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Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3) 2021, 641-650

Research Article

Ni Nanoparticles on Reducible Metal Oxides (Sm2O3,

CeO2, ZnO) as Catalysts for CO2 Methanation
Athirah Ayub, Hasliza Bahruji*, Abdul Hanif Mahadi

Centre for Advanced Material and Energy Sciences, Universiti Brunei Darussalam, Jalan Tungku
Link, BE1410, Brunei Darussalam.

Received: 4th May 2021; Revised: 6th July 2021; Accepted: 6th July 2021
Available online: 8th July 2021; Published regularly: September 2021

Abstract
The activity of reducible metal oxide Sm2O3, CeO2, and ZnO as Ni nanoparticles support was investigated for CO2
methanation reaction. CO2 methanation was carried out between 200 °C to 450 °C with the optimum catalytic ac-
tivity was observed at 450 °C. The reducibility of the catalysts has been comparatively studied using H 2-
Temperature Reduction Temperature (TPR) method. The H2-TPR analysis also elucidated the formation of surface
oxygen vacancies at temperature above 600 °C for 5Ni/Sm 2O3 and 5Ni/CeO2. The Sm2O3 showed superior activity
than CeO2 presumably due to the transition of the crystalline phases under reducing environment. However, the
formation of NiZn alloy in 5Ni/ZnO reduced the ability of Ni to catalyze methanation reaction. A highly dispersed
Ni on Sm2O3 created a large metal/support interfacial interaction to give 69% of CO 2 conversion with 100% selec-
tivity at 450 °C. The 5Ni/Sm2O3 exhibited superior catalytic performances with an apparent phase transition from
cubic to a mixture of cubic and monoclinic phases over a long reaction, presumably responsible for the enhanced
conversion after 10 h of reaction.

Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA
License (https://creativecommons.org/licenses/by-sa/4.0).

Keywords: Ni nanoparticles; metal oxides (Sm2O3, CeO2, ZnO); CO2; methanation

How to Cite: A. Ayub, H. Bahruji, A.H. Mahadi (2021). Ni Nanoparticles on Reducible Metal Oxides (Sm 2O3,
CeO2, ZnO) as Catalysts for CO2 Methanation. Bulletin of Chemical Reaction Engineering & Catalysis, 16(3), 641-
650 (doi:10.9767/bcrec.16.3.10948.641-650)

Permalink/DOI: https://doi.org/10.9767/bcrec.16.3.10948.641-650

1. Introduction drogenation potential [3] and the surface oxygen

vacancy [4]. Ceria (CeO2) is generally used as
Utilization of CO2 as carbon feedstock via the
support for CO2 methanation, and as a promoter
conversion to methane has been identified as a
to enhance surface oxygen vacancy of the cata-
sustainable technology to produce renewable en-
lysts [5,6]. In order to design active catalysts for
ergy [1]. CO2 reduced under H2 gas at atmos-
the reaction, several parameters are modified
pheric pressure to form methane in the presence
for example Ni dispersion [7], Ni reducibility [8]
of metal catalysts. In order to overcome the
and CO2 adsorption capacity [9]. On the non-
thermodynamic of the reaction, investigation is
reducible support such as Al2O3 and zeolite, Ce
carried out to synthesis catalysts with high
was shown to improve metal-support interaction
methanation potential [2]. Modification of metal
and reducibility of the catalysts [10]. Promoters
oxide with metal nanoparticles increases the hy-
such as K and Ba are added to improve the re-
ducibility of Cu by covering the surface of Al2O3
* Corresponding Author. support that allowed Cu to be easily accessible
Email: [email protected] (H. Bahruji) [11]. The reducibility of metal oxide provides the

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 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 642

flexibility of the catalyst surface during CO 2 2. Materials and Methods

methanation which mostly was associated with
2.1 Preparation of the Catalysts
the presence of surface defect [12]. Depending
on the degree of reducibility, reducible metal All the catalysts were prepared using wet-
oxide, such as CeO2, decreases the CO coverage ness impregnation method. Ni(NO3)2 at 5% of
on Ru metal center, to ensure the dissociation weight loading was dissolved in 10 mL of wa-
of H2 can occur for the generation of methane ter. The amount of Ni loading was kept at 5%
[13]. However, on a non-reducible metal oxide for all catalysts. The Ni(NO3)2 solution was
such Al2O3, the catalytic activity is largely cor- added into metal oxide supports, CeO2, Sm2O3,
related with the basicity of the catalyst [13]. and ZnO, and stirred for 3 h at 60 °C to ensure
The activity of CeO2, Sm2O3, and ZnO as re- thorough dispersion. The catalysts were dried
ducible oxides support will be investigated in at 200 °C for 2 h and then calcined at 500 °C
improving Ni activity for CO2 methanation. for 3 h in air with a heating rate of 10 °C/min.
CeO2 represented as among the mostly investi-
gated metal oxide for CO2 methanation reac- 2.2 Characterization of the Catalysts
tion [14,15]. The oxidation states of cerium are
X-ray powder diffraction (Shimadzu XRD-
interchangeable between 4+ and 3+, with the
700 X-ray Diffractometer) was carried out to
Ce3+ ions signified the presence of oxygen va-
analyze the crystalline structure of the cata-
cancies and the migration of sub-surface oxy-
lysts by utilizing Cu-K radiation at  = 1.54
gen [16]. Rare-earth metal oxide Sm2O3 was re-
Å, with operating conditions of 60 kV and 50
ported as promoter for CO2 methanation that
mA. The scanning angle range, 2θ, was 10–70°
exhibited high activity, stability and coke re-
with a scan rate of 2°/min. The crystalline
sistance when incorporated with Ni/SBA-15
structure size was calculated using Scherrer’s
catalysts [17]. As a support, the Sm2O3 showed
equation (Equation (1)).
high activity when loaded with 39% of Ni to
give ~71% of CO2 conversion to methane at 300 k
D= (1)
°C [18]. ZnO is another interesting reducible  cos 
metal oxide as catalyst support, however its re-
where D is the crystallite size (nm),  is the
ducibility is associated with the ability to
wavelength of x-ray (1.54 Å), θ is the peak posi-
transfer the charge to fill the d-band of metal
tion (radians), k is Scherrer constant and  is
for the formation of metal alloy [19,20]. ZnO
the FWHM (radians).
was reported as active support for CO2 hydro-
Surface area, average pore volume and pore
genation to methanol when impregnated with
diameter of the catalysts were determined by
Pd due to the formation of Pd-Zn alloy that can
N2 adsorption at 77 K (Micromeritics ASAP
stabilize formate intermediate [21–23]. In this
2020). The samples were degassed under car-
study, the catalytic activity of Ni supported on
bon degassing conditions for 2 h at 300 °C.
reducible metal oxides, CeO2, Sm2O3, and ZnO
Brunauer-Emmett-Teller (BET) equation was
were investigated for CO2 methanation at dif-
used to calculate the catalysts’ surface area
ferent reaction temperatures. Reducible metal
and Barret-Joyner-Halenda (BJH) equation for
oxide has the ability to release electron under
pore volume and diameter calculation.
reducing environment for dissociation of C−O
H2 Temperature-Programmed Reduction
bond, however the reducible support can also
(ChemBET Pulsar TPR/TPD, equipped with
change the structural and electronic properties
TCD) was performed to study the catalysts’ re-
of Ni. Due to the reducibility of these support,
ducibility of NiO species on the catalyst sur-
the presence of continuous hydrogen gas as re-
face. Catalysts undergone pre-treatment in N2
ducing agent in CO2 methanation also modified
stream with flow of 75 mL/min at 100 °C for 1
the structure of the catalysts. This study eluci-
h and later cooled down to 40 °C in the same
date the changes on Ni nanoparticles activity
gas stream. Catalysts were later heated to 900
when exists in metallic and alloy states upon
°C with a heating rate of 10 °C/min in a
impregnation on reducible support. Compara-
5%H2/N2 gas mixture with a flow rate of 75
tive H2−TPR analysis is used to provide under-
ml/min.
standing on the dispersion and the reducibility
of Ni, meanwhile X-ray Diffraction (XRD), N2
2.3 Catalytic Testing
adsorption, and Transmission Electron Micros-
copy (TEM) are employed for structural and CO2 methanation reaction was conducted in
morphology analysis. a stainless-steel plug flow reactor at atmos-
pheric pressure and reaction temperature

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 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 643

ranging from 200 to 450 °C. 0.5 g of catalyst Where xCO2(%) is the CO2 conversion, SCH4(%) is
was placed in a tubular fixed bed reactor and the CH4 selectivity, SCO(%) is the CO selectivi-
reduced in situ with H2 gas (99.9%) with flow ty, YCH4(%) is the CH4 yield, and m is the num-
rate of 20 mL/min at 450 °C for 3 h. The cata- ber of moles of the gases.
lysts were cooled down to room temperature
and CO2/H2/N2 (15%/60%/25%) gases at 20 3. Results and Discussion
ml/min were flowed in the reactor for catalytic
3.1 XRD Analysis
reaction. The gas effluent from reactor was an-
alyzed by GC (Shimadzu GC-2014) after 1h. Figure 1 showed the XRD analysis of
Reaction temperature was increased by 50 °C 5Ni/CeO2, 5Ni/Sm2O3, and 5Ni/ZnO after calci-
every hour and data were recorded. CO2 con- nation in air at 500 °C and reduction in H 2 for
version (Equation (2)), CH4 (Equation (3)) and 3 h at 400 °C. For 5Ni/CeO2, the characteristic
CO selectivity (Equation (4)), and CH 4 yield peaks of CeO2 were observed at 2θ = 28.6°,
(Equation (5)) were calculated as follows: 33.1°, 47.5°, 56.4°, 59.2°, and 69.4° (JCPDS
043-1002). For 5Ni/Sm2O3, the peaks assigned
 mCH 4 + mCO 
xCO2 =    100% (2) to Sm2O3 cubic crystalline phases were ob-
 mCH 4 + mCO2 + mCO  served at 2θ = 28.2°, 32.7°, 46.9°, and 55.6°
(JCPDS 043-1029) [15]. For 5Ni/ZnO, the
 mCH 4  characteristic peaks of ZnO were observed at
SCH 4 =    100% (3) 2θ= 31.9°, 34.5°, 36.3°, 47.5°, 56.7°, 62.9°,
 mCH 4 + mCO  66.4°, 68.0°, and 69.2° (JCPDS 036-1451).
Small NiO peaks were observed in Ni/Sm2O3 at
 mCO 
SCO =    100% (4) 2θ = 37.4° and 42.0°, corresponding to the NiO
 mCH 4 + mCO  nanoparticles with estimated sizes of ~1.2 nm.
In the 5Ni/CeO2, no peak associated with NiO
YCH 4 = xCO2  SCH 4 (5) was observed that may be due to the formation
of highly disperse Ni nanoparticles [24]. The
additional peak was observed at 2θ = 23.9° on
5Ni/ZnO catalyst which indicated the for-
mation of Ni-Zn alloy.

3.2 N2 Adsorption-Desorption Analysis

N2 analysis was carried out to investigate
the textural properties of the catalysts. Figure
2 presented the N2 adsorption-desorption iso-
therms and pore size distributions of
5Ni/Sm2O3, 5Ni/ZnO, and 5Ni/CeO2 after calci-
nation at 500 °C for 3 h. Based on the IUPAC
isotherm classification, all the catalysts dis-
played Type III isotherm, which is a typical
feature of a non-porous material [25].
5Ni/Sm2O3 and 5Ni/CeO2 showed the presence
of H3-hysteresis loop at high P/Po that suggest-
ed the formation porous structure [26]. The
Type H3 loop at high P/Po was produced from
the adsorption of multi-layer metastability and
delayed capillary condensation which occurs in
slit-shaped macropores or non-rigid aggregates
of plate-like particles resulted from a low level
of pore curvature and flexibility of the aggre-
gate structure [26]. Table 1 summarized the
textural properties of the catalysts calculated
using BET equation. The 5Ni/CeO2 showed the
highest surface area (15 m2/g) followed with
5Ni/ZnO (13 m2/g) and 5Ni/Sm2O3 (9 m2/g). The
Figure 1. XRD patterns of 5Ni/CeO2,
plot of pore size distribution showed the pres-
5Ni/Sm2O3 and 5Ni/ZnO after calcination at
ence of pores at ~21 nm on 5Ni/TiO2 catalysts
500 °C and reduction at 450 °C.

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 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 644

Figure 2. (a) N2 adsorption-desorption isotherm plot and (b) pore size distribution for 5Ni/CeO 2,
5Ni/Sm2O3, and 5Ni/ZnO after calcination at 500 °C.

Figure 3. H2-TPR profiles of 5Ni/CeO2, 5Ni/Sm2O3 and 5Ni/ZnO after calcination at 500 °C.

Table 1. Physical and textural properties, and CO2 conversion of Ni on CeO2, Sm2O3, and ZnO. Reaction
temperature: 450 °C.
Pore Volume Pore Size Ni sites
Catalyst SBET (m2/g) XCO2 (%) SCH4 (%)
(cm3/g) (nm) (mmol/g)
5Ni/CeO2 15 0.0431 2.3, 3.3 6.8 67.6 99.5
5Ni/Sm2O3 9 0.0419 2.0, 11.0 18.5 69.3 100
5Ni/ZnO 13 0.0421 2.1 5.2 26.6 99.5

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 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 645

presumably due to the formation of interparti- Sm2O3 to SmO in the absence of Ni [31]. It is
cle mesopores. suggested that the reduction peak of Sm2O3
was reduced to temperature below 700 °C due
3.3 H2−TPR Analysis to the H2 spillover from Ni. The reduction peak
of NiO was overlapped with the reduction peak
Temperature Programmed Reduction (TPR)
of Sm2O3 thus produced a broad TPR profile on
was carried out on the catalysts to investigate
Ni/Sm2O3. The Sm2O3 was reduced at tempera-
the reducibility and the dispersion of Ni parti-
ture below 700 °C, significantly lower than the
cles (Figure 3). In general, the reducibility of Ni
reduction of CeO2 which was occurred at tem-
catalyst was determined based on the position
perature above 700 °C. The results implied the
of the reduction peak at 250–500 °C due to re-
tendency of Sm2O3 to generate oxygen vacan-
duction of NiO to metallic Ni. 5Ni/ZnO showed
cies under H2 flow was higher than CeO2.
the first reduction peak centered at 470 °C and
was accompanied with a broad reduction peak
3.4 TEM-EDX Analysis
between 550–700 °C. The first reduction peak
was associated with the reduction of -type TEM analysis was carried out to determine
NiO species, generally reduced at low- the morphology of 5Ni/Sm2O3 catalyst and to
temperature region (300–500 °C) [27,28]. acquire the average diameter of Ni particles.
Meanwhile, the broad reduction peak observed 5Ni/Sm2O3 was calcined in air and reduced in
between 550–700 °C was due to the segregation hydrogen gas prior to the TEM analysis. Figure
of ZnO to Ni-Zn alloy [29]. The presence of Ni- 4 showed the representative TEM image of
Zn alloy was evidenced from the XRD analysis 5Ni/Sm2O3 with its corresponding EDX analy-
(Figure 1). The 5Ni/CeO2 showed the first re- sis. Ni was well distributed on Sm2O3 surface
duction peak appeared at 350 °C and a small evidenced from the formation of spherical
peak at 290 °C. The multiple H 2 consumption shapes particles as shown in a small red circle.
peaks indicated the differences between inter- The particle size of Ni nanoparticles was ana-
action of NiO species with the metal oxide sup- lyzed using ImageJ and the average diameter
port [30]. Increasing the temperature to 900 °C was determined at ~2 nm. The EDX elemental
showed a broad reduction peak started at 600 analysis of 5Ni/Sm2O3 further confirmed the
°C and was continuously increased at tempera- presence of Ni at ~5% loading. The elemental
ture above 900 °C. At temperature above 600 mapping also indicated the homogeneous dis-
°C, the oxygen in ceria surface was removed persion of Ni on Sm2O3.
when reacted with H2, releasing water and cre-
ating surface oxygen vacancies [30]. The vacan- 3.5 Catalytic Activity
cies were formed from the reduction of Ce4+ to
CO2 methanation was carried out 200–450
Ce3+ under H2 flow. The 5Ni/Sm2O3 showed a
°C at atmospheric pressure (Equation (6)). Pri-
broad reduction profile of NiO with the peak
or to the reaction, the catalyst was reduced in-
centered at 411 °C. Sm2O3 was reduced at tem-
situ at 450 °C under H2 flow for 3 h. Table 1
perature above 700 °C due to reduction of

Figure 4. HRTEM-EDX analysis of 5Ni/Sm2O3 catalyst.

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 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 646

summarized the physicochemical properties Ni5Ga3 alloy was also observed on Ga2O3 sup-
and the catalytic performances of all the cata- port, responsible for enhanced methanol for-
lysts at 450 °C. The 5Ni/CeO2 showed 67.6% of mation from CO2 [35]. There is also possibility
CO2 conversion with 100% selectivity towards that NiZn alloy further catalyzed the resulting
methane. When Ni was impregnated onto methane into CO via dry reforming reaction
Sm2O3, the conversion of CO2 was slightly in- [36]. Therefore, the efficiency of Ni alloy in
creased to 69.3% at 100% selectivity to me- 5Ni/ZnO catalyst for methanation reaction was
thane. If the reaction was carried out using reduced to give only 26.6% of CO2 conversion at
5Ni/ZnO, the CO2 conversion was observed at 450 °C, with CO was also determined as the re-
26.6% with 99.5% selectivity to methane. Un- sult of reverse water gas shift reaction
like CeO2 and Sm2O3, ZnO showed a relatively (Equation (7)).
low catalytic conversion presumably due to the
formation of Ni-Zn alloy on the catalysts that CO2 (g) + 4H2 (g) ↔ CH4 (g) + 2H2O (g)
reduced the activity of Ni towards methanation ΔH298K = −165 kJ/mol (6)
reaction. In CO2 methanation reaction, it was
reported that Ni must be in its zero oxidation CO2 (g) + H2 (g) ↔ CO (g) + 2H2O (g)
states to catalyze hydrogen dissociation [32]. ΔH298K = −41.2 kJ/mol (7)
The use of ZnO as support, formed Ni-Zn alloy
that changed the electronic properties of Ni. CO2 methanation was carried out further at
The charge transfer from Ni to Zn transformed different reaction temperatures to study the
the metallic Ni with zero oxidation state to be performance of Ni on reducible metal supports
partially positive charged NiZn [33]. The NiZn at low temperatures (Figure 5, Table 2). All the
promoted the formation of CO2 hydrogenation catalysts were seen to be inactive at both 200
to C2 products due to further hydrogenation of °C and 250 °C but methane formation was
formate intermediates [34]. The formation of starting to observe at 300 °C, in exception for
5Ni/ZnO catalyst. Evidently, 5Ni/Sm2O3
showed the highest activity at low tempera-
tures with the CO2 conversion at 300 °C was
measured at 20.1%. The reactivity was then
followed by 5Ni/CeO2 and 5Ni/ZnO. At the vari-
ation of reaction temperatures, both 5Ni/CeO2
and 5Ni/Sm2O3 displayed 100% CH4 selectivity.
However, for 5Ni/ZnO, as reaction temperature
increased over 350 °C, 5Ni/ZnO only demon-
strated 73.7% selectivity towards methane,
with CO was produced as a side product. The
production of methane was enhanced at 450
°C, to give 87% selectivity with 26.6% conver-
sion of CO2.

3.6 Stability Studies of Ni/Sm2O3

To further investigate the stability of
5Ni/Sm2O3, catalytic reaction was carried out
Figure 5. CO2 methanation on 5Ni/Sm2O3,
for 28 h at 300 °C. Figure 6(a) showed the CO 2
5Ni/CeO2 and 5Ni/ZnO at temperatures be-
conversion was measured at 20% at the first 60
tween 200 °C to 450 °C.

Table 2. Catalytic activity of Ni on CeO2, Sm2O3 and ZnO at different reaction temperatures.

Temperature CO2 Conversion (%) CH4 Selectivity (%)

(°C) 5Ni/CeO2 5Ni/Sm2O3 5Ni/ZnO 5Ni/CeO2 5Ni/Sm2O3 5Ni/ZnO
200 0 0.2 0 0 100 0
250 0 1.9 0 0 100 0
300 1.3 20.1 0 100 100 0
350 8.1 31.8 3.5 100 100 73.7
400 27.7 59.4 10.5 100 100 87.0
450 52.1 69.3 26.6 99.5 100 94.7

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 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 647

min into the reaction. The conversion was sig- with a minimal bond energy [38]. Although the
nificantly improved after 2 h to give ~32% con- transition between cubic to monoclinic phase in
version and the conversion was stable for the Sm2O3 was reported at high temperatures
next 10 h of reaction. It is interesting to note ~1000 °C [39], there was a possibility that im-
that CO2 conversion was improved to ~51% at pregnation with Ni and annealing under H 2
15 h of reaction and the conversion was main- gas reduced the temperature for the phase
tained until 28 h. The XRD of the catalysts af- transformation. HRTEM analysis of Ni/Sm2O3
ter 5 h and 28 h were analyzed to determine further confirmed the presence of cubic and
the structural changes of 5Ni/Sm2O3 (Figure monoclinic phases (Figure 4). The distances be-
6(b)). XRD analysis of 5Ni/Sm2O3 following 5 h tween planes were measured to be 0.318 nm
reaction showed no significant differences on which corresponded to the (222) planes of cubic
the structure of the catalysts. All the peaks cor- phase Sm2O3 [31], meanwhile the monoclinic
responded to the Sm2O3 in the cubic crystal phase was identified with the shorten lattice
structure were visible, according to JCPDS spacing at 0.27 nm due to shorter distance be-
043-1029. When the XRD analysis was carried tween the ions with a minimal bond energy of
out on 5Ni/Sm2O3 after 28 h catalytic reaction, the monoclinic phase [38].
the new peak corresponded to Ni metal at 2θ = The activity of Ni nanoparticles was signifi-
47° was gained significant enhancement in in- cantly enhanced when Sm2O3 was used as sup-
tensity suggesting the NiO nanoparticles was port mainly due to the increase of Ni dispersion
sintered to form large Ni crystallites. Two new on Sm2O3. Despite the surface area of Sm2O3
peaks corresponded to Sm2O3 with monoclinic was significantly lower than ZnO and CeO 2,
phase were observed at 27° and 39.8° (JCPDS the number of Ni active sites on 5Ni/Sm2O3
card no 042-1464) [37]. The transition of Sm2O3 were determined at 18.5 mmol/g, which were
phase from cubic to monoclinic implied the in- higher than 5Ni/CeO2 at 6.8 mmol/g and
crease of catalytic activity after 10 h of reaction 5Ni/ZnO at 5.6 mmol/g. Apart from the disper-
maybe due to the formation of more active sion, the reducibility of metal nanoparticles al-
Sm2O3 sites due to the prolonged reduction un- so played an important role during the catalyt-
der CO2/H2/N2 mixed gas during reaction. Cu- ic reaction Surface oxygen vacancies improved
bic phase was characterized by a larger dis- the adsorption and dissociation of CO2. The en-
tance between the ions with isometric and ergy required for the formation of vacancies in
higher entropy, meanwhile monoclinic struc- reducible oxides was relatively low compared to
ture had a shorter distance between the ions the non-reducible metal oxide. The activity of

Figure 6. (a) CO2 methanation of 5Ni/Sm2O3 at 350 °C for 28 h; and (b) XRD analysis of post reaction
5Ni/Sm2O3 catalyst after 5 h and after 28 h.

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 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 648

non-reducible oxide support was generally cor- quirements. Biomass and Bioenergy, 133,
related with its basicity such as Al2O3 and zeo- 105447. DOI: 10.1016/j.biombioe.2019.105447
lite [40]. The dissociated hydrogen on Ni, was [3] Garbarino, G., Riani, P., Magistri, L., Busca,
spilled over to metal oxide support that can be G. (2014). A study of the methanation of car-
used to form oxygen vacancies. The Sm2O3 and bon dioxide on Ni/Al2O3 catalysts at atmos-
CeO2 with 4+ oxidation states reduced to 3+ pheric pressure. International Journal of Hy-
under hydrogen created oxygen vacancies to fa- drogen Energy, 39(22), 11557–11565. DOI:
cilitate CO2 adsorption. The proximity of 10.1016/j.ijhydene.2014.05.111
Ni/support interfacial contact in 5Ni/Sm2O3 [4] Everett, O.E., Zonetti, P.C., Alves, O.C., de
compared to 5Ni/CeO2, due to the formation of Avillez, R.R., Appel, L.G. (2020). The role of
highly dispersed metal nanoparticles, assisted oxygen vacancies in the CO2 methanation em-
the formation of oxygen vacancies. The highly ploying Ni/ZrO2 doped with Ca. International
dispersed Ni nanoparticles created a larger Journal of Hydrogen Energy, 45(11), 6352–
6359. DOI: 10.1016/j.ijhydene.2019.12.140
metal/support interaction, which was identified
as the active sites for CO2 methanation. Pro- [5] Makdee, A., Chanapattharapol, K.C.,
longed catalytic reaction further reduced the Kidkhunthod, P., Poo-arporn, Y., Ohno, T.
Sm2O3 via hydrogen spill over, which trans- (2020). The role of Ce addition in catalytic ac-
formed the cubic phase into monoclinic phase. tivity enhancement of TiO2-supported Ni for
CO2 methanation reaction. RSC Advances,
The combination of highly exposed metallic Ni
10(45), 26952–26971. DOI:
and the continuous formation of oxygen vacan- 10.1039/D0RA04934D
cies on Sm2O3 created Ni-VOx-Sm sites which
were essential for CO2 methanation [41]. [6] Gac, W., Zawadzki, W., Rotko, M., Słowik, G.,
Greluk, M. (2019). CO2 Methanation in the
Presence of Ce-Promoted Alumina Supported
4. Conclusion
Nickel Catalysts: H2S Deactivation Studies.
The activity of 5Ni/Sm2O3 was investigated Topics in Catalysis, 62(5), 524–534. DOI:
as catalysts for methanation reaction and com- 10.1007/s11244-019-01148-3
pared to another reducible oxide supports CeO2 [7] Zeng, L., Wang, Y., Li, Z., Song, Y., Zhang, J.,
and ZnO. The importance of metallic Ni to cata- Wang, J., He, X., Wang, C., Lin, W. (2020).
lyze methanation was further consolidated by Highly Dispersed Ni Catalyst on Metal–
the non-reactivity of 5Ni/ZnO catalysts due to Organic Framework-Derived Porous Hydrous
the formation of Ni-Zn alloy. Ni was highly dis- Zirconia for CO2 Methanation. ACS Applied
persed on Sm2O3 thus created a high interfacial Materials & Interfaces, 12(15), 17436–17442.
DOI: 10.1021/acsami.9b23277
contact for efficient formation of oxygen vacan-
cies during catalytic reaction. The enhance- [8] Guilera, J., del Valle, J., Alarcón, A., Díaz, J.
ment of CO2 conversion after 10 h of reaction A., Andreu, T. (2019). Metal-oxide promoted
implied the formation of oxygen vacancies were Ni/Al2O3 as CO2 methanation micro-size cata-
continuously formed during the reaction, re- lysts. Journal of CO2 Utilization, 30, 11–17.
DOI: 10.1016/j.jcou.2019.01.003
sulting in the transition of Sm2O3 crystal phase
from cubic to monoclinic. [9] Le, M.C., Van, K.L., Nguyen, T.H.T., Nguyen,
N.H. (2017). The Impact of Ce-Zr Addition on
Acknowledgement Nickel Dispersion and Catalytic Behavior for
CO2 Methanation of Ni/AC Catalyst at Low
Authors would like to acknowledge Univer- Temperature. Journal of Chemistry, 2017,
siti Brunei Darussalam Research Grant UB- 4361056. DOI: 10.1155/2017/4361056
D/RSCH/URC/RG(b)/2019/012 for funding of [10] Daroughegi, R., Meshkani, F., Rezaei, M.
the project. (2021). Enhanced low-temperature activity of
CO2 methanation over ceria-promoted Ni-
References Al2O3 nanocatalyst. Chemical Engineering
Science, 230, 116194. DOI:
[1] Su, X., Xu, J., Liang, B., Duan, H., Hou, B., 10.1016/j.ces.2020.116194
Huang, Y. (2016). Catalytic carbon dioxide hy-
drogenation to methane: A review of recent [11] Bansode, A., Tidona, B., von Rohr, P.R., Ura-
studies. Journal of Energy Chemistry, 25(4), kawa, A. (2013). Impact of K and Ba promot-
553–565. DOI: 10.1016/j.jechem.2016.03.009 ers on CO2 hydrogenation over Cu/Al2O3 cata-
lysts at high pressure. Catalysis Science &
[2] Boggula, R.R., Fischer, D., Casaretto, R., T e c hno lo gy , 3 (3 ), 7 67 – 7 7 8. D O I:
Born, J. (2020). Methanation potential: Suita- 10.1039/C2CY20604H
ble catalyst and optimized process conditions
for upgrading biogas to reach gas grid re-

Copyright © 2021, ISSN 1978-2993

 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 649

[12] Takano, H., Shinomiya, H., Izumiya, K., [21] Bahruji, H., Armstrong, R.D., Ruiz Esquius,
Kumagai, N., Habazaki, H., Hashimoto, K. J., Jones, W., Bowker, M., Hutchings, G.J.
(2015). CO2 methanation of Ni catalysts sup- (2018). Hydrogenation of CO2 to dimethyl
ported on tetragonal ZrO2 doped with Ca2+ ether over Brønsted acidic PdZn catalysts. In-
and Ni2+ ions. International Journal of Hydro- dustrial & Engineering Chemistry Research,
gen Energy, 40(26), 8347–8355. DOI: 57(20), 6821–6829. DOI:
10.1016/j.ijhydene.2015.04.128 10.1021/acs.iecr.8b00230.
[13] Dreyer, J.A.H., Li, P., Zhang, L., Beh, G.K., [22] Bahruji, H., Bowker, M., Jones, W., Hayward,
Zhang, R., Sit, P.H.L., Teoh, W.Y. (2017). In- J., Ruiz Esquius, J., Morgan, D.J., Hutchings,
fluence of the oxide support reducibility on G.J. (2017). PdZn catalysts for CO2 hydro-
the CO2 methanation over Ru-based catalysts. genation to methanol using chemical vapour
Applied Catalysis B: Environmental, 219, impregnation (CVI). Faraday Discussions,
715–726. DOI: 10.1016/j.apcatb.2017.08.011 197(0), 309–324. DOI: 10.1039/C6FD00189K
[14] Atzori, L., Cutrufello, M.G., Meloni, D., Mon- [23] Bahruji, H., Esquius, J.R., Bowker, M.,
aci, R., Cannas, C., Gazzoli, D., Sini, M.F., Hutchings, G., Armstrong, R.D., Jones, W.
Deiana, P., Rombi, E. (2017). CO2 methana- (2018). Solvent Free Synthesis of PdZn/TiO2
tion on hard-templated NiOCeO2 mixed ox- Catalysts for the Hydrogenation of CO2 to
ides. International Journal of Hydrogen Ener- Methanol. Topics in Catalysis, 61(3-4), 144–
gy, 42(32), 20689–20702. DOI: 153. DOI: 10.1007/s11244-018-0885-6
10.1016/j.ijhydene.2017.06.198
[24] Rui, N., Zhang, X., Zhang, F., Liu, Z., Cao, X.,
[15] Fukuhara, C., Hayakawa, K., Suzuki, Y., Ka- Xie, Z., Zou, R., Senanayake, S.D., Yang, Y.,
wasaki, W., Watanabe, R. (2017). A novel Rodriguez, J.A., Liu, C. (2021). Highly active
nickel-based structured catalyst for CO2 Ni/CeO2 catalyst for CO2 methanation: Prepa-
methanation: A honeycomb-type Ni/CeO2 cat- ration and characterization. Applied Cataly-
alyst to transform greenhouse gas into useful sis B: Environmental, 282, 119581. DOI:
resources. Applied Catalysis A: General, 532, 10.1016/j.apcatb.2020.119581.
12–18. DOI: 10.1016/j.apcata.2016.11.036
[25] Thommes, M., Kaneko, K., Neimark, A.V.,
[16] Tok, A.I.Y., Du, S.W., Boey, F.Y.C., Chong, Olivier, J.P., Rodriguez-Reinoso, F., Rouquer-
W.K. (2007). Hydrothermal synthesis and ol, J., Sing, K.S.W. (2015). Physisorption of
characterization of rare earth doped ceria na- gases, with special reference to the evalua-
noparticles. Materials Science and Engineer- tion of surface area and pore size distribution
ing: A, 466(1), 223 –229. DOI: (IUPAC Technical Report). Pure and Applied
10.1016/j.msea.2007.02.083 Chemistry, 87(9-10), 1051–1069. DOI:
10.1515/pac-2014-1117
[17] Taherian, Z., Yousefpour, M., Tajally, M.,
Khoshandam, B. (2017). A comparative study [26] Alothman, Z.A. (2012). A Review: Fundamen-
of ZrO2, Y2O3 and Sm2O3 promoted Ni/SBA-15 tal Aspects of Silicate Mesoporous Materials.
catalysts for evaluation of CO2/methane re- Materials, 5(12), 2874–2902. DOI:
forming performance. International Journal 10.3390/ma5122874
of Hydrogen Energy, 42(26), 16408–16420.
[27] Dias, Y.R., Perez-Lopez, O.W. (2020). Carbon
DOI: 10.1016/j.ijhydene.2017.05.095
dioxide methanation over Ni-Cu/SiO2 cata-
[18] Ilsemann, J., Sonström, A., Gesing, T.M., lysts. Energy Conversion and Management,
Anwander, R., Bäumer, M. (2019). Highly Ac- 2 0 3 , 1 2 2 1 4 . D O I :
tive Sm2O3-Ni Xerogel Catalysts for CO2 10.1016/j.enconman.2019.112214.
Methanation. ChemCatChem, 11(6), 1732–
[28] Lv, C., Xu, L., Chen, M., Cui, Y., Wen, X., Wu,
1741. DOI: 10.1002/cctc.201802049
C., Yang, B., Wang, F., Miao, Z,. Hu, X.,
[19] Brix, F., Desbuis, V., Piccolo, L., Gaudry, É. Shou, Q. (2020). Constructing highly dis-
(2020). Tuning Adsorption Energies and Reac- persed Ni based catalysts supported on fi-
tion Pathways by Alloying: PdZn versus Pd brous silica nanosphere for low-temperature
for CO2 Hydrogenation to Methanol. The CO2 methanation. Fuel, 278, 118333. DOI:
Journal of Physical Chemistry Letters, 11(18), 10.1016/j.fuel.2020.118333.
7672–7678. DOI: 10.1021/acs.jpclett.0c02011
[29] Qi, J., Hu, X. (2020). The loss of ZnO as the
[20] Ojelade, O.A., Zaman, S.F., Daous, M.A., Al- support for metal catalysts by H2 reduction.
Zahrani, A.A., Malik, A.S., Driss, H., Shterk, Physical Chemistry Chemical Physics, 22(7),
G., Gascon, J. (2019). Optimizing Pd:Zn molar 3953–3958. DOI: 10.1039/c9cp06093f.
ratio in PdZn/CeO2 for CO2 hydrogenation to
[30] Lee, J., Ryou, Y., Chan, X., Kim, T.J., Kim,
methanol. Applied Catalysis A: General, 584,
D.H. (2016). How Pt Interacts with CeO2 un-
117185. DOI: 10.1016/j.apcata.2019.117185
der the Reducing and Oxidizing Environ-
ments at Elevated Temperature: The Origin

Copyright © 2021, ISSN 1978-2993

 Bulletin of Chemical Reaction Engineering & Catalysis, 16 (3), 2021, 650

of Improved Thermal Stability of Pt/CeO2 [37] Sone, B.T., Manikandan, E., Gurib-Fakim, A.,
Compared to CeO2. The Journal of Physical Maaza, M. (2015). Sm2O3 nanoparticles green
Chemistry C, 120(45), 25870–25879. DOI: synthesis via Callistemon viminalis' extract.
10.1021/acs.jpcc.6b08656 Journal of Alloys and Compounds, 650, 357–
362. DOI: 10.1016/j.jallcom.2015.07.272
[31] Kang, J.-G., Min, B.-K., Sohn, Y. (2015). Syn-
thesis and characterization of Sm(OH)3 and [38] Barad, C., Kimmel, G., Hayun, H., Shamir,
Sm2O3 nanoroll sticks. Journal of Materials D., Hirshberg, K., Gelbstein, Y. (2020). Phase
S c i e nc e , 50(4), 1958–1964. DOI: Stability of Nanocrystalline Grains of Rare-
10.1007/s10853-014-8760-8 Earth Oxides (Sm2O3 and Eu2O3) Confined in
Magnesia (MgO) Matrix. Materials, 13(9),
[32] Zhou, G., Liu, H., Cui, K., Jia, A., Hu, G.,
2201. DOI: 10.3390/ma13092201
Jiao, Z., Liu, Y., Zhang, X. (2016). Role of sur-
face Ni and Ce species of Ni/CeO2 catalyst in [39] Zinkevich, M. (2007). Thermodynamics of ra-
CO2 methanation. Applied Surface Science, re earth sesquioxides. Progress in Materials
3 8 3 , 2 4 8 – 2 5 2 . D O I : Science, 52(4), 597–647. DOI:
10.1016/j.apsusc.2016.04.180 10.1016/j.pmatsci.2006.09.002
[33] Samanta, A., Das, S., Jana, S. (2020). Ultra- [40] Sholeha, N.A., Jannah, L., Rohma, H.N.,
small intermetallic NiZn nanoparticles: a Widiastuti, N., Prasetyoko, D., Jalil, A.A.,
non-precious metal catalyst for efficient elec- Bahruji, H. (2020). Synthesis of Zeolite NaY
trocatalysis. Nanoscale Advances, 2(1), 417– from Dealuminated Metakaolin as Ni Sup-
424. DOI: 10.1039/C9NA00611G port for CO2 Hydrogenation to Methane.
Clays and Clay Minerals, 68(5), 513–523.
[34] Zhang, XD., Liu, K., Fu, JW., Li, HM., Pan,
https://doi.org/10.1007/s42860-020-00089-3
H., Hu, JH., Liu, M. (2021). Pseudo-copper
Ni-Zn alloy catalysts for carbon dioxide reduc- [41] Tada, S., Nagase, H., Fujiwara, N., Kikuchi,
tion to C2 products. Frontiers of Physics, 16, R. (2021). What Are the Best Active Sites for
63500. DOI: 10.1007/s11467-021-1079-4 CO2 Methanation over Ni/CeO2?. Energy &
Fuels, 35(6), 5241–5251. DOI:
[35] Goyal, R., Lee, W.J., Sameer, S., Sarkar, B.,
10.1021/acs.energyfuels.0c04238
Chiang, K., Bordoloi, A. (2020). CNx stabi-
lized Ni-Ga nanoparticles for CO2 hydrogena-
tion: Role of preparation methods. Catalysis
Today, 343, 48–55. DOI:
10.1016/j.cattod.2019.03.031
[36] Sokolov, S., Radnik, J., Schneider, M.,
Rodemerck, U. (2017). Low-temperature CO2
reforming of methane over Ni supported on
ZnAl mixed metal oxides. International Jour-
nal of Hydrogen Energy, 42(15), 9831–9839.
DOI: 10.1016/j.ijhydene.2017.01.013.

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