-
thanum in perovskite catalysts of the La1 – xSrxCoO3
Co/La2O3-doped La4Ga2O9 catalyst (LaCo1 – xGaxO3
as a precursor) showed a high ethanol selectivity, sta-
bility, and resistance to sintering and carbon deposi-
tion in the Fischer–Tropsch synthesis using a simu-
lated gas mixture comparable to bio-synthesis gas [5].
The effect of partial substitution of the metal at the
A-sites of a perovskite-like Gd2 – хSr1 + хFe2O7 (х = 0,
0.1, 0.2, 0.3, 0.4) layered oxide was studied previously
[6]. It was found that the nonisovalent substitution of
Sr2+ for Gd3+ leads to distortion of the structure and
implementation of the heterovalent state of iron atoms
(Fe3+ and Fe4+), which affects the olefin selectivity in
the CO hydrogenation process. It was shown that that
Gd2 – xSr1 + xFe2O7 with x = 0.3 exhibited the highest
selectivity for unsaturated hydrocarbons (ethylene and
propylene) in carbon monoxide hydrogenation.
Light olefins, such as ethylene, propylene, and
butylene, are commonly used for the synthesis of
type led to the inhibition of the Fischer–Tropsch syn- naphtha conversion products (e.g., solvents, paints,
thesis process, which was attributed by the cited polymers). The conventional methods for the produc-
authors to a change in the complex oxide structure and tion of light olefins (pyrolysis and liquid-phase cata-
the transition from a rhombohedral to less stable cubic lytic cracking of straight-run gasoline and the FCC
1307

1308
SHESHKO et al.
process) were not able to satisfy the high market tion at –196°С (Quadrasorb SI). Prior to adsorption
demand because of the low olefin selectivity and the measurements, all samples were degassed at 300°C for
high cost of petroleum feedstocks [7]. In recent years, 5 h to remove residual moisture and other volatile sub-
studies aimed at searching for alternative methods for stances.
the production of light olefins have been conducted
The oxidation state of Fe and Mn was studied by X-ray
[8–11]. The reforming of coal, natural gas, and bio-
photoelectron spectroscopy (Thermo Fisher Scientific
mass provides an alternative route for light olefin syn-
Escalab 250Xi) using AlKα radiation (λ= 0.1541 nm) as an
thesis. Some processes, such as methanol to olefins
excitation source.
(MTO) and syngas via dimethyl ether to olefins
Catalytic testing procedure. Catalytic activity in carbon
monoxide hydrogenation was tested in a U-shaped fixed-
bed quartz flow reactor with a 100-mg weighed portion of
the catalyst diluted with quartz (weight of 500 mg, a frac-
tion of 0.25–0.5 nm) placed into it. The reactor was placed
in a temperature-controlled furnace; temperature was
measured/controlled using a K-type thermocouple placed
into the center of the catalytic bed without direct contact.
The process temperature was increased from 523 to 708 K.
The reaction was run at a pressure of 1 atm and a gas mix-
ture flow rate of 1.5 L/h (CO : H2 = 1 : 2). In all tests, the
samples were used without prereduction. Analysis of the
reaction mixture above the catalyst surface was conducted
on a Kristall 5000.2 gas chromatograph equipped with a
stainless steel column filled with the Porapak Q sorbent
and sequentially connected thermal conductivity and
flame ionization detectors. The rate of formation of reac-
tion products (specific catalytic activity) R (mol/(h gcat))
was determined from the constancy of chromatographic
peaks.
(SDTO) in the presence of zeolite catalysts have
already been implemented in industry. The main dis-
advantages of these technologies are the high operat-
ing costs and the rapid catalyst deactivation [12].
The aim of this study is to compare the catalytic
activity of GdFeO3 and GdMnO3 complex oxides
containing different cations at the B-sites in carbon
monoxide hydrogenation.
EXPERIMENTAL
Sample synthesis procedure. Initial reagents were
reagent grade Gd(NO3)3 ⋅ 6H2O (Specifications TU
6–09–4676–83), high-purity grade Mn(NO3)2
⋅
6H2O and Fe(NO3)3 ⋅ 9H2O (TU 6–09–02–553–96),
citric acid, and an ammonia solution.
The Gd(Fe,Mn)O3 compounds were synthesized
by the sol–gel method in accordance with the citrate–
nitrate technique [13, 14]. Gd(NO3)3 ⋅ 5H2O and
Mn(NO3)2 ⋅ 6H2O/Fe(NO3)3 ⋅ 9H2O compounds
taken in a stoichiometric amount were dissolved in
distilled water; the resulting solution was mixed with
an aqueous solution of citric acid; after that, to main-
tain pH 6, an ammonia solution was added dropwise
under permanent stirring. The prepared solution was
held at a temperature of 353–363 K to obtain a wet gel,
which was slowly heated in air to a temperature of
523 K, at which ignition and intense gas evolution
were observed. After ignition, the sample was calcined
with a gradual increase in temperature from 523 to
723 K for 30 min and then held at 723 K for 2 h. The
resulting powders were crushed (homogenized) in an
agate mortar, pelletized, and calcined in a muffle fur-
nace at a temperature of 1073 K for 1 h.
Carbon monoxide conversion was calculated by
the formula
n
– n
i,inlet
(1)
Xi =
i,outlet ×100%,
n
i,inlet
where ni,inlet and ni,outlet are the amount of carbon mon-
oxide at the inlet and outlet of the reactor, respectively.
The rate of formation was calculated by the formula
K x Si w
Vloopmcat
Ri =
,
(2)
where Kx is the correction coefficient for the ith reac-
tion product; Si is the peak area, mm2; Ri is the rate of
formation of the ith reaction product per gram of cat-
alyst; w is the volume flow rate of the reaction mixture,
1–1.5 L/h; Vloop is the chromatograph loop volume,
0.001 L; and mcat is the weight of the catalyst metal
phase, g.
Investigation procedures. The phase composition of
the catalysts before and after catalytic tests was studied
by X-ray powder diffraction analysis (Rigaku Mini-
Flex II instrument) at room temperature (CuKα radi-
ation, an angular range of 2θ = 20°–60°, a scan rate of
5°С/min). The crystalline phases were identified
using the PDF2 database.
Reaction product selectivity was calculated by the
formula
The morphology and chemical composition of the
surface before and after catalytic processes were stud-
ied using an emission scanning microscope (Zeiss
Merlin and Zeiss Supra 40VP) equipped with an
energy dispersive spectroscopy system.
The specific surface area of the compounds before the sum of the rates of formation of the ith reaction
catalytic reactions was determined by nitrogen adsorp- products per gram of catalyst, mol/(h gcat).
R
 R
i
(3)
Si =
×100%,
i
where Ri is the rate of formation of the ith reaction
product per gram of catalyst, mol/(h gcat) and ΣRi is
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CARBON MONOXIDE HYDROGENATION
(a) (b)
1309
1
1
30 35 40 45 50 55 60
20 25
30 35 40 45 50 55 60
20 25
20 25
SiO2
C
2
2
30 35 40 45 50 55 60
30 35 40 45 50 55 60
20 25
2θ, deg
2θ, deg
Fig. 1. XDR patterns of (a) GdFeO and (b) GdMnO oxides: (1) before and (2) after catalytic processes.
3
3
RESULTS AND DISCUSSION
adsorption of CO occurs at room temperature, and the
behavior of the curves is identical for the two samples
(Fig. 3).
The diffraction patterns of the samples measured
before catalytic tests (Fig. 1) show that all the synthe-
sized compounds obtained are single-phase materials,
because the diffraction peaks are in good agreement
with the data from the PDF2 database: GdFeO3 (01-
072-9908) and GdMnO3 (01-070-9199). An analysis
of the phase composition after catalytic tests shows
that the phase composition of GdFeO3 remains
unchanged during reactions, while the diffraction pat-
tern of GdMnO3 shows the presence of C (PDF#00-
041-1487); in addition, the presence of SiO2
(PDF#01-077-1725), which was used to prevent the
catalyst surface from sintering, is observed for the
tested samples.
After establishment of the adsorption equilibrium,
up to a temperature of 573 K, the composition of the
gas phase (СО + Н2) remained almost unchanged,
and the transition to the catalytic temperature range
(596–708 K) was accompanied by the formation of
СО2. This process was particularly pronounced in the
presence of gadolinium ferrite; this fact can be appar-
ently attributed to a more intense occurrence of the
Bell–Boudoir reaction 2СО → СО2 + С to form the
active carbon [15].
In addition, CO2 can be formed during the reaction
of an adsorbed COads molecule either with the surface
oxygen of perovskite (OS) or with oxygen released
during the dissociative adsorption of CO; that is,
СОads + ОS → СО2 [15]. In the presence of sample 1
(GdMnO3), the CO conversion was ~70% and varied
only slightly with increasing temperature, while in the
presence of sample 2 (GdFeO3), the CO conversion
was slightly lower—at a level of ~60% (Fig. 3c).
Since the behaviors of the curves describing the
temperature dependences of CO conversion and CO
content in the reaction mixture did not differ signifi-
cantly for the studied catalysts, it can be assumed that
only carbon particles formed during dissociative
adsorption in the region of noncatalytic temperatures
are involved in the formation of the reaction products.
In the presence of all the tested samples, the hydro-
genation reaction products were C1–C6 hydrocarbons;
the main products were methane, ethylene, propyl-
ene, and butylene. The formation of all the products
began even at 523 K and increased with increasing
temperature; however, at T > 623 K, the rates of for-
mation of C3–C6 hydrocarbons decreased (Table 1).
The specific surface area determined by the low-
temperature nitrogen adsorption method (Brunauer–
Emmett–Teller method) for GdFeO3 and GdMnO3
was 3.0 and 8.5 m2/g, respectively.
Scanning electron microscopy data show that the
synthesized compounds have similar morphologies
and consist of crystalline particles with an average size
of 100–200 nm (Fig. 2). However, a slight agglomera-
tion of particles is observed after catalytic tests. The
energy dispersive analysis of the surface of the studied
compounds shows that, after catalytic processes, car-
bon is present on the sample surface; however, the
quantitative content of carbon cannot be determined,
because of its uneven distribution over the catalyst sur-
face.
X-ray photoelectron spectroscopy studies of the
catalysts showed that the GdFeO3 compound com-
prises Fe in the 3+ state (Fe 2p3/2 binding energy of
~710.9 eV), while the GdMnO3 compound comprises
Mn in the 2+ and 3+ heterovalent state (Mn 2p3/2 bind-
ing energy of ~641.48 eV).
Carbon monoxide hydrogenation was run in a tem-
A comparison of the rates of formation of the main
perature range of 523–708 K at a CO : H2 ratio of 1 : 2. products (methane, ethylene, butylene, СО2) in the
Analysis of the content of the reactants in the gas presence of the studied samples revealed that the
phase at the catalyst surface showed that an intense replacement of Mn (sample 1) by Fe (sample 2) at the
PETROLEUM CHEMISTRY Vol. 59 No. 12 2019

1310
SHESHKO et al.
(b)
(a)
200 nm
100 nm
(c)
(d)
200 nm
200 nm
Fig. 2. SEM images of (a, b) GdFeO and (c, d) GdMnO : (a, c) before and (b, d) after catalytic reaction.
3
3
140
120
100
80
(a)
(b)
(c)
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0
75
70
65
60
55
50
60
40
1
2
20
550 600 650 700 750
550 600 650 700 750
550 600 650 700 750
500
500
500
T, К
T, К
T, К
Fig. 3. Temperature dependences of (a) carbon monoxide and (b) carbon dioxide content in the gas phase during adsorption and
hydrogenation and (c) temperature dependences of CO conversion at a CO : H ratio of 1 : 2.
2
B-site of the perovskite structure causes a significant and their difference [16]. The difference between the
adsorption energies of CO and H2 on the Fe surface is
less than that on the Mn surface; these energies them-
selves are not extremely high; therefore, the energy
barrier to the reaction of adsorbed CO and H2 will be
small. These values correlate well with the CO conver-
sion obtained and specific catalytic activity of the
samples.
increase in specific catalytic activity, i.e., an increase
in the rates of formation of the main reaction products
(Table 1). Since catalytic synthesis occurs via the reac-
tion of chemisorbed reagents, it is reasonable to expect
correlation of the catalytic activity and selectivity of
transition metals with both the absolute values of the
heat of adsorption of CO and H2 on the metal surface
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CARBON MONOXIDE HYDROGENATION
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Table 1. Rate of formation R of the main products of the hydrogenation reaction at a CO : H2 ratio of 1 : 2
R(CH4),
R(C2H4),
R(C2H6),
R(C3H6),
R(C4H8), R(C4H10), R(C5H10),
Sample
T, K
μmol/(g h) μmol/(g h) μmol/(g h) μmol/(g h) μmol/(g h) μmol/(g h) μmol/(g h)
GdMnO3
<600
>700
<600
>700
1.08
6.79
303.23
2536.01
0.27
2.64
90.82
726.89
0.07
0.07
6.45
0.05
0.04
36.42
0
2.39
0.28
6.37
0.27
0.03
0.35
9.00
1.21
1.03
2.69
2.16
GdFeO3
39.33
30.48
A variation in the catalyst composition led to a GdMnO3 and GdFeO3 samples can be associated with
change in the quantitative ratio of hydrogenation
products. For example, in the presence of the
GdMnO3 catalyst, the content of methane and light
different diffusion rates of weakly bound atomic
hydrogen across the catalyst surface (the spillover
effect). Apparently, at low temperatures, in the pres-
olefins in the reaction mixture at T = 673 K was 40 and ence of the manganese-containing samples, the CHx
35%, respectively; in the case of complex oxides in
which iron was completely replaced with manganese,
the amount of methane increased to 71%, while
the olefin content decreased to 26%; the fraction of
C5–C6 hydrocarbons also decreased. It should be
noted that, for manganese-containing sample 1, in the
temperature range up to 673 K, the rates of formation
of butylene were almost an order of magnitude higher
than the rates of formation of ethylene (Fig. 4). Fur-
ther increase in temperature provoked a decrease in
the rates of formation of butylene and a significant
increase in the rates of formation of ethylene. In the
case of sample 2 (GdFeO3), the amount of butylene
was negligible (Fig. 4).
radicals react with each other to form mostly butylene.
An increase in the process temperature leads to an
increase in the mobility of both the CHx particles and
atomic hydrogen; it is this factor that is responsible for
an increase in the amount of the produced ethylene.
Calculations of total olefin selectivities during
hydrogenation indicated that the introduction of man-
ganese into the B-site of the perovskite lattice contrib-
utes to an increase in the process selectivity for light
olefins (C2–C4), as evidenced by Fig. 5. Thus, at tem-
peratures of 623–673 K, in the presence of the
GdFeO3 sample, the olefin selectivity was about 25%;
in the case of the manganese-containing sample,
selectivity achieved 80%, which is higher than the val-
ues described in [18, 19] for iron–manganese cata-
lysts.
Earlier [17], it has been speculated that, during car-
bon oxide hydrogenation, iron-generated CHx radi-
cals can be transferred through the gas phase (the jum-
pover effect) to the manganese oxide surface, which nates of the Arrhenius equation made it possible to
hardly contains sorbed hydrogen; it is this place where determine the effective activation energies for the for-
the subsequent recombination of these radicals to ole- mation of products and the logarithms of the pre-
fins occurs. Difference in the catalytic activities of the exponent characterizing the number of active sites.
The processing of the test data in the linear coordi-
0.003
0.002
0.001
0
(a)
(b)
0.8
0.6
0.4
0.2
0
Ethylene
Butylene
550
600
650
700
750
550
600
650
700
750
500
500
T, К
T, К
Fig. 4. Temperature dependences of the rates of ethylene and butylene formation over (a) GdMnO and (b) GdFeO .
3
3
PETROLEUM CHEMISTRY Vol. 59 No. 12 2019

1312
100
SHESHKO et al.
surface, which hardly contains sorbed hydrogen; it is
this place where the subsequent recombination of
these radicals to olefins occurs. Differences in the cat-
alytic activity of the samples are attributed to different
diffusion rates of weakly bound atomic hydrogen (НI)
across the catalyst surface (the spillover effect). Our
results are in good agreement with this assumption: at
low temperatures, in the presence of the manganese-
containing samples, the CHx radicals react with each
other to form mostly butylene. An increase in the pro-
cess temperature leads to an increase in the mobility of
both CHx particles and atomic hydrogen; it is this fac-
tor that is responsible for an increase in the amount of
the produced ethylene. The nature of the 3d metal in
GdBO3 does not affect the coking rate of the catalysts;
the two catalyst systems showed resistance to carbon
deposition.
1
2
80
60
40
20
0
573
623
T, К
673
708
523
Fig. 5. Light olefins selectivity over (1) GdMnO and
3
(2) GdFeO during hydrogenation at a CO : H ratio of
3
2
1 : 2.
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.
The effective activation energies for the formation of
methane eff (СН4) were 67 and 70 kJ/mol for sam-
Еа
ples 1 and 2, respectively (negligible differences
between 1 and 2), while lnK0(СН4) for sample 1 was
significantly lower than that for sample 2 (–1.05 and
5.7, respectively). Apparently, a decrease in the num-
ber of active sites affected the decrease in the rates of
formation of products in the presence of the manga-
nese-containing sample. An opposite tendency was
observed for the formation of olefins: at close lnK0 val-
ues (3.46 and 3.49), the effective activation energies
for sample 1 were higher (98 kJ/mol vs. 65 kJ/mol for
sample 2).
FUNDING
This work was supported by Russian Foundation for
Basic Research, project no. 17-03-00647.
Preparation of the publication was supported by the
RUDN University Program 5-100.
Thus, the comprehensive physicochemical study of
the samples after catalytic processes has shown the fol-
lowing:
(i) Temperature and reaction medium do not affect
the structure of the GdВO3 (B = Fe, Mn) complex
oxide; the phase composition of the catalyst remains
unchanged.
CONFLICT OF INTEREST
The authors declare that there is no conflict of interest
regarding the publication of this manuscript.
ADDITIONAL INFORMATION
(ii) The high-temperature process leads to particle
agglomeration, which results in a decrease in the spe-
cific surface area of the samples. Elemental analysis
has shown the presence of carbon on the surface of the
studied perovskites; in addition, deposition occurs
unevenly. However, since all the catalytic characteris-
tics of the complex oxides are maintained for a long
time (50 h), it can be assumed that most of the surface
carbon is involved in the reaction and exhibits activity.
T.F. Sheshko, ORCID: https://orcid.org/0000-0003-
4176-4085
E.B. Markova, ORCID: https://orcid.org/0000-0003-
2735-2893
A.A. Sharaeva, ORCID: https://orcid.org/0000-0001-
6465-7368
T.A. Kryuchkova, ORCID: https://orcid.org/0000-
0001-6810-9756
(iii) The substitution of manganese for iron in the
GdFeO3 catalyst leads, on the one hand, to a change
in CO conversion and, on the other hand, to a signifi-
cant increase in olefin selectivity in the cohydrogena-
tion of carbon oxides. It has been speculated that iron-
generated CHx radicals are transferred through the gas
phase (the jumpover effect) to the manganese oxide
I.A. Zvereva, ORCID: http://orcid.org/0000-0002-
6898-3897
I.V. Chislova, ORCID: http://orcid.org/0000-0001-
5212-5014
L.V. Yafarova, ORCID: http://orcid.org/0000-0001-
7572-2209
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10. J. Zhang, X. Wang, L. Ma, X. Yu, Q. Ma, S. Fan, and
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PETROLEUM CHEMISTRY Vol. 59 No. 12 2019