Effects of Support Structure and Composition on the Activity of Cu–Ni Catalysts for Methanol Steam Reforming

Article abstract of DOI:10.1134/S0020168519120100

Abstract—: We have studied the catalytic activity of Cu–Ni bimetallic catalysts on yttrium-, tin-, zinc-, and niobium-doped zirconia and ceria supports for methanol steam reforming (MSR), a process for hydrogen production, and examined the effect of the nature of the dopants and annealing temperature on the structure and particle size of the oxide supports and the catalytic activity of the metal oxide composites. In all cases, the addition of heterovalent ions improved the catalytic activity of the materials for the MSR process in comparison with undoped zirconia. The highest hydrogen yield was reached in the case of catalysts doped with niobium and yttrium oxides.

Full text of DOI:10.1134/S0020168519120100

ISSN 0020-1685, Inorganic Materials, 2019, Vol. 55, No. 12, pp. 1230–1236. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Neorganicheskie Materialy, 2019, Vol. 55, No. 12, pp. 1305–1312.
Effects of Support Structure and Composition on the Activity
of Cu–Ni Catalysts for Methanol Steam Reforming
a,
a
a
a
a, b, c
A. A. Lytkina *, N. A. Bakuleva , N. V. Orekhova , M. M. Ermilova , and A. B. Yaroslavtsev
a
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, Moscow, 119991 Russia
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 119071 Russia
b
c
Higher School of Economics (National Research University), Myasnitskaya ul. 20, Moscow, 101000 Russia
*e-mail: lytkina@ips.ac.ru
Received May 10, 2019; revised June 6, 2019; accepted June 21, 2019
Abstract—We have studied the catalytic activity of Cu–Ni bimetallic catalysts on yttrium-, tin-, zinc-, and
niobium-doped zirconia and ceria supports for methanol steam reforming (MSR), a process for hydrogen
production, and examined the effect of the nature of the dopants and annealing temperature on the structure
and particle size of the oxide supports and the catalytic activity of the metal oxide composites. In all cases,
the addition of heterovalent ions improved the catalytic activity of the materials for the MSR process in com-
parison with undoped zirconia. The highest hydrogen yield was reached in the case of catalysts doped with
niobium and yttrium oxides.
Keywords: methanol steam reforming, hydrogen production, bimetallic catalysts, oxide supports, support
effect
DOI: 10.1134/S0020168519120100
INTRODUCTION
CO + H O ↔ CO + H ,
2
2
2
(3)
0
Because of the environmental pollution with fuel
ΔH2
= −41.2 kJ/mol.
98 K
combustion products, a search for new, environmen-
tally friendly energy sources is becoming a more and
more critical issue with every passing year. One prom-
ising approach is to produce electrical energy with the
use of fuel cells. In connection with this, hydrogen is
becoming one of the most highly demanded products
for alternative power generation technologies [1–6].
However, it is rather difficult to transport and store.
One solution to these problems is hydrogen produc-
tion from liquid raw materials, such as lower alcohols
The most frequently used catalysts are copper and
Group VIIIB metals, which offer high catalytic activ-
ity and hydrogen selectivity. One way of improving the
stability of such catalysts and reducing their cost is by
adding a second metal [12–16]. Catalytic systems in
current use typically have the form of metal nanopar-
ticles on a support, which often consists of oxides [17–
22]. In such a case, according to a bifunctional mech-
anism, alcohol conversion steps occur on metal atoms,
and the support provides centers for activation of the
water, which emphasizes the importance of adequately
[7–11].
Methanol steam reforming (MSR) takes place at choosing the support. The structure and chemical
relatively low temperatures (200–350°C) and has high composition of a support make it possible to influence
hydrogen selectivity. The MSR process involves, in the activity and selectivity of the catalytic composite as
addition to the intended reaction (1), methanol a whole.
decomposition reaction (2) and the reaction of the
forming CO with water (3), resulting in the formation
of a mixture of hydrogen, carbon dioxides, and a small
amount of carbon monoxide:
Zirconia is of considerable interest as a support of
metallic catalysts for the MSR process [23–26]. In a
number of studies, it was shown to act as a promoter
for copper-containing catalysts [27]. Zirconia can
exist in several crystalline polymorphs. A particular
structure can be obtained by adjusting the heat treat-
ment temperature and the nature and concentration of
dopants [28]. Besides, the use of dopants leads to a
higher disorder and mobility of the oxygen sublattice
CH OH + H O ↔ CO + 3H ,
3
2
2
2
(1)
0
ΔH2
= 49.7 kJ/mol;
98 K
CH OH ↔ CO + 2H ,
3
0
2
(
2) of zirconia and an increase in the number of active
centers, presumably due to structural defects, on the
ΔH2
= 90.2 kJ/mol;
98 K
1230

EFFECTS OF SUPPORT STRUCTURE AND COMPOSITION
1231
catalyst surface [29, 30]. Potentially attractive dopants (20 mL/min) for 3 h at 350°C in order to reduce the
3+
3+
2+
2+
include heterovalent ions (Y , Sc , Ca , and Mg ), metals. According to electron probe microanalysis
whose presence leads to the formation of vacancies in data, the nickel : copper ratio in all of the samples was
a sublattice, which ensure high oxygen mobility, and near the intended value.
elements capable of redox transformations, such as
The specific surface area and pore size of the sup-
ports and catalysts were determined by BET measure-
ments with an ASAP-2020N porosimeter (Micromer-
itics, the United States). The phase composition of the
samples was determined by X-ray diffraction on a
cerium and tin [31, 32]. Interest in SnO in heteroge-
2
neous catalysis is aroused primarily by its ability to act
as an efficient catalyst for oxidation, especially in reac-
tions involving CO [33], which we believe could
improve the selectivity of catalysts for MSR. Niobium
oxide serves a dual function: it increases the density of
lattice defects and, despite its low redox activity, is
capable of ensuring an increase in the activity of cata-
lysts for oxidation and dehydrogenation reactions
Rigaku D/MAX 2200 diffractometer (CuK radia-
α1
tion). For data processing and qualitative analysis, we
used Rigaku Application Data Processing software.
The crystallite (coherent scattering domain (CSD))
size was evaluated from the width of X-ray diffraction
peaks using the Scherrer formula:
[
34–37].
Previously, we studied Ni–Cu catalysts supported
kλ
on zirconia with a tetragonal and a monoclinic struc-
ture [24]. The objectives of this work were to produce
Ni–Cu bimetallic catalysts supported on zirconia and
ceria doped with yttrium, tin, zinc, and niobium and
test the resultant catalysts in methanol steam conver-
sion in the temperature range 200–350°C.
d =
,
(4)
(
)
B − b cos θ
where k = 0.89 is the Scherrer constant, λ = 1.5406 Å
is the X-ray wavelength used, B is the full width (2θ) at
half maximum of the diffraction peak, b is instrumen-
tal broadening (2θ), and θ is the Bragg angle.
MSR was conducted at atmospheric pressure in a
conventional tubular reactor (tube length, 21.5 cm;
inner diameter, 0.9 cm) in the temperature range 200–
EXPERIMENTAL
Synthesis of catalysts, physicochemical characteri-
zation, and catalytic experiments. Undoped zirconia
was prepared via precipitation with a concentrated
ammonium hydroxide solution from zirconyl nitrate,
ZrO(NO ) (99%, Aldrich), at pH 9 as described in
400°C. A sample of a catalyst (weighing 0.3 g) was
mixed with granulated quartz (size fraction 1–3 mm)
and placed in the central part of the reactor. The reac-
tor was heated to the required temperature by an elec-
tric furnace, while the catalyst was exposed to flowing
argon (20 mL/min). The temperature in the reactor
was measured by a Chromel–Alumel thermocouple.
Prior to each series of experiments, the catalyst was
3
2
detail previously [38]. ZrO –0.1Y O , ZrO –0.1SnO ,
2
2
3
2
2
ZrO –0.1ZnO, ZrO –0.1Nb O , and CeO –0.1SnO
2
2
2
2
5
2
samples were prepared by a similar procedure, via pre-
cipitation from zirconyl nitrate, ZrO(NO ) (99%,
3
∙
2
reduced with a H (5%) + Ar flow (20 mL/min) at a
2
Aldrich); cerium nitrate, Ce(NO )
6H O
2
3
3
temperature of 350°C for 3 h. A liquid mixture of
(
99.995%); yttrium nitrate, Y(NO ) ∙ 6H O (reagent
3 3 2
methanol with water (stoichiometric molar ratio of 1 :
grade); tin(IV) chloride, SnCl ⋅ 5H O (98%, Aldrich), 1) was fed to an evaporator using an Instilar 1488 Dix-
4
2
niobium chloride, NbCl (99.8%, Acros); and zinc ion infusion pump. The unreacted water and alcohol
5
acetate, Zn(CH COO) ⋅ 2H O (analytical grade, were condensed in a glass receiver cooled to +1°C.
3
2
2
The composition of the uncondensed reaction prod-
ucts was determined on an LKhM 8MD gas chro-
matograph using a thermal conductivity detector,
helium carrier gas, and columns packed with a Pora-
pak T stationary phase (for water, methanol, and other
Aldrich). The hydrous oxides obtained in the first step
were annealed in air for 5 h at a temperature of 400°C
in a muffle furnace to ensure crystal structure forma-
tion. To assess the effect of annealing temperature on
the physicochemical characteristics of the materials,
some of them were further annealed at 800°C.
oxygenates) and activated carbon (for CO and CO ).
2
The hydrogen and methane concentrations in the
reaction products were determined on a Chrom-4
chromatograph equipped with a thermal conductivity
detector and zeolite column (CaA Zeosorb phase, Ar
carrier gas). Chromatograms were analyzed using
Ecochrom software.
Methanol conversion X (mol %) and reforming
selectivity (S, %) were assessed from the analytical
data using the following equations:
The resultant samples were sequentially impreg-
nated with aqueous solutions of Сu(NO ) · 3H O
3
2
2
(
>98%) and Ni(NO ) · 6H O (≥98.5%, Aldrich). The
3 2 2
amounts of the solutions were adjusted so that the total
metal content was 20% of the weight of the support.
The nickel : copper ratio in the samples was 1 : 4,
which was optimal for the Cu–Ni system according to
previously reported data [24]. The suspension thus
prepared was dispersed by ultrasonication for 1 h.
Next, the excess water was evaporated at 100°C in a
drying oven. The resultant catalysts were annealed in
n
− n
CH OH,out
CH OH,in
3
3
X CH3OH
=
×100%,
(5)
air at 400°C for 3 h and in a flow of 5% H /Ar
nCH3OH,in
2
INORGANIC MATERIALS Vol. 55 No. 12 2019

1232
LYTKINA et al.
111
ture of 400°C. The observed reflections from the
ZrO –Y O and CeO –SnO samples can be indexed
2
2
3
2
2
in cubic symmetry. Note that no lines attributable to
tin oxide or yttria were detected, which suggested the
formation of solid solutions (Fig. 1, scans 5, 6). It is
220
3
11
2
00
worth noting that the lines of CeO were slightly
2
shifted to larger angles, due to the partial substitution
6
5
4+
of Sn cations, having a smaller ionic radius (0.69 Å),
4+
for Ce ions (0.97 Å) upon the formation of the solid
solution. The cubic cell parameter of the CeO –SnO
2
2
2
20
solid solution is 5.4018 ± 0.0009 Å, which is slightly
smaller than the value characteristic of the cubic cell of
undoped ceria (5.4111 Å). By contrast, doping with
yttrium in the ZrO –Y O system leads to an increase
311
2
00
2
2
3
0
11
in the lattice parameter of ZrO (a
= 5.1233 Å)
2
ZrO −Y O
2 2 3
0
20
3+
due to the substitution of Y cations, having a larger
4
3
4+
ionic radius (0.93 Å), for Zr (0.84 Å) and the forma-
tion of solid solutions.
1
11
In the case of tin doping of zirconia, the effect is
much weaker. Like the undoped sample annealed at
220
2
00
4
00°C, this material crystallizes in monoclinic sym-
011
metry (Fig. 1, scans 1, 2). Note that its X-ray diffrac-
tion pattern shows reflections from both zirconia and
tin oxide, pointing to lower tin solubility in the crystal
lattice of zirconia.
2
After annealing at 400°C, the ZrO –ZnO and
2
1
ZrO –Nb O samples had the form of poorly crystal-
2
2
5
lized materials containing tetragonal zirconia
nanoparticles and an X-ray amorphous phase, which
was represented by a broad halo in the X-ray diffrac-
tion patterns of these samples (Fig. 1, scans 3, 4).
20
30
40
θ, deg
50
60
2
Fig. 1. Partial X-ray diffraction patterns of the materials
annealed at 400°C: (1) ZrO , (2) ZrO –SnO , (3) ZrO –
Raising the annealing temperature to 800°C led to
2
2
2
2
the formation of monoclinic ZrO in the zinc oxide-
2
Nb O , (4) ZrO –ZnO, (5) ZrO –Y O , (6) CeO –SnO .
2
5
2
2
2
3
2
2
doped sample (Fig. 2, scan 1), but there was also a
weak reflection corresponding to a tetragonal struc-
ture. In addition, zinc oxide was present as an individ-
ual phase, with well-defined reflections in the X-ray
diffraction pattern of the sample.
nCO2,out
S =
×100%,
(6)
nCO2,out + nCO,out
In the niobium-doped system, after annealing at
where nCH3OH,in and nCH3OH,out are the amounts of deliv-
8
00°C zirconia was present as a tetragonal phase
ered and unreacted methanol, respectively, and
(
Fig. 2, scan 2). In addition, there were weak reflec-
nCO2,out and nCO,out are the amounts of carbon dioxide
and carbon monoxide in the reaction products. Prod-
uct yields were evaluated as the amount of the corre-
sponding reaction product (in moles) formed per gram
of the metals present in the catalyst per hour. The gas
hourly space velocity (GHSV), calculated as the ratio
tions from niobium oxide. Thus, in this case, niobium
partially dissolved in zirconia to form an imperfect
tetragonal structure.
Table 1 summarizes some characteristics of the
synthesized supports (BET and X-ray diffraction
results). There is a tendency for the specific surface
area of the materials to decrease as a result of doping.
At the same time, the crystallite size of the major oxide
phase changes little. The particle size evaluated from
BET data exceeds the crystallite size by one to two
orders of magnitude, which is due to agglomeration of
the nanoparticles. Raising the annealing temperature
3
of the gas inflow rate (765 cm /h) to the catalyst bed
–1
volume, was 172 h , and this parameter remained
unchanged in all catalytic tests.
RESULTS AND DISCUSSION
Structural and morphological characteristics of the leads to the formation of a material with a smaller spe-
catalysts and support. Figure 1 shows X-ray diffraction cific surface area and a considerably larger particle size
patterns of the samples after annealing at a tempera- (Table 1). In view of this, in preparing catalytic sys-
INORGANIC MATERIALS
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EFFECTS OF SUPPORT STRUCTURE AND COMPOSITION
1233
111
Cu–Ni
11
1
002
020
113
2
1
012
2
111
111
20
25
30
35
40
θ, deg
45
50
55
60
2
220
022
011
211
Fig. 3. X-ray diffraction patterns of the (1) Ni –
0.2
300
021
Cu /ZrO and (2) Ni –Cu /CeO –SnO catalysts.
1
0.8
2
0.2
0.8
2
2
2
0
30
40
θ, deg
50
60
Activity of the catalysts for the MSR process.
According to the present data, all of the materials
studied have high selectivity in the intended reaction
for hydrogen production: at least 99.5% for all of the
catalysts even at high temperatures.
2
Fig. 2. Partial X-ray diffraction patterns of the samples
annealed at 800°C: (1) ZrO –ZnO, (2) ZrO –Nb O .
2
2
2 5
Figure 4 shows temperature dependences of the
hydrogen yield and methanol conversion for the cata-
lysts obtained in this study. The samples based on
undoped zirconia and the Cu–Ni/CeO –SnO cata-
tems we subsequently used supports annealed at
400°C.
2
2
The reflections in the X-ray diffraction pattern of lyst had the lowest catalytic activity. As shown earlier
4
+
3+
Cu–Ni catalysts supported on oxide systems corre-
[
31], the concentration of Ce and Ce cations on
spond to copper, which prevails in the composition of the surface of a catalyst determines in many respects
the catalysts (Fig. 3). At the same time, there is a well- the catalytic activity of composites. Note that a
3
+
4+
defined shift of the reflections from copper, pointing
to the formation of solid solutions. The cubic cell
decrease in the amount of Ce cations relative to Ce
led to a reduction in alcohol conversion and hydrogen
parameter of the Cu –Ni alloy obtained is 3.6162 ± yield. It seems likely that doping of ceria with tetrava-
0.8
0.2
0
.0007 Å. It is also worth noting that the reflections lent tin occurs to a significant degree on the particle
from the metals are somewhat narrower than those surface and leads to a decrease in the surface concen-
from the oxide supports, suggesting that the particle tration of trivalent cerium ions, which is responsible
size of the metals exceeds that of the supports. The for the low catalytic activity of the resultant material.
crystallite size of the metals is about 20 nm, that is, The Cu–Ni/ZrO
–SnO
2
sample also had relatively
2
about twice that of the supports.
low activity, which can be interpreted as evidence that
Table 1. Specific surface area and characteristic particle sizes of the catalysts under study, evaluated from BET and X-ray
diffraction results
Crystallite size, nm
Average particle size from BET
2
Material
S, m /g
data, nm
ZrO2
M Oy
x
ZrO2
CeO –SnO (10%)
155 ± 8
75 ± 3
52 ± 2
49 ± 2
59 ± 2
14 ± 1
134 ± 4
47 ± 2
40
80
10 ± 1
11 ± 1
13 ± 1
8 ± 1
—
—
2
2
ZrO –Y O (10%)
70
2
2
3
ZrO –SnO (10%)
120
100
4 ± 2
—
2
2
ZrO –ZnO (10%) (400°С)
5 ± 2
2
ZrO –ZnO (10%) (800°С)
33 ± 1
8 ± 2
24 ± 1
—
2
ZrO –Nb O (10%) (400°С)
45
2
2
5
ZrO –Nb O (10%) (800°С)
12 ± 1
17 ± 1
2
2
5
INORGANIC MATERIALS Vol. 55 No. 12 2019

1234
LYTKINA et al.
а)
(
Cu–Ni/ZrO2
1.0
Cu–Ni/CeO –ZnO
2
2
Cu–Ni/ZrO –ZnO
2
0
0
0
0
.8
.6
.4
.2
0
Cu–Ni/ZrO –Y O
3
2
2
Cu–Ni/ZrO –SnO
2
2
Cu–Ni/ZrO –Nb O
2
2
5
150
200
250
Temperature, °C
300
350
(b)
7
6
5
4
3
2
0
0
0
0
0
0
10
0
1
50
200
250
Temperature, °C
300
350
Fig. 4. Temperature dependences of the (a) H yield and (b) methanol conversion for the catalysts obtained.
2
tin oxide has low water adsorption capacity. However,
as was expected, no carbon dioxide was detected in of the samples doped with niobium and yttrium
reaction products to within the accuracy of chroma- oxides. As shown above, the ZrO –Y and ZrO
tography even in high-temperature tests of the tin- Nb O materials have a cubic and a tetragonal struc-
The highest hydrogen yield was reached in the case
O
–
2
2
2
3
2
5
doped samples.
ture, respectively. This points to a higher activity of the
INORGANIC MATERIALS
Vol. 55
No. 12
2019

EFFECTS OF SUPPORT STRUCTURE AND COMPOSITION
1235
catalyst supported on the high-temperature ZrO
4. Abe, J.O., Popoola, A.P.I., Ajenifuja, E., and
Popoola, O.M., Hydrogen energy, economy and stor-
age: review and recommendation, Int. J. Hydrogen En-
ergy, 2019, vol. 44, pp. 15 072–15 086.
2
polymorphs. The addition of trivalent or pentavalent
metal ions leads to higher disorder and mobility in the
oxygen sublattice of the oxide and increases the num-
ber of active centers, presumably due to structural
defects, on the catalyst surface. Moreover, Table 1
demonstrates that the specific surface area of the nio-
bium oxide-containing support is considerably larger,
which can be interpreted as evidence for higher activity
of the catalyst supported on the finer oxide particles.
5
. Naruki, E., Shimoda, E., Goshome, K., Yamane, T.,
Nozu, T., and Maeda, T., Construction and operation
of hydrogen energy utilization system for a zero emis-
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8
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. Miranda, P.E., Hydrogen energy, Sustainable and Pe-
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CONCLUSIONS
The present results lead us to conclude that
changes in the composition and structure of an oxide
support can influence the activity of sorption centers,
the tendency of the support toward oxygen and/or
proton transport processes, and its ability to partici-
pate in redox processes. In all cases, the addition of
heterovalent ions improved the catalytic activity of the
samples in comparison with undoped zirconia, proba-
bly because of the higher disorder and mobility in the
oxygen sublattice of the oxide, and increased the num-
ber of active centers, presumably due to structural
defects, on the catalyst surface.
. López-Tenllado, F.J., Hidalgo-Carrillo, J., Montes-
Jiménez, V., Sánchez-López, E., Urbano, F.J., and
Marinas, A., Photocatalytic production of hydrogen
from binary mixtures of C-3 alcohols on Pt/TiO : in-
2
fluence of alcohol structure, Catal. Today, 2019,
vol. 328, pp. 2–7.
A higher lattice symmetry of oxide supports allows 10. Li, Sh., Zheng, H., Zheng, Y., Tian, J., Jing, T.,
a higher hydrogen yield to be reached in the MSR pro-
cess catalyzed by Cu–Ni materials. Catalytic activity
has been shown to increase in the sequence Cu–
Chang, Jo-Sh., and Ho, Sh.H., Recent advances in hy-
drogen production by thermo-catalytic conversion of
biomass, Int. J. Hydrogen Energy, 2019, vol. 44,
pp. 14266–14278.
Ni/ZrO
(monoclinic)
<
Cu–Ni/ZrO –SnO
2 2
2
1
1. Chiu, Y.J., Chiu, H.C., Hsieh, R.H., Jang, J.H., and
Jiang, B.Y., Simulations of hydrogen production by
methanol steam reforming, Energy Proc., 2019,
vol. 156, pp. 38–42.
(
monoclinic) < Cu–Ni/ZrO –ZnO (monoclinic) <
2
Cu–Ni/ZrO –Nb O (tetragonal) ≈ Cu–Ni/ZrO –
2
2
5
2
Y O (cubic).
2
3
1
2. Lytkina, A.A., Orekhova, N.V., and Yaroslavtsev, A.B.,
Catalysts for the steam reforming and electrochemical
oxidation of methanol, Inorg. Mater., 2018, vol. 54,
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FUNDING
This work was supported by the Russian Federation
Ministry of Science and Higher Education (agreement no. 13. Kim, D.H., Kim, J.H., Jang, Y.S., and Kim, J.C., Hy-
drogen production by oxidative steam reforming of
methanol over anodic aluminum oxide-supported Cu–
Zn catalyst, Int. J. Hydrogen Energy, 2019, vol. 44,
pp. 9873–9882.
RFMEFI58617X0053) and CNRS, France (project no.
8200SF).
3
1
4. Tahay, P., Khani, Y., Jabari, M., Bahadoran, F., and
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Translated by O. Tsarev
INORGANIC MATERIALS
Vol. 55
No. 12
2019