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Performance and structural features of

LaNi0.5Co0.5O3 perovskite oxides for the dry
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Cite this: New J. Chem., 2019,

43, 10763 reforming of methane: influence of the
preparation method
Maryam Mousavi and Ali Nakhaei Pour *

Received 15th April 2019,
Accepted 12th June 2019
DOI: 10.1039/c9nj01805k
rsc.li/njc
LaNiO3 and LaNi0.5Co0.5O3 as Ni-based perovskite-type oxides were synthesized via the co-precipitation
method and the activity of the catalysts was evaluated in the methane dry reforming reaction with CO2.
The structure of the prepared perovskites was changed by using magnetized water and was characterized by
means of XRD, BET, SEM, TEM, TPR, and TPH techniques. The result demonstrated that the catalytic activity
and the stability of LaNi0.5Co0.5O3 were less than those of LaNiO3 while the coke resistance was higher for
the LaNi0.5Co0.5O3 catalyst. On the other hand, it was proved that the presence of free Ni phase in the non-
treated samples provided the higher initial activity in comparison to the magnetized ones. The trend for the
amount of the deposited carbon over the surface of the spent catalysts was as follows: LaNiO3 (none) 4
LaNiO3 (treat) 4 LaNiCoO3 (none) 4 LaNiCoO3 (treat).

1. Introduction transition elements, respectively, responsible for the thermal

Today, synthesis gas (syngas) has received substantial attention
as an opportunity to achieve significant progress in the field of
transportation, because of its usage in the process of hydrogen
production.1–4 Syngas is produced through diverse methods,
such as the partial oxidation of methane (POM), steam reform-
ing of methane (SR), auto-thermal reforming of methane (ATR),
and dry reforming of methane (DRM).5–7 Among the available
techniques, DRM has attracted great attention because it is an
appropriate method to obtain varied oxygenates and hydrocarbons.8
Nickel (Ni) and some noble metals are known as the active
catalysts for the DRM process, due to low cost, particular redox
properties, and great initial activity to enhance the DRM
efficiency.9,10 However, it is a hard task to prevent the sintering
of the Ni and carbon deposits during the DRM process at high
temperatures.11 Recently, many reports have been published
on sintering and carbon resistant catalysts for the DRM
reaction.12–14 In addition, Ni-based bimetals supported on
SiO2 are expected to be one hopeful class of catalysts due to
their high thermal stability and high specific surface area for
DRM.15 Catalysts derived from perovskite-type oxide precursors
have been introduced that fulfill the requirement for thermal
stability.16 The perovskite-type oxides have a general formula of
ABO3, in which A and B are alkaline earth or lanthanide and
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad,
P.O. Box: 9177948974, Mashhad, Iran. E-mail: a.nakhaei@um.ac.ir,
nakhaeipoura@yahoo.com; Fax: +98 5138795457; Tel: +98 5138795457
resistance and the catalytic activity under harsh conditions.16–18
The perovskite-type oxides produce particles with a nanometer size
and a great metallic dispersion under the reduction process. The
high dispersion of the metal phase is obtained by an efficient
application of the catalyst precursors through controlled segrega-
tion of the active phase.19,20
Up to now, the LaNiO3 perovskite catalyst has been exten-
sively applied to fulfill the stability requirement and also, to
produce greatly dispersed Ni particles under the reduction
process. The activity of the catalyst can be changed by varying
the particle size of the active phase.21–23 Hence, the partial
substitution in both the A and B positions of the perovskites is
applied as an approach to obtain Ni particles with different
sizes. Besides, the improvement of the catalyst resistance can
be achieved by the synergistic effects between Ni and the metal
in the B position of the LaNiO3 perovskite.10,24 Moradi et al.
proved that the Ni substitution by Zn could change the required
temperature for the Ni reducibility, which obtained a high
conversion activity to CH4 and CO2.25 Valderrama et al. also
reported that the partial Ni substitution by Co achieved an
increase in the CH4 and CO2 conversions accompanied by
inhibition of the carbon formation.26 Song et al. confirmed
that the Fe substitution could enhance the stability of the
LaNiO3 perovskite in the DRM process.27 Gao et al. reported
that the Ni metal size in the Ni–Co catalyst supported on silica
is controlled by the Co addition and the Ni–silica interaction
is controlled by the interaction between the Co and silica
support.28 The work by Bian and Kawi showed that high

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carbon-resistance of the Ni–Co phyllosilicate catalysts was
partly attributed to the affinity of Co towards the oxygen
species.29 In addition, the effect of other supports on the
Ni–Co bimetallic systems in DRM is evaluated in a previous
report.8
The previous studies show that the structure of the LaNiO3
perovskites can be significantly affected by the preparation
method.30 Moreover, some parameters can change the perovs-
kite structure, such as the metal loading (the density of the Ni
metal on the surface), the applied solvents or precursors for the
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impregnation, etc. On the other hand, the solvent properties
including its surface tension and viscosity can be affected by
the magnetic field.31–36
In the present work, we study the preparation of the LaNiO3
and La Ni0.5Co0.5O3 perovskite structures through the precipi-
tation method by applying a magnetized and non-magnetized
solvent. Besides, the effect of Ni2+ substitution by Co2+ in the B
positions of the perovskite structure has been investigated on
the catalyst activity, product selectivity, and coke deposition.
2. Experimental
2.1. LaNi1 xCoxO3 perovskite preparation
The LaNiO3 and LaNi0.5Co0.5O3 perovskites were synthesized by the
co-precipitation method. Stoichiometric amounts of Ni(NO3)2
6H2O,
Co(NO3)2
6H2O and La(NO3)3
6H2O were dissolved in distilled
water and stirred continuously at 80 1C for 2 h. On the other
hand, the stoichiometric amount of ammonium carbonate was
dissolved in distilled water in a separate solution. Afterward, the
second solution was slowly added to the first one at 80 1C under
continuous stirring and aged for 3 h. The prepared precipitates
were filtered and washed with deionized water several times
until it become colorless. The prepared samples were dried
overnight at 120 1C, and calcined in air at 850 1C for 10 h.
Two series of perovskite samples were prepared using distilled
water and magnetized distilled water (MW). The magnetized
distilled water was prepared using a magnetic field (6500 G) several
times as reported previously.34
2.2. Characterization
Phase analyses of the calcined perovskites were determined by
X-ray diffraction (XRD) in a Philips PW-1840 X-ray diffracto-
meter using a Cu Ka radiation source (l = 1.541 Å) to identify
the crystalline structure.
The specific surface areas, total pore volume and average
pore diameter of the calcined perovskites were determined
by N2 physisorption at 77 K using a Micrometrics ASAP 2010
automated system. Before each measurement, 50 mg of the
sample was degassed under vacuum at 573 K for 2 h. The
specific surface areas of the materials were calculated by
the Brunauer–Emmett–Teller (BET) model and the pore size
distribution from the desorption branch of the isotherms using
the Barrett–Joyner–Halenda (BJH) method.
Transmission electron microscopy (TEM) observations
were conducted using an LEO 912AB electron microscope.
10764 | New J. Chem., 2019, 43, 10763--10773 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019
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The samples for TEM were dispersed in ethanol assisted by
the ultrasonic technique. The surface morphologies of the
calcined perovskites were investigated by a scanning electron
microscope (SEM, LEO 1450VP, Germany) with a field emission
filament.
Hydrogen temperature programmed reduction (H2-TPR)
experiments were carried out by using a Micromeritics TPD-
TPR model 2900 instrument. The hydrogen amount during the
reduction was measured using a thermal conductivity detector
(TCD). Typically, 50 mg of sample was loaded in a quartz
reactor, the reduction gas of 5.1% H2/N2 was introduced, and
TCD results monitored the hydrogen consumption.
The amount of coke deposition on the active sites of
the spent catalysts was determined through the temperature
programmed hydrogenation (TPH) assignment.6,7 The spent
catalyst is treated in the hydrogen stream and the coke deposited
is converted into methane. The TCD detector analyzes the amount
of methane produced from the TPH process and the amount of
deposited carbon is calculated.
2.3. Reactor apparatus and activity-testing procedure
The catalytic reaction was carried out under atmospheric
pressure using a fixed-bed quartz reactor with an inner diameter
of 1.2 cm.7,21 The flow rate of the gases was controlled by the
electronic mass flow-meter (Brooks 5850). The calcined catalyst
(0.1 g) was located in the reactor and reduced by diluted hydrogen
(4% volume ratio of H2/N2) with a gas hourly space velocity (GHSV)
of 6 L h 1 gcata 1 at 1223 K for 12 h, before reaction. The catalytic
activity was studied at 823–1073 K temperature range, with
GHSV = 18 L h 1 gcata 1 at atmospheric pressure. The feed
consisted of CO2 (499.99%), and CH4 (499.99%) with a molar
ratio CH4/CO2 = 1.
The analysis of the reactant/product mixtures was per-
formed by using a gas chromatograph equipped with two
sequence connected packed columns, Propack Q and Molecular
Sieve 5A accompanied by argon as a carrier gas.
3. Results and discussion
3.1. Specific surface area
The specific surface area, pore volume and mean pore diameter
of the prepared catalysts are given in Table 1. As expected for
the perovskite structures, these results indicated that the sur-
face area of the catalysts was significantly low. As shown in
Table 1, by substituting nickel by cobalt in the LaNi0.5Co0.5O3
catalyst, the surface area was decreased. In addition, the
perovskite samples prepared with magnetized water have a
lower surface area. As shown in Table 1, the total pore volume
and the average pore diameter are reduced in samples prepared
using magnetized treatment water.
3.2. X-ray diffraction studies
The XRD patterns of the fresh catalysts after calcination and
reduced catalysts are shown in Fig. 1. As shown in Fig. 1 for
the fresh catalysts, peaks due to the perovskite phases are
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Table 1 Textural properties of the prepared catalysts

Crystallite sizeb (nm)

BET surface Pore volumea Mean pore Metal oxide
Catalyst area (m2 g 1) (cm3 g 1) diametera (nm) reduction (%) Ni Co
LaNiO3 non 4.9 0.021 19.3 78.3 22 —
LaNiO3 treat 4.4 0.016 17.4 76.6 18 —
LaNi0.5Co0.5O3 non 3.8 0.014 14.6 87.2 24 22
LaNi0.5Co0.5O3 treat 3.2 0.011 12.8 85.6 21 20
a b
These values were calculated by the BJH method from the adsorption isotherm. These values were calculated using Scherrer’s equation from
XRD results.
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dominant in the XRD patterns of the catalysts. Fig. 1(a and b)
represents the XRD patterns of the LaNiO3 sample prepared by
non-treatment and magnetized water, respectively. As shown in
these patterns, the diffraction peaks at 23.21, 32.81, 47.31, and
58.41 are characteristic of the rhombohedral (R3% m) structure of
the LaNiO3 perovskite (JCPDS 33-0711) as the main phase of our
prepared samples by non-treatment and magnetized water.20
The additional peaks at 26.71 and 31.21 are related to cubic
La2O3 (JCPDS-220369) and at 43.21 and 37.31 are related to the
NiO cubic phase (JCPDS-780643), which confirms that the NiO
and La2O3 phases exist in addition to the main LaNiO3 phase.20
The presence of the NiO and La2O3 phases was related to the
segregation of small nickel oxide to the surface of the LaNiO3
perovskite.
The XRD results show that the presence of the NiO and La2O3
phases in the fresh sample prepared by the magnetized water is
less than in the non-treatment sample. Thus, co-precipitation of
the samples in magnetized water prepared more pure LaNiO3
perovskite, due to the lower surface tension and higher viscosity of
the magnetized water.35 Our previous results show that the
magnetized water reduces the growth rate of the particles while
increases the rate of nucleation in the precipitation process.34
Fig. 1(c and d) represents the XRD patterns of the LaNi0.5Co0.5O3
samples prepared by non-treatment and magnetized water,

Fig. 1 XRD patterns of the fresh and reduced catalysts. (a) LaNiO3 non-treatment, (b) LaNiO3 treatment, (c) LaNiCoO3 non-treatment, (d) LaNiCoO3
treatment.

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respectively. As shown in Fig. 1(c), for the LaNi0.5Co0.5O3 fresh
sample prepared by non-treatment water, the diffraction peak
at 331 can be observed to be dual, compared with what it is for
LaNiO3, which is related to the formation of the separate phase
of LaNi0.5Co0.5O3 and LaCoO3.37 In addition, the position of the
reference peak for LaNiO3 (2y = 32.81) shifts with the addition of
Co content (Fig. 1) suggesting the formation of LaNi0.5Co0.5O3 solid
solution.26 These separated peaks decreased in the XRD pattern
of the LaNi0.5Co0.5O3 perovskite fresh sample prepared by
magnetized water in Fig. 1(d), which indicates a higher purity
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of the LaNi0.5Co0.5O3 perovskite phase in this sample. However,
the partial substitution of the Ni3+ (r = 60 pm) by Co3+ (r = 61 pm),
in the LaNi0.5Co0.5O3 system, increases the B–O distance in the
perovskite-type structure and produced an increase in the
rhombohedral cell parameter from 5.457 Å for LaNiO3 to
5.462 Å in the LaNi0.5Co0.5O3 perovskite prepared by non-
treatment and 5.466 Å in the LaNi0.5Co0.5O3 perovskite
prepared by magnetized water.17,26,38 Higher increase in the
rhombohedral cell parameter for the magnetized prepared sample
is related to the greater presence of Co in the LaNi0.5Co0.5O3
perovskite structure. Thus, co-precipitation of the samples in the
magnetized water prepared purer LaNi0.5Co0.5O3 perovskite, due to
lower surface tension and higher viscosity of the magnetized
water.35
As shown in Fig. 1, after reduction at 900 K for 1 h, the
typical peaks attributed to the LaNiO3 and LaNiCoO3 perovs-
kites disappeared, while the characteristic diffraction peaks
related to La2O3 (2y = 29.1, 30.1, 39.5, 46.4, and 55.71), metallic
Fig. 2 The SEM images of the prepared catalysts. (a) LaNiO3 non-treatment, (b) LaNiO3 treatment, (c) LaNiCoO3 non-treatment, (d) LaNiCoO3
treatment.
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Ni0 (2y = 45.1, 53.1, and 77.11) and metallic Co0 (2y = 42.1, and 47.91)
appeared. These results show that LaNiO3 and LaNi0.5Co0.5O3
perovskites collapsed after the reduction, forming metallic Ni0
and Co0 nanoparticles dispersed on the La2O3 support.39–41 The
crystallite size of the metallic Co and Ni was also determined by
applying Scherrer’s equation using the peak located at 45.11 for
Ni and 47.91 for cobalt in the reduced samples and presented in
Table 1.3,42,43 These results show that the metallic particle size is
reduced in the treatment catalysts.
3.3. SEM and TEM results
The surface morphologies and homogeneity of the prepared
catalysts were analyzed by the SEM images in Fig. 2. As shown
in Fig. 2, all the calcined catalyst particles are in the form of
pseudo-spherical particles with aggregates of smaller nano-
particles. In addition, some voids were formed during the
calcination due to the decomposition of nitrate in starting salts
of the catalysts. By substitution of nickel by cobalt, the macro-
porosity increased and the morphology of the prepared per-
ovskites is changed due to the formation of solids with more
defects. However, as shown in Fig. 2b, the samples prepared by
magnetized water show higher voids and macro-porosity in the
surface decoration of the prepared samples.
The TEM photographs for the fresh and reduced samples in the
non-treatment and magnetized water are demonstrated in Fig. 3. It
can be found that the nanoparticles in the LaNiO3 perovskite
prepared by non-treatment water have pseudo-spherical shapes,
with the average particle size of the nanoparticles about 51 nm.

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Fig. 3 The TEM images of fresh (A) and reduced catalysts (B) and metal particle size distribution for the reduced catalysts. (a) LaNiO3 non-treatment,
(b) LaNiO3 treatment, (c) LaNiCoO3 non-treatment, (d) LaNiCoO3 treatment.
As shown in Fig. 3b, the average particle size of the catalyst
prepared by magnetized water is lower and about 42 nm. More-
over, a weak agglomeration is observed for both catalysts. In
Fig. 3c, it can be observed that the presence of cobalt into the
perovskite structure, increases the catalyst particle size. Fig. 3
shows the formation of the metallic Ni0 and Co0 nanoparticles
after the reduction of the LaNiO3 and LaNi0.5Co0.5O3 perovskites at
900 K for 1 h. In addition, the particle size distributions of the
metal nanoparticles are shown in Fig. 3. The TEM image and
calculated particle size distribution of the reduced LaNiO3
perovskite showed that smaller and more uniform metallic
Ni0 nanoparticles dispersed on the La2O3 support for treatment
catalysts were obtained.39–41 It was found that the metallic
particle size becomes larger after the cobalt substitution and
as shown in Table 1, the TEM results are in good agreement
with the XRD results.28,29
3.4. Temperature-programmed reduction (TPR) of the
samples
The reduction behavior of the perovskites prepared by non-
treatment and magnetized water was investigated, and the
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results are presented in Fig. 4. Fig. 4(a and b) represent
the TPR profiles of the LaNiO3 sample prepared by the non-
treatment and magnetized water, respectively. The LaNiO3
sample prepared by the non-treatment water exhibited three
main reduction peaks at 583 K, 653 K and 813 K (Fig. 4a).
However, the sample prepared by the magnetized water shows
two main reduction peaks at 663 K and 798 K (Fig. 4b). The low-
temperature reduction peak located at 583 K for the first
sample, which is overlapping with the higher peak is related
to the NiO species located on the LaNiO3 perovskite, which are
weakly interacting with the surface.44 This reduction peak is
not seen in the TPR profile of the LaNiO3 perovskite prepared
by magnetized water, because often the NiO species are appear-
ing in the perovskite structure, based on the XRD results.
The second peak in the TPR profile of the LaNiO3 perovskite
prepared by non-treatment water (Fig. 4a), or the first peak in
the TPR profile of the LaNiO3 perovskite prepared by magnetized
water (Fig. 4b) indicates the reduction of the Ni3+ to Ni2+ with
attendant formation of La2Ni2O5 as follows:20,45
2LaNiO3 + H2 - La2Ni2O5 + H2O (1)
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samples due to the presence of Co in the B positions of the LaNiO3

perovskite. As discussed in the XRD section, the presence of Co
in the B positions increased the cell parameter, which promotes
the mobility of lattice oxygen to the surface and its removal by
the reducing gas.38 Further presence of Co in the B site of the
LaNi0.5Co0.5O3 perovskite structure for the sample prepared by
magnetized water causes the reduction process to start at lower
temperatures than others. In the cases of the LaNi0.5Co0.5O3
perovskite structure, the sample prepared by non-treatment
water had a relatively higher intensity in the first peak com-
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pared with LaNiO3, due to the larger amount of hydrogen

consumption at the first peak caused by the segregated NiO
phase. As shown in Table 1, the metal oxide reduction (%) of
the LaNi0.5Co0.5O3 perovskites is higher than that of the LaNiO3
perovskites. In addition, the LaNi0.5Co0.5O3 perovskite prepared by
non-treatment water shows higher metal oxide reduction (%) than
the LaNi0.5Co0.5O3 perovskite prepared by magnetized water.

3.5. Catalytic activity

The catalytic activity results of the prepared catalysts were
Fig. 4 The reduction behavior of the perovskites prepared by non-
treatment and magnetized water. (a) LaNiO3 non-treatment, (b) LaNiO3 carried out by increasing the reaction temperature from 823
treatment, (c) LaNiCoO3 non-treatment, (d) LaNiCoO3 treatment. to 1073 K as shown in Fig. 5.

While the high-temperature peak is associated with the reduction

of the Ni2+ ions in the reduced phase to Ni0 and La2O3, as
follows:16,45

La2Ni2O5 + 2H2- La2O3 + 2Ni + 2H2O (2)

Based on the stoichiometric consumption of hydrogen in

reactions (1) and (2), if LaNiO3 is the only phase present in
the sample prepared by non-treatment water, the ratio of the
second to the first reduction peak should be equal to 2.
However, our results show that this ratio is equal to 1.6 for
the LaNiO3 perovskite prepared by non-treatment water and
1.9 for the LaNiO3 perovskite prepared by magnetized water, which
suggests that a small amount of a separate NiO phase is also present
in both samples. These results confirm the XRD data showing the
presence of the separated phase of NiO in the prepared LaNiO3
perovskite. The metal oxide reduction (%) is reported in Table 1. As
shown in this Table the amount of metal oxide reduction of the
LaNiO3 perovskite prepared by the non-treatment water is higher
than the LaNiO3 perovskite prepared by the magnetized water, due
to the higher free NiO phase in this catalyst.46
Fig. 4(c and d) represents the TPR profiles of the LaNi0.5Co0.5O3
perovskite prepared by the non-treatment and magnetized water,
respectively. As shown in Fig. 4, the reduction profile of the
LaNi0.5Co0.5O3 samples prepared by treatment and non-
treatment water was similar to that of the LaNiO3 precursors
although the first and second reduction peaks shifted toward
lower temperatures. Since the Co2+ reduces to Co0 at lower
temperatures than Ni2+, it is expected that the generated Co0
Fig. 5 The catalytic activity results of the prepared catalysts were carried
crystallites favor the reducibility of the nickel cations via out by increasing the reaction temperature from 823 to 1073 K; (~) LaNiO3
spillover of the H-atoms from the Co crystallites.20 In addition, non-treatment, (’) LaNiO3 treatment, (m) LaNiCoO3 non-treatment, (K)
lower temperatures of the reduction process for the LaNi0.5Co0.5O3 LaNiCoO3 treatment.

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As shown in Fig. 5, the catalytic activities increased with
increasing reaction temperature which can be expected for the
endothermic dry reforming reaction of methane (DRM).
CH4 + CO2 2 2CO + 2H2 DH0298K = 247 kJ mol
As shown in Fig. 5, CH4 conversion is lower than CO2
conversion for all catalysts, due to the presence of side reac-
tions such as reverse water-gas shift (RWGS) reaction (4), which
is favored at high temperature.
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reduction and thus the nickel dispersion on those supports can
be significantly improved. The more uniform activity of the
catalysts prepared by treatment water can be related to higher
concentrations of perovskite in the precursors of the catalysts
1
(3) before reduction.
Fig. 6 shows the temperature-dependent H2/CO ratio and
Table 2 lists the hydrogen, CO and water production rates
for the treatment and non-treatment catalysts. The water
production indicated that the RWGS reaction occurs in parallel
with the DRM reaction in our reaction conditions.

CO2 + H2 2 CO + 2H2O DH0298K = 41 kJ mol 1

(4)
As shown in Fig. 5, the catalytic activity of LaNi0.5Co0.5O3 is
lower than that of the active LaNiO3, indicating that the
interaction between the metallic species Ni0–Co0 reduced the
DRM activity of the catalyst. The lesser activity of cobalt
than nickel in the DRM reaction reduced the DRM activity of
the LaNi0.5Co0.5O3 perovskite, in which the nickel atoms are
replaced by cobalt in the structure of the catalyst.10,26,28
As shown in Fig. 5, the initial activities for the catalysts
prepared by non-treatment water are higher than the others.
It is accepted that the perovskite precursors present high
metallic dispersion when they undergo in situ reductions. The
XRD results indicate that the presence of free nickel phase in
the non-treatment samples is simply reduced and provides
more initial activity for the catalysts prepared by non-treatment
water, which is shown in Fig. 5. It has been proved that the LaNiO3
type perovskite precursors converted to La2O3 support after
Commonly, the H2/CO ratio is somewhat lower than the
stoichiometric value (unit), due to the presence of RWGS
(eqn (4)) and reverse Boudouard reaction (eqn (5)).
CO2 + C(s) 2 2CO DH0298K = 171 kJ mol 1
(5)
Due to the presence of these side reactions along with the main
DRM reaction, additional carbon monoxide is produced and
causes the H2/CO ratio to be less than 1. As shown in Fig. 6, a
lower H2/CO ratio is produced from the cobalt substituted
perovskite. It is proven that on the surface of the reduced
catalysts, CO2 dissociation occurs on the surface of the La2O3
supports. Interaction of the La2O3 supports with CO2 can result
in the formation of the La2O2CO3 species as follows (eqn (6)),
which facilitates the reverse Boudouard reaction (eqn (5)).
La2O2CO3 + C–Ni - La2O3 + 2CO + Ni (6)
It has been confirmed that the addition of Co to the LaNiO3
catalyst facilitated the La2O2CO3 formation during the DRM
reaction. Lower H2/CO ratio for the LaNi0.5Co0.5O3 catalysts can
be related to this ability of Co-promoter.

3.6. Deactivation studies of the catalysts

Catalyst deactivation is a major concern in the development of
nickel-based catalysts for the dry reforming reaction that occurs
due to carbon deposition on the surface of the catalyst and
sintering of the catalyst active sites.15,47,48 The most possible
reaction at high temperatures leading to the carbon deposition
is methane decomposition (eqn (7)) which is an endothermic
reaction.

CH4 - 2H2 + C(s) DH0298K = 17.9 kJ mol 1

(7)

In addition, the carbon deposition on the surface of the

Fig. 6 The temperature-dependent H2/CO ratio results of the prepared catalysts in the DRM reaction may be done by the Boudouard
catalysts were carried out by increasing the reaction temperature from 823 reaction (eqn (8)).
to 1073 K; (~) LaNiO3 non-treatment, (’) LaNiO3 treatment, (m) LaNiCoO3
non-treatment, (K) LaNiCoO3 treatment. 2CO 2 CO2 + C(s) DH0298K = 171 kJ mol 1
(8)

Table 2 Production rates of hydrogen, carbon monoxide, water, and carbon deposition on the spent catalysts at 1023 K after 24 h TOS
1
Production rate (mol gcat h 1) TPH results
1
Catalyst H2 CO H2O CH4 formation (mmole CH4) Total carbon (mg gcat h 1)
LaNiO3 non 0.956 1.040 0.042 47.5 23.7
LaNiO3 treat 0.936 1.015 0.039 38.2 19.1
LaNi0.5Co0.5O3 non 0.831 0.949 0.059 36.4 18.2
LaNi0.5Co0.5O3 treat 0.790 0.902 0.056 30.4 15.2

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Fig. 7 The methane and CO2 conversions as a function of time on stream
(TOS) obtained for the DRM reaction at 1023 K over prepared catalysts; (~)
LaNiO3 non-treatment, (’) LaNiO3 treatment, (m) LaNiCoO3 non-treatment,
(K) LaNiCoO3 treatment.
In order to consider the durable stability of the perovskite
catalysts for the DRM reaction, the reaction was carried out at
1023 K for 24 h under CH4/CO2 = 1.0. The methane and CO2
conversions as a function of time on stream (TOS) obtained for
the DRM reaction at 1023 K over the prepared catalysts are
shown in Fig. 7.
The kind and the amount of the deposited coke on the spent
catalysts were determined by the TPH method.49–51 In this
method, the deposited coke was quantified from the CH4
formed during its combustion and classified according to the
combustion temperature. The amount of coke deposited on
the spent catalysts is listed in Table 2 and TPH profiles of the
spent catalysts are shown in Fig. 8. In TPH profiles of the spent
catalysts, the peak around 800 K can be endorsed to amorphous
carbon species on the nickel atoms, and the strong peak
around 1050 K may be attributed to the inert graphitic
carbon.52,53 It seems that the type of carbon deposited on the
catalysts, regardless of the method of catalyst preparation and
the presence of cobalt, is the same for all of them and the
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Fig. 8 TPH profiles of the spent catalysts; (a) LaNiO3 non-treatment, (b)
LaNiO3 treatment, (c) LaNiCoO3 non-treatment, (d) LaNiCoO3 treatment.
existence of the inert graphitic carbon was responsible for the
deactivation of the catalysts. However, as shown in Table 2, the
amount of carbon deposited over the surface of the spent
catalysts increased as the following sequence: LaNiO3 non 4
LaNiO3 treat 4 LaNiCoO3 non 4 LaNiCoO3 treat.
Raman spectroscopy is particularly well suited to the mole-
cular morphology characterization of carbon materials. The
Raman spectra of the used catalysts (Fig. 9) show two bands
that are related to the D and G vibration modes of the carbon
materials. The D band is associated with the disorder-induced
scattering from sp2 carbons and the band G is related to the
scattering from the inplane bond-stretching motion of pairs of
C sp2 atoms.54 The position and line width of the D band are
changed with the allotropic forms of carbon.44 As shown in
Fig. 9, the D band located at about 1350 cm 1 with a line
width from 40 to 80 cm 1 and a G band located at 1580 and
1600 cm 1 suggests the presence of graphite and multi-walled
carbon nanotubes (MWNTs). The intensities of these bands
decreased in the following order: LaNiO3 non 4 LaNiO3 treat 4
LaNiCoO3 non 4 LaNiCoO3 treat, which represents decreasing of
the deposited carbon on the spent catalysts and confirms
previous TPH results.
For the catalysts derived from the magnetized water treat-
ment, more constant conversions were observed during the
TOS of the reaction, due to a higher phase of the perovskite-
type structure and less amorphous NiO phases. Two major
reasons for its more uniform activity of the treatment prepared

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Fig. 9 Raman spectra of the spent catalysts; (a) LaNiO3 non-treatment, (b)
LaNiO3 treatment, (c) LaNiCoO3 non-treatment, (d) LaNiCoO3 treatment.
catalysts can be considered, uniform La2O3 support and Ni
particle size. The La2O3 phase is prepared after the reduction
and a mono-disperse nickel phase is prepared on the surface
of the La2O3 phase (TEM results). On the exterior of the
reduced Ni/La2O3 catalyst, methane dissociation happens on
the nickel nanoparticles, whereas carbon dioxide dissociation
occurs on the surface of La2O3 as a basic support. Interaction
of the La2O3 supports with carbon dioxide can create the
La2O2CO3 species that oxidize carbon deposits on the neigh-
boring nickel atoms and produce CO and regenerate active
species (eqn (6)).
It has been confirmed that the size of the nickel
particle plays a key role in its resistance towards carbon
deposition. Aramouni et al. studied the effect of nickel size
on carbon formation during DRM by thermodynamic analysis
and found that the formation of carbon on larger metal
particles is more desirable. The free nickel oxides produced
larger particles and nickel atoms in the perovskite structure
produce smaller and more uniforms Ni0 particles, after the
catalyst reduction. Higher carbon deposition and catalyst
deactivation in the non-treatment prepared catalysts can be
related to higher free nickel oxide in these catalysts. In
addition, the activation of catalysts occurs during the DRM
reaction in situ, because of a reducing atmosphere formed by
the reaction gases (CH4, CO, H2) that promotes the formation
of the reduced nickel species over the La2O3 support. But rapid
coke formation on the free nickel phase protects them from
this in situ reduction atmosphere in the non-treatment
catalysts.
Recently, it has been verified that the accumulation of Co on
the LaNiO3 catalyst facilitated the La2O2CO3 formation during
the DRM reaction, which resulted in lower carbon deposition
over the surface of the LaNiCoO3 catalysts and more uniform
activity during the DRM reaction.
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4. Conclusion
The LaNiO3 and LaNi0.5Co0.5O3 nanoparticles were prepared
through the co-precipitation method by using distilled and
magnetized distilled water. The XRD analysis clarified that
the partial Ni2+ substitution by Co cations enhanced the
rhombohedral cell parameter in the non-treated LaNi0.5Co0.5O3
perovskite. Besides, the parameter in the treated LaNi0.5Co0.5O3
is more than that of the non-treated ones. TPR analysis indicated
that although the first and second reduction peaks shifted toward
low temperatures, the reduction profiles of the treated and
non-treated LaNi0.5Co0.5O3 samples are similar to those of
the LaNiO3 precursors. The catalytic activity of the prepared
catalysts enhanced with increasing temperature. The CH4 con-
version is less than the CO2 conversion for all catalysts, due to
the presence of some side reactions such as the reverse water-
gas shift reaction. The partial substitution of the B-site cation
in the perovskite induced a decrease in the catalytic activity.
However, the initial activities for the non-treated catalysts are
higher than the others. The TPH results proved that the type of
deposited carbon on the catalysts is the same for all of them,
regardless of the preparation method of the catalyst and the
presence of CO2+. The trend for the amount of the deposited
carbon over the surface of the spent catalysts was as follows:
LaNiO3 (none) 4 LaNiO3 (treat) 4 LaNiCoO3 (none) 4 LaNi-
CoO3 (treat).
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors of this work appreciate the financial support from
the Ferdowsi University of Mashhad, Iran (Grant No. 3/39109).
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