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The tendency of supports to generate oxygen

Cite this: DOI: 10.1039/d1cy01915e
vacancies and the catalytic performance of Ni/
ZrO2 and Ni/Mg(Al)O in CO2 methanation†
O. E. Everett Espino,ab P. C. Zonetti,b R. R. Celin,c L. T. Costa, c
O. C. Alves, c

J. C. Spadotto,a L. G. Appel b and R. R. de Avillez *a

Received 21st October 2021,
Accepted 3rd January 2022
DOI: 10.1039/d1cy01915e
rsc.li/catalysis
Ni/ZrO2, Ni/Mg(Al)O, and Ni/SiO2 catalysts were employed in CO2 methanation. The catalysts were
characterized by XPS, XRF, XRD (Rietveld refinement method), TPR, EPR, BET, CO2 + H2-TPSR, CO + H2-
TPSR, CO2-TPD, CO-TPD, S/TEM-XEDS, and DFT calculations. The catalytic performance of these catalysts
in CO2 methanation was analyzed employing a conventional microreactor. CO2 consumption and
formation rates of the products were obtained under differential conditions. The Ni/ZrO2 catalyst exhibited
the highest activity and selectivity for the methanation of CO2 compared to Ni/Mg(Al)O and Ni/SiO2. The
Mg-based catalyst reaches the Ni/ZrO2 performance at high temperatures. Some authors have proposed
that CO rupture or formate decomposition (the rate-limiting step of CO2 methanation) occurs on pairs of
oxygen vacancy–cus sites. DFT calculations showed that oxygen vacancies improve CO adsorption and
dissociation over the Ni/ZrO2 catalyst. For Ni/ZrO2, the vacancies are generated by the insertion of Ni in
the ZrO2 lattice (DRX) and by the defects of ZrO2 oxide (EPR), whereas Mg(Al)O shows intrinsic vacancies
(EPR). Ni/ZrO2 exhibits the same metallic area compared with Ni/Mg(Al)O. However, the former is more
active and selective than Ni/Mg(Al)O at a large temperature range, showing that H2 dissociation is not the
rate-limiting step. Indeed, the Zr-based catalyst generates H2O or eliminates oxygen, generating vacancies
at much lower temperatures than Ni/Mg(Al)O (CO2 + H2-TPSR and CO + H2-TPSR). However, at higher
temperatures (>400 °C), the catalytic behavior of these two catalysts is similar. Indeed, the elimination of
H2O and oxygen vacancy formation are easier for both catalysts under these conditions. Thus, this work
shows that the catalytic performance of Ni-based catalysts is associated with the support's facility to
release O (reducibility).

1. Introduction energies. Thus, storage is mandatory always to deliver energy

Currently, it is widely accepted that climate changes generated
by the greenhouse effect have damaged the flora, fauna, and
humankind. In this context, the increase in CO2 concentration
in the atmosphere is associated with global warming. Since the
contribution of fossil fuels to this phenomenon is very relevant,
considerable efforts have been made to replace these fuels with
renewable ones. Nowadays, the most promising ones, i.e., wind
and solar energies, are already used worldwide. However,
intermittence is one of the most critical features of these
a
Departamento de Engenharia Química e de Materiais, Pontifícia Universidade
Católica do Rio de Janeiro, Rua Marquês de São Vicente, 225, Gávea, 22451-900,
Rio de Janeiro, RJ, Brazil. E-mail: avillez@puc-rio.br
b
Divisão de Catálise, Biocatálise e Processos Químicos, Instituto Nacional de Tecnologia,
Av Venezuela 82, sala 518, Praça Mauá, 20081-312, Rio de Janeiro, RJ, Brazil
c improving the methanation catalyst performance are essential
Instituto de Química, Universidade Federal Fluminense, Campos de Valonginho s/n,
Centro, 24020-141, Niterói, RJ, Brazil
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
d1cy01915e
when there is demand. Among the many technologies
proposed for energy storage, “power-to-gas” (PtG) stands out.
Briefly, PtG can be described as follows. H2 is produced by H2O
electrolysis employing the energy surplus when the energy
demand is lower than the generation. Then, synthetic natural
gas (SNG) can be generated from the stored CO2 and H2.
Methane is widely used as fuel, especially in the domestic
heating, transport, and industrial sectors. According to
Ducamp et al.,1 the PtG technology enables the possible
interconnection of electrical and gas networks, bringing energy
management benefits. Nowadays, the SNG production cost is
higher than that of natural gas (NG), according to Guilera
et al.'s2 cost analysis of SNG production in a PtG facility. Their
data showed that the methanation process capital expenditure
(CAPEX) is relevant for SNG feasibility. Therefore, studies on
to the PtG technology deployment.
Many metals like Ru, Mn, Rh, Fe, Ni, and Co are employed in
CO2 methanation. Due to its low cost and good reactivity, nickel

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is the most used and studied. Many supports are proposed for
this reaction, for example, Al2O3, CeO2, La2O3, MgO, MgAlO,
SiO2, ZrO2, zeolites, TiO2, and CeO2–ZrO2.3 Our group's previous
work has shown that Ni supported on monoclinic ZrO2 is a very
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promising catalyst for CO and CO2 methanation.4
Nowadays, the key role of the O vacancies in CO2
methanation has different understandings. It was proposed
that the metal–support interaction in the presence of O
vacancies increases the CO2 and CO methanation rates.5,6
Taking into account that the reaction occurs on the support,
it was suggested that the oxygen vacancies enhance the CO2
adsorption7–11 by CO generation and O deposition on the O
vacancies or by carbonate generation. Alternatively, the O
vacancies are associated with CO dissociation or formate
decomposition to methoxy species, both suggested as the
rate-limiting step of the methanation reaction. The CO2
methanation mechanisms employing vacancy–cus pairs12 are
described in detail in the Results and discussion section.
Indeed, new catalyst preparation procedures have been
employed to promote the generation of O vacancies and the
catalytic behavior and also to better describe the role of these
defects in CO2 methanation.13–16
Using Ni/ZrO2 doped with Ca, our group observed that
both mechanism suggestions, via CO or formates, seem to be
acceptable. After doping ZrO2 with Ca, the amount of CO2
adsorbed increased. Moreover, Ca generates extrinsic O
vacancies on ZrO2. Therefore, more O vacancy–cus pairs were
created, increasing the number of sites for CO dissociation or
formate decomposition to methoxide. Thus, the activity of
the catalyst increases.16
It is worth noting that O vacancies should be recovered to
close the catalytic cycle. In other words, O should be removed
from the crystal defects. This subject is rarely discussed in
the literature. Nonetheless, Rodríguez et al.17 observed that
adding Pr to CeO2 increases the rate of vacancy recovery.
Ni supported on Mg(Al)O has been proposed as a catalyst
for CO2 methanation by many authors. Mg(Al)O is a mixed
oxide derived from hydrotalcite-like precursors. This catalyst
shows a large metallic and surface area, excellent stability,18
and high activity and selectivity at high temperatures.
However, it exhibits a poor performance at low
temperatures.19 The addition of La, Ce, Zr, Co, Fe, and V as
promoters to Ni/Mg(Al)O improves its catalytic behavior at
low temperatures.19–22 According to some authors, the
promoters increase the catalyst's reducibility.20 Rodrigues
et al.,23 studying the reverse water gas shift (RWGS) reaction
employing electron paramagnetic resonance (EPR), observed
the presence of oxygen vacancies in the Ni/Mg(Al)O catalyst.
However, the literature does not associate the tendency to
generate oxygen vacancies with the catalytic behavior of Ni/
Mg(Al)O in CO2 methanation.
This work aims to improve the knowledge related to the
role of the oxygen vacancies in CO2 methanation, specifically
to describe the correlation between catalyst support
reducibility and the O vacancy recovery step of this reaction.
Hence, the catalysts Ni/ZrO2 and Ni/Mg(Al)O are compared
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concerning their catalytic behavior and physicochemical
properties. The Ni/SiO2 catalyst is employed as a reference.
This work generates additional information associated with
CO2 methanation by using DFT calculations.
2. Experimental procedures
2.1 Preparation of the catalyst
The catalysts Ni/ZrO2, Ni/SiO2, and Ni/Mg(Al)O were
synthesized by a wet impregnation method using
Ni(NO3)2·6H2O as a precursor. Norpro Saint Gobain supplied
ZrO2 (monoclinic) and SiO2 (amorphous) and SASOL the
Mg(Al)O mixed oxide (MgO : Al2O3 = 70 : 30%). The Ni
concentrations for Ni/ZrO2, Ni/SiO2, and Ni/Mg(Al)O catalysts
were 5 wt%, 10 wt%, and 5 wt%, respectively. After the
impregnation, the solids were dried overnight and calcined
at 500 °C for 5 h in an air flow (20 mL min−1).
2.2 Catalyst passivation procedure
Firstly, the catalysts were treated at 500 °C for 30 min under
a N2 flow (30 mL min−1). Afterward, the Ni/ZrO2 and Ni/SiO2
catalysts were reduced at 500 °C for 30 min under a pure H2
flow (30 mL min−1), whereas Ni/Mg(Al)O was treated at 700
°C for 30 min under a N2 flow (30 mL min−1) and reduced at
700 °C for 60 min under a pure H2 flow (30 mL min−1). After
the reduction step, the catalysts were cooled to room
temperature under a N2 flow. The passivation procedure was
carried out around −60 °C using a cryogenic cooling bath
under a 4% O2/N2 flow (30 mL min−1) for 1 h. Finally, the
solids remained at room temperature for 1 h under a 4% O2/
N2 flow.23
2.3 Characterization of the catalysts
The specific surface area of the catalysts and supports was
evaluated with N2 physisorption and the Brunauer–Emmett–
Teller (BET) method using a Micromeritics ASAP 2010
analyzer. The samples were oven-dried at 100 °C for 24 h.
The solids were positioned inside the apparatus and heated
under vacuum at 350 °C for 2 h. N2 adsorption was carried
out at −196 °C.
The chemical composition analyses were carried out using
a Bruker S8 Tiger wavelength dispersive X-ray fluorescence
spectrometer (WDXRF) equipped with a rhodium tube
operated at 30–60 kW. A semi-quantitative method (QUANT-
EXPRESS/Bruker) determined the metal content incorporated
into the prepared catalysts.
CO2 temperature-programmed desorption (CO2-TPD)
experiments employed a microreactor coupled to a Dycor
mass spectrometer (Ametek Process Instruments). The Ni/
ZrO2 and Ni/SiO2 catalysts (500 mg) were treated at 500 °C (5
°C min−1) for 30 min under a He (30 mL min−1) flow before
being reduced with 10% H2/N2 (30 mL min−1) for 30 min. Ni/
Mg(Al)O was treated at 700 °C (5 °C min−1) for 30 min under
a He (30 mL min−1) flow and reduced at the same
temperature under 10% H2/N2 (30 mL min−1) for 60 min.
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After the reduction, all samples were cooled under a He flow
(30 mL min−1) until they reached room temperature. Then,
the samples were exposed to CO2 (30 mL min−1) for 1 h at
room temperature. Next, CO2-TPD measurements were
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carried out by heating the samples at 10 °C min−1 up to 500
°C under a He flow (80 mL min−1). The fragment m/z = 44
(CO2) was continuously monitored during the analysis. In
order to classify basic sites according to their strength (weak,
medium, and strong), the TPD profiles were deconvoluted in
Gaussian curves. The weak basic sites are assigned to a curve
that exhibits a maximum at a temperature lower than 127 °C,
medium basic sites between 127 °C and 307 °C, and strong
basic sites above 307 °C.
Temperature-programmed surface reaction of CO2 and H2
(CO2 + H2-TPSR) and CO + H2 methanation (CO + H2-TPSR)
experiments employed a microreactor coupled to a Dycor
mass spectrometer (Ametek Process Instruments). The
samples (500 mg) were pretreated using the same procedure
described in the methodology of the CO2-TPD. They were
then exposed to CO2 (20 mL min−1) or CO (20 mL min−1) for
30 min at room temperature. After that, the TPSR
measurements were carried out by heating the samples up to
500 °C (10 °C min−1) under a pure H2 flow (20 mL min−1).
The fragments m/z = 15, m/z = 28, m/z = 44, and m/z = 18,
assigned to CH4, CO, CO2, and H2O, respectively, were
continuously monitored.
The temperature-programmed reduction (TPR) analyses
were performed using Micromeritics AutoChem II
equipment. Firstly, the Ni/ZrO2 and Ni/SiO2 catalysts were
dried at 500 °C under a N2 flow (30 mL min−1) for 30 min.
After that, they were reduced at 500 °C for 30 min with a
10% H2/N2 flow and purged for 15 min under a N2 flow.
Then, they were calcined at 500 °C for 30 min under a
synthetic air flow (30 mL min−1), and the samples were
cooled under a N2 flow (30 mL min−1) until they reached
room temperature. The same process was applied to Ni/
Mg(Al)O, except for the reduction conditions of 700 °C for 1
h. The analysis was conducted under a 10% H2/N2 mixture
(50 mL min−1) from 30 to 900 °C (10 °C min−1). The ZrO2
oxide shows strong basic sites which react with CO2 of the
air, generating carbonate species which can be reduced
during the TPR procedure, consuming H2 and changing the
TPR profiles. Thus, the TPR pretreatment comprises two
steps, reduction and reoxidation of the samples.
The CO temperature-programmed desorption (CO-TPD)
analyses employed a microreactor coupled to a QMG 220
Prisma Plus mass spectrometer from Pfeiffer Vacuum GmbH.
The ZrO2 and Mg(Al)O samples (400 mg) were oxidized at 500
°C under synthetic air (30 mL min−1) for 60 min. CO
adsorption occurred at 25 °C for 30 min (60 mL min−1) under
a 3% CO/He mixture. Desorption was carried out from 25 °C
to 500 °C, at a flow rate of 80 mL min−1, maintained at 500
°C for 1 h. Fragment m/z = 44 (CO2) was continuously
monitored during desorption.
The rate of cyclohexane dehydrogenation was used as an
indirect measure of the Ni surface area.24,25 The Ni/ZrO2 and
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Ni/SiO2 samples were heated at 500 °C (5 °C min−1) for 30
min under a N2 flow rate of 30 mL min−1. Then, the
reduction step used the same temperature with pure H2 for
another 30 min. The Ni/Mg(Al)O catalyst was heated at 700
°C for 30 min under a N2 flow and reduced with pure H2 at
700 °C for 1 hour. This reaction was carried out at
atmospheric pressure using a conventional system with a
fixed-bed microreactor. It was monitored by online gas
chromatography equipped with a flame ionization detector
(FID). The cyclohexane vapors were generated in a saturator
(12 °C) using H2 as carrier gas (90 mL min−1). The H2/C6H12
ratio was 13.
The electron paramagnetic resonance (EPR) spectra of the
reduced supports of ZrO2 and Mg(Al)O were obtained using an
ESP 300 Bruker spectrometer at a frequency of 9.7 GHz. The
microwave power, field scan, and amplitude modulation were
20 mW, 0–6000 G, and 5 G, respectively. Before the analyses,
the samples (150 mg) were submitted to the following
pretreatment: firstly, the ZrO2 oxide was treated at 500 °C for
30 min under a He flow (30 mL min−1). Next, it was reduced at
500 °C for 30 min under a pure H2 flow (30 mL min−1) and then
cooled to room temperature under an Ar flow (30 mL min−1).
The same process was applied to Mg(Al)O, except for the
following conditions. It was oxidized at 700 °C under a He flow
(30 mL min−1) for 30 min and reduced at the same temperature
for 60 min under a pure H2 flow (30 mL min−1). Finally, the
reactors containing the samples with Ar were carefully sealed
and transported to the EPR equipment.
X-ray diffraction (XRD) patterns of the calcined and
reduced passivated catalysts were obtained using a D8-
Discover diffractometer equipped with a copper tube, a nickel
filter, and a Lynxeye solid-state detector with Cu Kα radiation
(λ = 0.15406 nm, tube tension 40 kV and current 40 mA). The
angular range varied from 10° to 90°, with 0.02° and 1 s per
step. Rietveld refinement technique was employed using
TOPAS software to quantitatively identify the different
crystalline phases present in the samples, their cell volumes,
lattice parameters, and site occupancies. The reduced
passivated catalysts were pretreated using the procedure
described above.
X-ray photoelectron spectroscopy (XPS) of the fresh
samples employed a Specs Phoibos-150 hemispherical
spectrometer equipped with a monochromatic source of
AlKα. The C1s photoelectron spectroscopy line at 284.6 eV
binding energy was used as a reference.
Scanning and transmission electron microscopy (S/TEM)
analyses were performed on a S/TEM JEOL JEM 2100F
microscope, under diffraction, with an X-ray energy
dispersive spectroscopy (XEDS) detector (Thermo Scientific)
and NSS 2.3 software. The Ni/Al(MgO) or NiZrO2 reduced
passivated nanoparticle samples were dissolved in
isopropyl alcohol and disaggregated for 15 min employing
ultrasound equipment; then, one drop of the solution was
placed on a copper grid with a carbon film. The reduced
passivated catalysts were pretreated using the procedure
described above.
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2.4 DFT calculations
DFT calculations were carried out using the Quantum
Espresso package26 under periodic boundary conditions.
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Projector augmented wave (PAW)27 was employed to describe
core electrons. Relaxation calculations were used to obtain
the optimized geometries with the convergence criteria for
energy and force of 2.0 × 10−5 Ry and 5.0 × 10−2 Ry/bohr,
respectively. The generalized gradient approximation (GGA)
proposed by Perdew, Burke, and Ernzerhof (PBE)28 was used
to treat the electronic exchange and correlation effects.
Grimme's semi-empirical method was used to describe the
long-range dispersion interactions.29 An energy cutoff of 30
Ry and Gaussian smearing of 0.01 Ry were used for the
monoclinic ZrO2. The Brillouin zone was sampled using a
Monkhorst–Pack 3 × 3 × 1 k-point mesh.30
The monoclinic phase shown in Fig. 1a was built from the
18190 ICSD crystallographic information files. The cell
structure has four 4-fold O and three 3-fold O atoms around
one Zr atom. The optimized lattice parameters, a = 5.17 Å, b
= 5.23 Å, c = 5.36 Å, and θ = 99.28°, are in good agreement
with the theoretical31–33 and experimental results.34 The slab-
building technique was applied to create the ZrO2 surfaces
Fig. 1 The bulk crystal structure of (a) monoclinic ZrO2, (b) the
monoclinic ZrO2 (111) surface model and (c) monoclinic ZrO−x with an
oxygen vacancy. The yellow spheres represent the oxygen vacancy.
The red spheres represent the oxygen atom, and the blue spheres
represent the zirconium atom.
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and to study the adsorption of CO. The model contains 36
atoms; there are 24 O atoms and 12 Zr atoms with three
multilayers in sequence (O–Zr–O–O–Zr–O–O–Zr–O), leaving a
10 Å wide vacuum region in the direction perpendicular to
the surface to prevent interactions between the periodic
images, as shown in Fig. 1b. One oxygen atom from the
zirconia slab was removed to account for vacancy formation
(denoted as ‘vac.’ in Fig. 1c). The oxygen vacancy formation
energy is defined as:
1
EOv ¼ Eslab‐VO þ EO2 − Eslab (1)
2
Eslab-VO is the total energy of the zirconia slab with a vacancy, EO2
is the calculated total energy for an O2 molecule, and Eslab is the
total energy of the zirconia slab without a vacancy. A negative
EOv value indicates that formation of the vacancy is favorable.
For all calculations, the atoms in the lower and middle layers
were fixed, but the atoms at the surface layers and the atomic
positions of the adsorbed CO molecule were optimized.
For the Ni atom adsorption on the ZrO2(111) surface
study, the Ni atom was firstly located 2 Å above the oxygen
atom. Then, the system was optimized, leaving the top layer
to relax together with the Ni atom, maintaining all the other
layers fixed. The binding energy (Eb) was determined as the
difference between the energy of the slab with the adsorbed
Ni atom ENi/ZrO2 and the sum of the energies of the clean
zirconium oxide EZrO2 and the Ni metal (ENi), as in eqn (2):
Eb = ENi/ZrO2 − (EZrO2 + ENi) (2)
Following similar studies,35,36 a negative adsorption
energy suggests that Ni atoms are more likely to spread
around the surface rather than aggregate. A positive
adsorption energy indicates that the Ni atoms prefer to
remain aggregated in the metal phase. The adsorption energy
for the systems was defined by:
Eads = E(CO/surface) − E(CO) − E(surface) (3)
E(CO/surface) is the total energy of the surface interacting with the
gas molecule of CO, and E(CO) and E(surface) are the energies of
the isolated gas and clean surface, respectively. Therefore, a
negative value means exothermic adsorption. The deformation
energy of the slabs can be obtained by eqn (4):
Edeform-slab = Eslab/ads − Eslab/isolated (4)
Eslab/ads and Eslab/isolated are the total energy of the optimized
and isolated slabs at the geometry after adsorption,
respectively. The adsorbate interaction energy on solid
surfaces was calculated by eqn (5):
Eint = ECO-slab − Eslab − ECO (5)
ECO-slab is the energy of a slab model of the chemisorbed CO
molecule on the surfaces; Eslab and ECO are the energies
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obtained by a single-point calculation after the final
structure. Finally, the projected density of states (PDOS) was
generated by self-consistent calculation using the pwscf
package.26 The charge transfer between the surfaces and the
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carbon dioxide molecule was achieved using Bader's analysis
software implemented by Henkelman.37,38 Charge–density
plots were prepared using the Crystalline Structures and
Densities (XCrySDen) program.39
2.5 The methanation of CO2 and CO
The treatment conditions of the catalysts before reactions are
described as follows: the Ni/ZrO2 and Ni/SiO2 catalysts were
dried at 500 °C (5 °C min−1) for 30 min under a flow of He of
30 mL min−1 and then at the same temperature they were
reduced with pure H2 at a flow rate of 30 mL min−1 for
another 30 min. The Ni/Mg(Al)O catalyst was dried at 700 °C
for 30 min under a He flow of 30 mL min−1, and it was
reduced with pure H2 (flow rate of 30 mL min−1) at 700 °C for
1 hour; all samples were cooled under He at a flow rate of 30
mL min−1 until it reached the reaction temperature.
CO2 methanation was carried out in a fixed bed reactor
monitored by an online Agilent GC-6880 gas chromatograph.
Catalytic tests were carried out using catalyst mass 200 mg,
flow rate 80 mL min−1, GHSV 4800 h−1, temperature 350 °C,
pressure 1 atm, and gas mixture composition CO2 : H2 : He =
10 : 40 : 50. Silicon carbide (800 mg) was used as a diluent to
avoid hot spots in the catalyst bed. The reactor diameter and
catalytic bed height were 22 mm and 1 cm, respectively. The
grain size was standardized by employing a strainer with an
opening of 0.053 mm (ABNT 270). The catalytic tests were
run for 14 h.
The CO and CO2 methanation rates were measured under
differential conditions (conversion <10%) at 350 °C, 1 atm.
Differential conditions were achieved employing the
following conditions (process of trial and error): Ni/ZrO2
catalyst (25 mg and 113 mL min−1), Ni/SiO2 catalyst (35 mg
and 82 mL min−1), and Ni/Mg(Al)O catalyst (27 mg and 44
mL min−1). The gas mixture molar composition was CO : He =
10 : 90 and CO2 : H2 : He = 10 : 40 : 50.
The CO2 conversion is defined by the ratio of the moles
CO2 consumed to the moles CO2 introduced in the feed. The
definition of the selectivity to one specific compound is the
ratio of the number of moles CO2 consumed to synthesize
this compound to the total number of moles CO2 consumed.
3. Results and discussion
3.1 Catalytic tests
Fig. 2 exhibits the CO2 conversion as a function of
temperature for the three prepared catalysts. The Ni/ZrO2
catalyst shows higher CO2 conversions than the Mg- and Si-
based catalysts, whereas the Ni/Mg(Al)O catalyst exhibits
almost the same conversion as Ni/SiO2 at temperatures
between 200 and 360 °C. At higher temperatures, the Ni/
Mg(Al)O shows higher conversions than Ni/SiO2, reaching the
Ni/ZrO2 catalyst conversion above 400 °C. The Mg-based
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Fig. 2 CO2 conversion versus temperature. The blue, yellow, and
black symbols represent Ni/ZrO2, Ni/Mg(Al)O, and Ni/SiO2,
respectively. The experimental conditions are as follows: catalyst mass
200 mg, H2/CO2 ratio 4 : 1, flow rate 80 mL min−1, and pressure 1 atm.
catalyst shows low activity at low temperatures. This result is
in line with the literature.19
Fig. 3 shows the selectivity of the Ni-based catalysts to
CH4 and CO at the same temperature range. The Ni/ZrO2
catalyst exhibits selectivity toward methane of around 98%
and very low to CO from 240 to 420 °C. Due to low CO2
conversions at low temperatures, selectivity to CH4 and CO of
Ni/Mg(Al)O and Ni/SiO2 are only observed above 300 °C and
270 °C, respectively. As the temperature increases, the Ni/
Mg(Al)O catalyst selectivity to CH4 increases as well, from
60% to 97%, whereas its selectivity to CO decreases. This
catalyst reaches the Ni/ZrO2 CH4 selectivity at 390 °C. As the
temperature increases, the Ni/SiO2 selectivity toward CO
decreases, and to CH4 increases. The selectivity of the Ni/SiO2
catalyst is the lowest to CH4 and the highest to CO.
The CO conversion and the selectivity of Ni/ZrO2, Ni/
Mg(Al)O, and Ni/SiO2 catalysts to CH4 at 350 °C are shown in
Fig. 4 and 5 as a function of time. The Ni/ZrO2 and Ni/Mg(Al)
O catalysts are quite stable for 14 hours on stream, but Ni/
SiO2 exhibits some deactivation (Fig. 5). This time span was
employed to generate a first observation related to the
deactivation of the catalyst during CO2 methanation.
However, this phenomenon should be studied at a higher
time on stream.
The Ni/ZrO2 catalyst exhibits the highest CO2
consumption and CH4 formation rate and the lowest CO
Fig. 3 Selectivity to CH4 (squares) and CO (triangles) versus
temperature. The catalyst colors and the experimental conditions are
the same as in Fig. 2.
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Fig. 4 Conversion versus time on stream at 350 °C. The experimental
conditions and the catalyst colors are the same as in Fig. 2.
Fig. 5 Selectivity to CO (dashed lines) and CH4 versus time on stream
at 350 °C. The experimental conditions and the catalyst colors are the
same as in Fig. 2.
formation rate (Table 1). The Ni/Mg(Al)O catalyst shows a
higher CH4 formation rate than Ni/SiO2, which seems to be
slightly more active according to the CO2 consumption rate.
These results corroborate the data presented in Fig. 2 and 3
and show that the supports' characteristics are relevant for
CO2 and CO methanation.1,40–46
3.2 Characterization of the catalysts
Table 2 shows the number of weak, medium, and strong
basic sites. As verified, Ni/ZrO2 shows the highest number of
weak, medium, and strong basic sites, whereas Ni/SiO2 is the
lowest. Fig. S1† shows the CO2-TPD spectra. Table 2 shows
that the oxide support defines the basicity of the catalyst.
This table also exhibits the specific area of the catalysts and
their Ni concentration obtained by X-ray fluorescence
analysis. The Mg-based catalyst shows the highest specific
area and the Si one the highest Ni concentration. Finally,
Table 2 displays very similar values of the cyclohexane
Table 1 CO2 consumption rate (−rCO2, mmol gcat−1 min−1), CH4 formation
rate (rCH4, mmol gcat−1 min−1), CO formation rate (rCO, mmol gcat−1 min−1)
for CO2 methanation at 350 °C
Catalyst Ni/ZrO2 Ni/Mg(Al)O
CO2 methanation
−rCO2 131 40
rCH4 122 23
rCO 9 17
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Table 2 Specific area (S, m2 g−1), chemical analysis (wt% Ni), number of
basic sites according to their strength (μmolCO2 gcat−1), and cyclohexane
consumption rate (–rC6H12, mmol gcat−1 min−1)
Ni/ZrO2 Ni/Mg(Al)O Ni/SiO2
Specific area 66 143 67
Ni 4.84 4.52 8.15
Number of weak basic sites 47 19 2
Number of medium basic sites 73 30 4
Number of strong basic sites 84 33 —
–rC6H12 3.9 3.9 3.1
dehydrogenation rates. Considering that this rate is directly
proportional to the Ni metallic area,24 it can be inferred that
the three catalysts show almost the same metallic area.
Indeed, the Ni content of the prepared catalysts was tuned to
obtain the same metallic area.
Fig. 6 shows the TPR profiles of the catalysts. The Ni/ZrO2
catalyst displays a peak at 329 °C, assigned to NiO reduction,
with two shoulders. According to Zonetti et al.,47 the shoulder
at a higher temperature can be associated with reduction of the
Ni species in the ZrO2 bulk. The Ni/Mg(Al)O catalyst exhibits a
very broad peak at 850 °C, which can be assigned to the
reduction of Ni2+ in the mixed oxide Mg(Al, Ni)O.23,48 It is well
described in the literature; Ni2+ can replace Mg2+ in the
periclase lattice.18,23,49,50 The reduction in the 250–600 °C range
might be attributed to NiO out of the mixed oxide. Only 75%
(Table S1†) of the Ni2+ in the Ni/Mg(Al)O catalyst was reduced,
whereas 93% was reduced for the Zr-based catalyst. Taking into
account the TPR profile, the pretreatment temperature
(reduction) employed in the catalytic tests of the Ni/Mg(Al)O
catalyst was 700 °C (see methodology).
Fig. 7 shows the EPR spectra of the ZrO2 and Mg(Al)O
reduced oxides. The ZrO2 spectrum shows paramagnetic
signals related to Zr3+ (g = 1.978 and 1.963), corresponding to
the coordinatively unsaturated (cus) sites. The ZrO2 and Mg(Al)
O spectra depict narrow signals at g = 2.06 and g = 2.05,
respectively, associated with ferromagnetic ordering, i.e.,
isolated vacancies.23,51,52 The EPR spectra were deconvoluted
employing Lorentz curves. It was inferred that the vacancy
concentration of the ZrO2 oxide is 1.6 times that of the Mg(Al)O
mixed oxide. Five equally spaced lines at the g = 2.00 region of
the Mg(Al)O EPR spectrum are probably due to Mn2+, which
may be a Mg(Al)O impurity. The Ni catalysts reduced were not
Ni/SiO2
62
14
48 Fig. 6 TPR profiles of the oxidized catalysts.
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Fig. S3† displays the XRD patterns of the calcined

catalysts. The Rietveld refinement of the oxidized Ni/ZrO2
indicates more Ni2+ in the ZrO2 monoclinic lattice than in
the reduced catalyst (see the Ni2+ occupancy factors of the
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monoclinic ZrO2 phase); as a result, the O2− occupancy

factors decreased. Thus, oxygen vacancies are created after
the calcination of the catalyst. The reduction pretreatment
favors the migration of Ni2+ to the ZrO2 surface, where it is
reduced to Ni0, leaving the ZrO2 lattice. After the reduction
Fig. 7 EPR spectra of ZrO2 and Mg(Al)O reduced oxides. process, some oxygen vacancies and Ni2+ are still present in
the ZrO2 lattice.
The XRD pattern of the Ni/Mg(Al)O reduced catalyst is also
shown in Fig. S2.† The peak related to the (0 0 2) face-
analyzed by EPR owing to the very intense signal generated by centered-cubic nickel, Ni0 (space group Fm3̄m), is visible (2θ
Ni0, which hides bands related to other species. = 51.7°). The other peaks are partially superposed with the
Fig. S2 and S3 (ESI†) depict the XRD patterns of reduced peaks diffracted by the cubic periclase (MgO), which also
and oxidized Ni/SiO2 as references of Ni0 and NiO, respectively. shows the Fm3̄m space group. The lattice parameter of the
Fig. S2† displays the XRD patterns of the reduced MgO is 0.41867 nm which is much smaller than that of
passivated catalysts. The Rietveld refinement (Table 3) normal nanocrystalline MgO (0.4212 nm)56,57 but identical to
suggests that some Ni2+ ions substitute Zr4+ ions of the ZrO2 the value found by Roelofs et al. who studied the thermal
lattice (see occupancy factors of the monoclinic ZrO2 lattice). decomposition of hydrotalcite at 723 K.58 This lattice
The smaller ionic radius of Ni2+ (0.069 nm) compared to Zr4+ parameter reduction may be attributed to the partial
(0.084 nm) favors the substitution of the latter by the former substitution of Mg2+ ions (ionic radius = 0.072 nm) by Al3+
in the ZrO2 lattice.53 Moreover, the Ni2+ and Zr4+ charge (ionic radius = 0.054 nm).18,22,23,59 The Rietveld refinement
difference creates oxygen vacancies.54,55 Table 3 also shows does suggest the presence of Al3+ ions substituting the Mg2+
the composition of the catalysts. It was observed that the ions in the periclase for both the oxidized and the reduced
total percentage of metallic Ni plus Ni present in NiO is Ni/Mg(Al)O catalysts. This substitution gives rise to a
consistent with the X-ray fluorescence analysis (Table 2). periclase solid solution with Mg2+ vacancies.60,61 However,
these vacancies are not observed by the Rietveld refinement.
According to Wang,61 the cationic vacancy concentration in
Table 3 Microstructural and crystallographic parameters determined by
periclase decreases after calcination. Thus, this mixed oxide
Rietveld refinement of XRD data
might show a very low concentration of cationic vacancies.
Catalysts Ni/ZrO2 Ni/Mg(Al)O Ni2+ also seems to be present in the periclase structure of the
Oxidized Reduced Oxidized Reduced oxidized Ni/Mg(Al)O catalyst (Table 3). However, it does not
(passivated) (passivated) generate vacancies due to its charge. The reduction
pretreatment also, in this case, favors the migration of Ni2+
ZrO2 (monoclinic)
from the mixed oxide lattice to the Mg(Al)O surface, where it
Occupancy O−2 (1) 0.92 0.94 is reduced to Ni0. XRD also shows a broad peak of MgAl2O4
O−2 (2) 0.97 0.99
Zr4+ 0.97 0.99
spinel with a tiny crystallite size.
Ni2+ 0.03 0.01 Table 3 also shows the mass percentage of the observed
nanocrystalline phases in the Ni/Mg(Al)O catalyst. The spinel-
MgO like phase could not be included due to its low crystallinity
Occupancy Mg2+ 0.44 0.6 and lack of an appropriate description.
Al3+ 0.52 0.4 Crystallite sizes determined by Rietveld fitting, integral
O−2 (1) 1 1
Ni2+ 0.04 0 breadth method, showed that the pure ZrO2 monoclinic is
about 10 nm and did not change with the Ni/ZrO2 catalyst's
Phases heat treatment. The oxidized Ni/ZrO2 catalyst showed a face-
Phase/wt% m-ZrO2 92.2 92.5 centered-cubic NiO phase with 14 nm and the reduced
t-ZrO2 2.3 2.1 catalyst showed a metallic nickel phase with 21 nm. Thus,
Ni0 0 4.2 0 2.6 the reduction treatment allowed the metallic crystallites to
NiO 5.4 1.2 0 0
MgO 99.1 97.2 grow. The crystallite size of the periclase formed during the
Al2O3 0.9 0.3 calcination of pure Mg(Al)O is about 3.3 nm. However, the
Cell volume/Å3 m-ZrO2 139.91 140.22 Ni/Mg(Al)O catalyst's crystallite size is about 4.6 nm for both
t-ZrO2 67.12 67.40
the reduced and the oxidized conditions. The crystallite size
Ni0 43.65 43.95
NiO 54.40 55.00 of the Ni0 formed during the reduction treatment of this
MgO 75.5010 73.39 catalyst is about 4.6 nm. For Ni/Mg(Al)O and Ni/ZrO2

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Table 4 XPS analysis of the oxidized Ni/Mg(Al)O and Ni/ZrO2 catalysts of crystalline nanoparticles, MgO and Ni0. However, an Al
Ni 2p3/2 binding Atomic
compound was not observed. Indeed, this element is in the
Catalyst energy/eV Species ratio MgO crystal forming the Mg(Al)O mixed oxide and, probably,
an amorphous phase component. XEDS analysis confirms
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Ni/Mg(Al)O 853.2 NiO (ref. 63) Ni/Mg 0.027

855.6 Ni2+ in the MgO lattice23
861.5 Satellite
Ni/ZrO2 852.9 NiO (ref. 63) Ni/Zr 0.03
855.5 Ni2+ in the ZrO2 lattice62
861.6 Satellite
Pure NiO 853.3 NiO (ref. 63)
(reference)
catalysts, the Ni0 and NiO phases, respectively, show
crystallite sizes of about the same dimension as the supports.
Fig. S4† displays the Ni 2p3/2 spectra of the oxidized
catalysts. Table 4 shows the Ni 2p3/2 binding energies and
their assigned species. It is interesting to stress that both
catalysts show the same following species: Ni2+ cation in the
Mg(Al)O and ZrO2 lattice and NiO.23,62 These species are in
line with the XRD results, except for NiO of the Mg-based
catalyst, which was not observed using XRD. It can be
suggested that this oxide shows small particles not detectable
by this technique.
Table 4 also shows the XPS atomic ratios of Ni/Mg and Ni/
Zr. It can be inferred that Ni/ZrO2 and Ni/Mg(Al)O present
similar Ni atomic concentrations on their surfaces. This result
is in line with cyclohexane dehydrogenation rates (Table 2),
which suggest that these catalysts show similar metallic areas.
The bright-field (BF) TEM image in Fig. 8a shows the
passivated reduced Ni/Mg(Al)O catalyst. The selected area
electron diffraction (SAED) pattern in Fig. 8b confirms that
the Ni/Mg(Al)O catalyst observed in Fig. 8a contains two types
the presence of Al, Mg, O, and Ni. Fig. 8c and d present the
corresponding centered dark-field (CDF) images of Fig. 8a
obtained from two different diffraction ring spots of the
SAED pattern (Fig. 8b). Fig. 8c shows the CDF image
generated with the (220) diffraction planes of MgO crystals.
Fig. 8d is the CDF image generated with the (200) diffraction
planes of Ni0 crystals of the catalyst. It is worth noting that
the nanoparticles of Ni/Mg(Al)O catalyst are well distributed
and not agglomerated (this observation was consistent in
several TEM analyses). The average Mg(Al)O particle size is
approximately 4.23 ± 2.27 nm, whereas that of Ni0 is 5.45 ±
2.57 nm, both agreeing with the XRD results. This result
suggests that Ni0 and Mg(Al)O particles might be
nanocrystals. See histograms (Fig. S5 and S6†).
Fig. 9 shows the BF image of the passivated reduced Ni/
ZrO2 catalyst and its corresponding STEM/XEDS maps of Ni,
Zr, and O. It is verified that this catalyst is constituted mostly
by spherical-like nanoparticles. STEM/XEDS results confirm
the presence of Ni, Zr, and O in this catalyst. However, unlike
what was observed for the Ni/Mg(Al)O catalyst, Ni seems to
be concentrated in specific regions of the support (this
observation was consistent in several STEM/XEDS analyses).
The ZrO2 average particle size is in the range of 13–14 nm.
This result is in line with the Rietveld fitting, which showed
that monoclinic ZrO2 was about 10 nm (this ZrO2 particle
seems to be a nanocrystal). The size of the Ni0 particle was
also measured. The value obtained is 25.03 ± 6.90 nm, which
is again in line with the XRD data.

Fig. 8 (a) BF-TEM image of Ni/Mg(Al)O catalyst; (b) SAED pattern obtained from (a); (c) and (d) centered dark-field (CDF)-TEM images obtained
from the spot marked with circles 1 and 2 in (b), respectively.

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Fig. 9 BF-STEM image of the Ni/ZrO2 catalyst and corresponding
STEM-XEDS of Ni, Zr, and O.
3.3 Computational study
DFT calculations were carried out to support the
experimental data and shed light on the possible mechanism
of the CO2 methanation surface from a microscopic point of
view. The ZrO2 (111) surface structure model, as shown in
Fig. 1b, exposes three multilayers, each of which includes
one zirconium layer enclosed between two oxygen layers in
the sequence O–Zr–O–O–Zr–O–O–Zr–O. The surface Zr–Zr
bond distance is 3.36 Å, and the Zr–O bond distance is 2.05
Å. The lattice constant of bulk ZrO2 is 5.17 Å. The CO was
initially positioned at 2.00 Å above the surface, and different
orientations have been compared for each initial adsorption
site. On the ZrO2 (111) surfaces, four initial adsorption sites
were tested for the CO molecule. The most favorable position
is on top of the Zr atom (Fig. 10).
As shown in Fig. 11, after full structural optimization,
the CO gas molecule preferred to adsorb on the Zr top site
of the Ni/ZrO2 (111) surface, showing the same behavior
observed with the ZrO2 (111) support. The adsorption energy
for CO on ZrO2 (111) is −0.35 eV. Luo et al.64 found a
similar behavior in their investigation of the adsorption of
CO on ZrO2 (111) and doped with Ca. The C–O bond
Fig. 10 Adsorption of CO onto the ZrO2 (111) surface. Red, cyan, and
gray spheres represent the O, Zr, and C atoms, respectively.
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Fig. 11 Adsorption of CO onto the Ni/ZrO2 (111) surface. Red, cyan,
green, and gray spheres represent O, Zr, Ni, and C atoms, respectively.
distance, 1.07 Å, is slightly shortened with respect to the
free molecule (1.14 Å); the C atom in CO is adsorbed on the
surface of the Zr atom, generating a new surface behaving
as a Brønsted acid site.
The results for this CO–Ni/ZrO2 system can be compared
with similar calculations made recently.36 Important
electronic states of the CO molecule before and after
adsorption are shown in Fig. 12. The distance between the
carbon atom and zirconium for this system is greater, with a
value of 2.04 Å and Eads of −1.83 eV.
Fig. 12 shows the density of states (DOS) for a single
molecule of CO (Fig. 12a) and the PDOS of the carbon atom
of CO adsorbed on the surface of the NiZrO2. Fig. 12a and b
clearly show that the electronic states of CO at approximately
−12.8, −10.5, and −7.8 eV (Fig. 12a) are reduced considerably
in energy as the CO binds to the Ni/ZrO2 surface (Fig. 12b).
The CO adsorption mechanism on the top site of Zr of Ni/
ZrO2 can be qualitatively explained as follows. The CO
molecule prefers to be adsorbed on the top site due to the
interaction of HOMO-5σ from CO, and this interaction
results in orbitals shifted to lower energies. Similarly, the 2π*
antibonding CO molecule orbitals that interact with Zr at the
Fig. 12 (a) Total density of states of the free CO (blue) and (b) the
partial density of states, PDOS, onto the Bader charge of the CO
(orange) molecule placed above the Ni/ZrO2 (111) surface.
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Fig. 13 (a) Doped Ni2/ZrO−x (111) represented by a nickel slab model
with one oxygen vacancy on the top surface. (b) Electron localization
function (ELF) plot for the Ni2/ZrO−x (111) surface with one fourfold
oxygen vacancy.
surface also expand and move towards the Fermi level, which
is slightly occupied, as shown in Fig. 12b.
The experimental results showed that zirconia oxide
doped with nickel generates vacancies responsible for
preferential CO adsorption.10 The effect of oxygen vacancy
and surface Ni substituting the Zr4+ ions was also
investigated. The Ni ion was placed near a fourfold oxygen
vacancy position (denoted as Ni2/ZrO−x), as shown in Fig. 13.
The vacancy formation energy for this environment was −5.35
eV; the Bader's charge analysis indicates a charge of 2.51 e−
on the Zr atom and 2.23 e− on each Zr atom neighboring
state upon the formation of the oxygen vacancy, indicating
that Zr atoms change their oxidation state from Zr4+ to Zr3+.
The removal of an oxygen ion from the ZrO2 (111) surface
leads to the localization of d orbital electrons in the vacancy
region. Hence, the highly favorable formation of a vacancy
can be attributed to the introduction of a localized electronic
charge of 2 e− with two unpaired electrons situated on two d
orbitals nearest to the formed vacancy, as in the case of a
vacancy in Ni/ZrO2 doped with nickel (denoted as Ni2/ZrO−x).
Fig. 13b shows the electron localization function (ELF)
mapped on the a plane that contains the vacancy. The ELF is
high in the oxygen vacancy region caused by doping with nickel,
showing that the electrons remain trapped at the defect site.
Calculations performed on the Ni2/ZrO−x (111) surface
with an oxygen O2− vacancy showed that CO is also adsorbed.
Fig. 14 shows the fourfold coordinated oxygen vacancy, which
changes the oxidation state from +4 to +3. The detected CO
interaction was a strong chemisorption type, with Eads,CO =
−3.80 eV, and the C atom bonds to two Zr atoms. Table 5
shows that the adsorbate CO molecule's Bader charges are
higher than that for the free molecule. The charge transfer of
−0.60 e− implies that the interaction between the surface and
the adsorbed molecule is very strong. It is important to note
that in the reduced Ni2/ZrO−x (111) surface, the molecule only
interacts with two atoms of the Zr3+ bridge type (located at
the top of the anionic vacancy generated by the insertion of
Ni into the ZrO2 lattice as shown in Fig. 14).
The mechanism of CO bridge adsorption over the Ni2/
ZrO−x nickel-doped surface can be explained by inspecting
the CO molecule and the surface electronic structure before
and after adsorption. The calculated partial density of states
(PDOS) of CO projected onto the C and O are plotted in
Fig. 15. For the free CO molecule, as observed in Fig. 15a, the
highest occupied molecular orbital (HOMO) is the degenerate
5σ orbital, and the lowest unoccupied molecular orbital
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Fig. 14 Adsorption of CO onto the Ni2/ZrO−x (111) surface. Red, cyan,
green, and gray spheres represent the O, Zr, Ni, and C atoms,
respectively.
Table 5 Adsorption energies, distances, interaction energy, deformation
for CO adsorbed on the ZrO2, Ni/ZrO2, and Ni2/ZrO−x surfaces
Total Bader charge (e−)
Adsorption Eads Eint Edeform-slab D
system (eV) (eV) (eV) (Å) Sum(CO) = 0.01(free)
CO–ZrO2 −0.35 −0.89 0.11 1.07 −0.07
CO–Ni/ZrO2 −1.28 −3.13 0.21 1.13 −0.19
CO–Ni2/ZrO−x −3.80 −5.89 2.90 1.19 −0.60
(LUMO) is the degenerate 2π antibonding orbital. Fig. 15b
shows the PDOS and Bader charge of the adsorbed CO
molecule in Ni2/ZrO−x. Compared to the free CO molecule,
the peak of 5σ and 4σ is significantly depressed in the
adsorbed CO due to the transfer of electrons from the CO to
the Zr atoms. The 2π* isolated CO molecule orbitals move to
the low-energy region below the Fermi level and hybridize
strongly with the Ni2/ZrO−x surface's higher valence band.
The significant elongation of the 2π orbital indicates a
strong interaction of the adsorbed molecule with the Ni2/
ZrO−x. The charge transfer of −0.60 e− induces the broadening
of the 2π* orbital and experiences an increase in electron
density upon adsorption, resulting from interacting with the
d orbitals of the Ni2ZrO−x surface, which results in an
elongation of the C–O bond (from 1.14 Å to 1.19 Å) due to
the antibonding nature of the 2π* orbital. Therefore, such a
process favors the dissociation of the CO molecule and
greatly influences the absorbed molecule.
The calculated adsorption energies are listed in Table 5. We
can find that adsorption on ZrO2 (111) (Ead = −0.35 eV) is less
stable than at Ni/ZrO2 (Ead = −1.28 eV). The adsorption of CO
over Ni2/ZrO−x is more favored than over Ni/ZrO2 and ZrO2 sites.
The present calculation is consistent with the literature
reports on the behavior of CO on the surface with vacancies.65
In this sense, it has been indicated that the interaction of CO
on the Ni2/ZrO−x (111) surface is very prominent when oxygen
vacancies are present.66 Indeed, Metiu et al.67 have shown that
low valence dopants turn the oxide surface into a Lewis base
that strongly favors CO adsorption. The calculated interaction
energies (Eint) for the system with CO are shown in Table 5.
This strong molecule (CO)/surface coupling was confirmed by
the interaction energy of −3.13 eV and −5.89 eV for the Ni/ZrO2
and Ni2/ZrO−x (111) surfaces, respectively, showing that the
molecule was strongly bonded to the surface by the presence of
oxygen vacancy. The deformation energy of the most stable Ni2/
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Fig. 15 (a) Total density of states of free CO (blue) and (b) PDOS onto
the Bader charge of the CO (red) molecule placed above the nickel-
doped Ni2/ZrO−x (111) surface with one oxygen vacancy.
ZrO−x was slightly higher than the deformation energy for the
ZrO2 and Ni/ZrO2 surfaces, according to Table 5. The weak
bond could explain the low deformation energy for ZrO2
between the carbon atom and the zirconium atoms, unlike Ni/
ZrO2 and Ni2/ZrO−x surfaces. These data suggest a continuous
weakening of the CO bond and consequently leads to an
increase of the adsorption energy due to oxygen vacancy. The
fourfold oxygen vacancy on the surface adjacent to the Zr atom
increased the stability and further improved CO molecule
adsorption. This feature could be attributed to oxygen leaving
two excess electrons on Zr4+ cations, filling the empty 4d
orbitals of the Zr4+ cations to form Zr3+. Such a process
positively influences the dissociation of the CO molecule.
3.4 Further results and discussion
Two mechanisms seem to describe this reaction better when
active supports are employed. The first assumes that the
adsorbed CO2 generates carbonate species that react with
monoatomic H species, formed by the parallel H2
dissociation on the metal, which spill over towards the
support. The CO2 adsorption occurs on the basic sites and
also on the oxygen vacancies. The carbonate species are
hydrogenated to formate species; these species are reduced
to methoxide species and after that decompose to CH4.
Finally, H reduces the surface recovering the vacancies, and
H2O is generated.8,68 The rate-limiting step is the dissociation
of the C–O bond of the formate species, which occurs on the
cus–oxygen vacancy pair. The second mechanism16,40,46,68,69
assumes that the adsorbed CO2 gives one of its O ions to an
anionic vacancy of the support and generates CO, which is
adsorbed on the oxide surface, allowing more time for the
following reactions. The H2 molecule dissociates on the
metal, and the monoatomic H species spill over to the oxide,
where they react with the O ion, generating H2O and
recovering the oxygen vacancy. This first step is the reverse
water gas shift (RWGS) reaction. The CO molecule interacts
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with the cus–oxygen vacancy pair, where it further
dissociates, freeing the carbon to be hydrogenated to CH4.
The CO dissociation, according to some authors, can be H-
assisted.68 The rate-limiting step is the CO dissociation on
the cus–oxygen vacancy pair. Again, the O will be removed
from the vacancy by the H species and will produce H2O.
Both mechanisms considered C–O bond dissociation as
the rate-limiting step, involving the cus–oxygen vacancy
pairs.7,8,10,11,16 Thus, the elimination of the O, i.e., the
recovery of the vacancies, is a critical step.
Fig. 3 and Table 1 show that all these catalysts generate
CO. This means that all these solids might synthesize CH4
according to the CO mechanism. The formate might be
related to the catalysts with active supports, i.e., Ni/ZrO2 and
Ni/Mg(Al)O. Indeed, in the case of Ni/ZrO2 and Ni/Mg(Al)O,
these mechanisms might occur concomitantly.
The Ni/SiO2 catalytic behavior shows that Ni can generate
CH4. However, its lower activity and selectivity to CH4 (Fig. 2
and 3) are associated with silica's inert character.70,71
Fig. 16 and 17 display the CO2 + H2-TPSR profiles for Ni/
ZrO2 and Ni/Mg(Al)O, respectively. Comparing the CH4 and
CO2 desorption, the Zr-based catalyst seems to adsorb more
CO2 than Ni/Mg(Al)O. Moreover, H2O desorption of Ni/ZrO2
(261 °C) occurs at much lower temperatures compared with
Ni/Mg(Al)O (361 °C). It is observed that the maximum
evolution of CH4 from the Mg-based catalyst occurs at 235
°C, whereas that of Ni/ZrO2 at 261 °C, suggesting that the
Mg-based catalyst is slightly more active. Thus, the
elimination of water and recovery of vacancies is more
difficult for the Ni/Mg(Al)O catalyst, which might impact the
activity and selectivity of this catalyst in CO2 methanation.
Fig. S7† exhibits the CO2 + H2-TPSR spectra related to Ni/
SiO2. The amount of CH4 generated is minimal compared
with Zr- and Mg-based catalysts. This result shows that the
primary role of Ni is H2 dissociation.
The CO + H2-TPSR spectra (Fig. 18) shows similar CH4
bands (intensity and maximum temperature) for both
catalysts. However, the H2O spectra are again different. Their
maxima are around 313 °C and 418 °C for Ni/ZrO2 and Ni/
Mg(Al)O, respectively, confirming again that it is difficult to
remove the oxygen of the Mg-based catalyst.
Fig. 19 displays the CO-TPD of ZrO2 and Mg(Al)O. Both
catalysts generate CO2. However, the CO2 band related to
ZrO2 occurs at a lower temperature, confirming that CO
Fig. 16 CO2 + H2-TPSR profile of reduced Ni/ZrO2.
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Fig. 17 CO2 + H2-TPSR profile of reduced Ni/Mg(Al)O.
oxidation is easier on this catalyst. Considering the Mars–Van
Krevelen mechanism, it can be inferred that ZrO2 is reduced
more easily than Mg(Al)O.
The XRD Rietveld refinement of the Ni/Mg(Al)O catalyst
does not show anionic (oxygen) vacancies, whereas the EPR
spectrum exhibits these vacancies. The samples analyzed by
XRD were reduced and passivated. This procedure might
eliminate the O superficial vacancies. The EPR data were
obtained from samples reduced but not passivated, which
might keep these vacancies. The Mg(Al)O particle and crystal
sizes are around 4.2 nm (TEM and XRD). Thus, the anionic
vacancies can be associated with the nanoparticle's intrinsic
defects.
Further, formation of cationic vacancies might be
expected due to the charge of Al3+ and Mg2+. However, these
vacancies were not observed. According to Wang et al.,61
these vacancies vanish due to high-temperature treatments.
XRD Rietveld refinement of oxidized and reduced Ni/ZrO2
catalysts does show Ni2+ in the ZrO2 lattice and O vacancies.
The EPR spectrum of ZrO2 (monoclinic) also exhibits O
vacancies. XPS analysis of the oxidized sample also shows the
presence of Ni2+ in the ZrO2 lattice (surface). Silva-Calpa et al.
showed that adding even small amounts of Zn, a lower-
valence dopant, to ZrO2 generates O vacancies and increases
O mobility.72 Thus, the reducibility of the ZrO2 is improved
by Ni in the ZrO2 lattice.
The SiO2 substrate is amorphous, so it does not allow the
classical definition of vacancies in its structure. Moreover,
recent DFT calculations show that the diffusion of neutral O
vacancies in amorphous SiO2 is unfeasible.73 Therefore, this
mechanism will not be available during the catalytic process.
Fig. 18 CO + H2-TPSR profile of reduced Ni/Mg(Al)O (yellow) and
reduced Ni/ZrO2 (blue).
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Fig. 19 CO-TPD profile of oxidized Mg(Al)O (yellow) and oxidized
ZrO2 (blue).
Thus, the ranking of the number of vacancies of the catalysts
is the following: Ni/Mg(Al)O < Ni/ZrO2.
Table 1 (CO2 methanation rates) depicts that increasing the
vacancy concentration of the catalysts decreases the CO
formation rates and increases the CH4 formation rates. As
described above, C–O rupture is considered the rate-limiting
step of the CO mechanism. According to the DFT calculations
(section 3.3), the vacancies facilitate the C–O dissociation,
weakening this bond and keeping this molecule adsorbed on
the surface. Thus, vacancies on the oxide surface promote the
CO and CO2 methanation reaction, in line with Table 1 results.
The Ni0 particle size of the Ni/ZrO2 reduced and passivated
sample, observed by TEM, is much larger than that of the Mg-
based catalyst. Considering that both catalysts show the same
Ni concentration (Table 2), the metallic surface area of Ni/
Mg(Al)O should be higher than that of the Zr-based catalysts.
However, the XPS data and cyclohexane dehydrogenation rates
showed that both catalysts have similar Ni0 metallic areas.
Indeed, the Ni/Mg(Al)O reduction process temperature is not
able to reduce all Ni (see TPR profiles, Fig. 6). It is proposed that
Ni substitutes Mg in the MgO structure, which forms a NiO–
MgO solid solution74 (see Table 3) and therefore is not available
as a metallic nickel. Moreover, the XRD data (Table 3) of the
reduced and passivated samples show that the amount of Ni0 of
the Mg-based catalyst is much lower than that of Ni/ZrO2. Thus,
the smaller particle size of Ni0 of the Mg-based catalyst would
generate a higher metallic area than Ni/ZrO2 but is
compensated for by the lower concentration of Ni0 on the Ni/
Mg(Al)O surface, which leads to a lower number of Ni0 particles.
The Ni/ZrO2 is more active than Ni/Mg(Al)O (Table 1) in the
CO2 methanation. Considering that both catalysts show the
same metallic area, it can be inferred that the dissociation of
H2 in the CO2 methanation is not kinetically relevant.
The XRD and EPR data show that after reduction
(pretreatment), much more vacancies are observed for the Zr-
based catalyst than for the Ni/Mg(Al)O catalyst. Table 1
exhibits that the ratio between the rate of CH4 formation of
Ni/ZrO2 and Ni/Mg(Al)O is 5.3 at 350 °C. However, on
increasing the temperature the Mg- and Zr-based catalysts
exhibited similar behavior, as observed in Fig. 2 and 3. Thus,
the number of vacancies generated after the reduction
process (pretreatment of the catalysts) seems not to be the
main factor for describing the catalytic behavior of these
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Catalysis Science & Technology
catalysts. The CO2 + H2-TPSR spectra of Ni/ZrO2 and Ni/
Mg(Al)O show that the former generates vacancies more
easily (H2O elimination). The mechanisms described above
suggest that the rate of O elimination from the supports is
Published on 03 January 2022. Downloaded by Pontifícia Universidade Catolica do Rio de Janeiro on 1/21/2022 5:12:09 PM.
intrinsically linked to the catalytic behavior. Thus, the
number of vacancies and the reducibility of the supports are
both relevant for catalyst activity and selectivity to CH4.
It is interesting to observe that the catalytic behavior of
Ni/Mg(Al)O changes with the temperature (Fig. 2 and 3). As
the temperature increases, the activity and selectivity to CH4
of the Mg-based catalyst increases and are very similar to that
of the Zr-based catalyst for temperatures higher than 400 °C.
It can be suggested that as the temperature increases, the O
elimination, i.e., vacancy generation, is easier. Therefore, the
performance of the Mg-based catalyst improves. It is worth
noting that the behavior of Ni/SiO2 improves in the CO2
methanation as the temperature of the reaction increases.
However, it did not reach the performance of the Mg- and Zr-
based catalysts.
According to Metiu,75 the higher the electrophilic
character of the surface, the easier the oxygen vacancies are
generated. Zirconium is much more electrophilic than Mg
and Al at low concentrations in Ni/Mg(Al)O. The rate-limiting
step of the CO2 methanation occurs on the oxygen vacancies.
Thus, the Ni/ZrO2 catalyst is more active than Ni/Mg(Al)O
due to the electrophilic character of its surface. At high
temperatures, the behavior of these catalysts becomes similar
due to the increased oxygen mobility under these conditions.
4. Conclusion
The Zr- and Mg-based catalysts are active and selective catalysts
for CO2 methanation. However, the latter should be employed
at high temperatures. This work shows that the activity and
selectivity of the Ni-based catalysts are determined by the
facility of the support to release O (reducibility).
The catalytic behavior of Ni/SiO2 is very poor compared
with that of the Mg- and Zr-based catalyst. Indeed, Ni0 can
generate CH4 from CO2 and contribute to the Ni/Mg(Al)O and
Ni/ZrO2 catalytic behaviors. The Ni/ZrO2 and Ni/Mg(Al)O
catalysts show the same metallic area. However, the former is
more active and selective than Ni/Mg(Al)O at a broad
temperature range, showing that H2 dissociation is not
kinetically relevant.
The intrinsic vacancies of the Mg(Al)O nanocrystal seem
to be very important for the Ni/Mg(Al)O catalyst performance.
In the case of Ni/ZrO2, the vacancies are both intrinsic and
extrinsic, generated by the Ni insertion in the ZrO2 lattice.
These vacancies are also certainly related to the ZrO2
reducibility and also relevant for the catalytic behavior.
DFT calculations pointed out that oxygen vacancies
promote CO adsorption and also C–O rupture, the rate-
limiting step of the CO2 methanation. Thus, the oxygen
vacancies are directly associated with the rate-limiting step of
the CO2 methanation. The DFT calculations are in line with
the catalytic behavior.
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Paper
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors are grateful to the Brazilian Center for Research in
Physics (CBPF-Brazil) for the access to the LABNANO Electron
Microscopy facilities and RPE laboratory for the EPR analysis.
We are also thankful to the LACAT/INT staff for the
characterization of the catalysts. The authors acknowledge
Saint-Gobain NorPro and also Sasol for supplying the supports.
This study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior – Brasil, (CAPES)
– Finance Code 001, and Conselho Nacional de
Desenvolvimento Científico e Tecnológico – CNPq, Brazil, CNPq
305095/2015-3. LT Costa is grateful for the funding provided by
FAPERJ, PRINT-CAPES, and CNPq fellowship 7.310459/2018-00.
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