i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1

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Highly stable M/NiOeMgO (M ¼ Co, Cu and Fe)

catalysts towards CO2 methanation

Yaddanapudi Varun, I. Sreedhar, Satyapaul A. Singh*

Department of Chemical Engineering, Birla Institute of Technology and Science (BITS) Pilani, Hyderabad Campus,
Jawahar Nagar, Kapra Mandal, Hyderabad, 500 078, India

highlights graphical abstract

NiOeMgO support was prepared

by combustion, precipitation and
sonochemical routes.

95% CO2 conversion is obtained

around 400 C with 2%Co/NiO
eMgO.

Co/NiOeMgO via sonochemical
route showed lowest activation
energy.

Reaction mechanism and kinetics
was developed based on
Langmuir-Hinshelwood model.

All M/NiOeMgO (M ¼ Fe, Co, and
Cu) catalysts are stable even after
50 h time.

article info abstract

Article history: NiOeMgO nanocomposites are synthesized using solution combustion, sonochemical, and
Received 5 June 2020 co-precipitation synthesis to understand the catalytic activity of CO2 methanation. Excel-
Received in revised form lent particle size distribution was noticed with the sonochemical routed synthesis method,
16 July 2020 and the CO2 conversions are found to be better with the same synthesis protocol. Surface
Accepted 23 July 2020 modifications in NiOeMgO composite were incorporated by doping M (M ¼ Co, Fe, and Cu).
Available online 12 August 2020 The active catalysts are characterized by X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron mi-
Keywords: croscopy (TEM) to understand physical, structural properties and surface morphology of
NiOeMgO nanocomposites the nanocomposites. All catalysts showed excellent catalytic activity for the conversion of
Sonochemical synthesis CO2 to methane and selectivity towards methane to be higher than 85%. However, 2%Co/
Reaction mechanism NiOeMgO showed the lowest activation energy of about 43 ± 2 kJ mol1 among other
CO2 methanation synthesized catalysts. The mechanism of CO2 methanation was investigated with the in-
Co, Fe, and Cu doping puts from temperature programming reduction with H2 (H2-TPR), and temperature pro-
Kinetics gramming desorption with CO2 (CO2-TPD) studies. Detailed reaction mechanism and
kinetics are investigated for all doped catalysts. M/NiOeMgO offered excellent stability up
to 50 h reaction time with high CO2 conversions and CH4 selectivities.

* Corresponding author.
E-mail address: [email protected] (S.A. Singh).
https://doi.org/10.1016/j.ijhydene.2020.07.212
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1 28717

© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

supports. Using an appropriate promoter is a simple idea to

Introduction boost catalytic efficiency. Cobalt (Co) be able to progress metal
dispersion, modify metal support interactions, and change the
Carbon dioxide (CO2) emissions are a vital source of interest surface basicity. These properties enhance the stability of the
worldwide due to global warming. An increase in CO2 emis- Co-promoted catalysts for longer durations [24e26]. Apart
sions will be continued for the next few decades. Studies have from metal oxide supports over Ni-based catalysts, zeolites
indicated that by 2040, 35.7 Gt of CO2 releases into the atmo- are other class of materials that presented higher activity at
sphere [1]. Therefore, it is essential to create an appropriate low temperatures. Kopula Kesavan et al. [27] found that YSZ
scheme for capturing and utilizing CO2 to decrease its con- reinforced Ni catalysts best catalytic performance towards
centration in the atmosphere. Membrane separation [2] CO2 methanation. No deactivation and variation in oxidation
techniques for carbon capture and storage have been lately states (from Ni0 to Ni2þ) was detected even after 30 h of re-
employed [3,4], however, they have limited scope for action, which offered long-term stability for CO2 methanation.
commercialization. Concerning the industrial use, many re- Another study on Ni doped YSZ having a tubular structured
searchers have investigated about storage and conversion of catalyst gave good catalytic CO2 conversion and methane
CO2 into reusable product [5,6], the main viewpoint of appli- selectivity (>70% and 99%) at 270  C [28]. Yanrong Li et al. [6]
cations are dry reforming of methane [7e12] and CO2 metha- demonstrated the integration of SiO2 into Ni-containing
nation [13,14]. Subsequently, the products like synthesis gas, magnesium catalysts stimulated the catalytic activity in CO2
methane, methanol, and dimethyl ether formed from these methanation reaction by making new core-shell nano-
reactions can be used as immediate raw material for in- structures. As a part of their study, NiOeMgO@SiO2 core-shell
dustries. Moreover, CH4 is one of the favorable hydrogen nanocomposite exhibited long-term stability of 100 h at
carriers [15] for the transportation and a low cost fuel in the 300  C, which is an extraordinarily active and selective cata-
form of natural gas [7,15]. lyst for CO2 methanation. However, role of the promoter has a
CO2 methanation is a highly exothermic reaction, catalysts limited focus on CO2 methanation studies in the literature.
for a proficient method essential to be lively at low tempera- In this study, the primary objective is to understand the
tures, very selective, and steady in real-world environments. importance of synthesis protocol on the factor of particle size
While performing this reaction, it has been reported that distribution of NiOeMgO. Second objective is to understand
carbon monoxide (CO) formation through the reverse water the role of surface basicity with respect doping different
gas shift reaction (r-WGS) is possible and it remains as un- transition metal over NiOeMgO. The effect of a synthesis
wanted by-product. In many studies, the selection for both protocol for support fabrication is investigated to enhance
CO2 and CO methanation catalysts was limited to ruthenium strong metal-support interaction (SMSI). In addition to the
and nickel catalysts due to their stability and selectivity. At support, MgO as a promoter is used to improve the adsorption
low temperatures, mainly ruthenium is more active and capacity of CO2 at a lower temperature by increasing the Lewis
vastly selective to generate methane [16e18]. Ni is known as basic sites. The third objective is intended to explore the as-
the least expensive and suitable material for CO2 methanation sociation between catalytic activity and physicochemical
in terms of selectivity apart from Ru. characteristics that concentrate on trimetallic composites
Several studies stated the Ni-based promoters presented deducing the function of assistance. The final objective is to
enhanced catalytic performance and high methane selectivity investigate the kinetics of CO2 methanation with the assis-
at low temperatures [14,19,20]. Ashok et al. [21] conveyed that tance of mechanistic aspects. As a part of this study, all these
the Ni/CeO2eZrO2 catalyst showed superior stability and catalysts are characterized by XRD, XPS, SEM, TEM, and BET
higher conversions of CO2 at 275  C, which specifies the low- for understanding surface and morphological characteristics.
temperature activity of catalyst performance. Similar studies Comprehensively, elucidating the reaction mechanism by
by Leiel Xu et al. [22] exhibited that the Ni-based catalysts tuning the surface basicity, detailed mechanistic and kinetic
doped with rare-earth materials prepared in mesoporous investigation over NiOeMgO supports is the primary focus
range, showed enhanced stability and rational conversions and novelty of our work.
rates of CO2 at shallow temperatures in between 225 and
250  C. The primary reason for such a predominant catalytic
activity is due to the interaction between the species of Ni over Experimental
rare earth metals. A recent study demonstrated that the Ni-
based ternary and quaternary oxides catalysts with CeO2 Materials
offer low-temperature methanation activity [23]. It has been
also reported that the Ni with alumina support catalyst as an Magnesium nitrate hexahydrate (Mg(NO3)2.6H2O), nickel ni-
active catalyst in CO2 methanation, however, this catalyst trate hexahydrate (Ni(NO3)2.6H2O), cobalt nitrate hexahydrate
falls short in the catalytic conversions compared to other (Co(NO3)2$6H2O), cupric nitrate trihydrate (Cu(NO3)2$3H2O),
28718 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1

iron (III) nitrate nonahydrate (Fe(NO3)3.9H2O), diethylenetri- stirring. 5 mL of hydrazine hydrate was added as a reducing
amine (DETA, C4H13N3), hydrazine Hydrate (NH2eNH2.H2O), agent; upon its addition, the pH was observed to be in the
polyethyleneglycol (PEG-400, C2nH4nþ2Onþ1), ethanol (C2H5OH, range of 9e10. After that vigorous stirring, the solution was
AR) were procured from Hychem Laboratories Pvt. Ltd., India. subjected to probe sonication employing a high-intensity
The selected gases for the experiments and analysis are CO2 probe sonicator (Vibra cell processors, India) operated at
(99.99%), H2 (99.99%), CH4 (48.4% rest N2), and CO (9.8% and rest 130 W and 20 kHz with 20 s ON and 15 s OFF cycle for 1 h. The
N2). All the gases were procured from Chemix gases, India. collected sample was kept in a hot air oven for drying at 120  C
for 2 h, and the dried powder calcined at 700  C for 2 h.
Catalyst synthesis
Characterization techniques
Catalyst synthesis by sonochemical method
In a typical methodology, 0.1 M of Ni (NO3)2.6H2O of 100 mL Rigaku X-ray diffraction instrument with Cu-Ka radiation
solution added to 0.25 M of Mg (NO3)2.6H2O of 100 mL solution. source was used at 40 kV and 30 mA for powder diffraction
4 mL of PEG-400 was added to the aqueous solution to control analysis. The diffractometer patterns are observed with a scan
the growth of nanoparticles. To the resulted viscous solution, speed of 2 /min and step size 0.02 , in the 2q range of 10 e90 .
4 mL of (DETA) was added to ensure adequate dispersion. A Belsorb surface analyzer used to determine the catalyst
Along with vigorous stirring, a high-intensity sonicator (Vibra surface area and pore volume at 77 K with a liquid N2 bath. The
cell Processors, India) with an output rate of 130 W for 5 h micrographs of all catalysts were recorded with a high vac-
(effective sonication time is 3 h), frequency of 20 kHz with 20 s uum and 20 kV using thermo-scientific, APEROS field-
ON and 15 s OFF cycle was applied to the resulting precursor emission scanning electron microscope (FESEM). SAED pat-
solution. The generated composite nanoparticles were terns and transmission electron microscopy images were
collected by centrifugation of the colloidal solution. The conducted with JOEL JEM 2100 P, and X-ray photoelectron
collected sample was washed with ethanol four times and spectra for 2% Co/Cu/Fe substituted NiOeMgO were collected
dried for 8 h at 120  C. The product was calcined at 700  C for using the AXIS ULTRA spectrophotometer with Al Ka radiation
4 h. Further, the material was well ground and used for cata- source. The spectra were standardized with graphitic carbon
lytic reactions. with a binding energy of 284.8 eV.

Catalyst synthesis by co-precipitation Temperature programming reduction with H2 (H2 e TPR)

A standard methodology has been rendered with the addition
of 0.1 M of 100 mL Ni(NO3)2.6H2O to 100 mL of 0.25 M of TPR studies were performed to know the reducible nature of
Mg(NO3)2.6H2O with continuous ageing of 2 h 1 M of NH4OH catalysts in the presence of hydrogen. In a typical study, 25 mg
solution was added dropwise until pH reaches ~9e10. The of catalyst was filled between the glass wool plugs at the core
colloidal solution was centrifuged to collect the precipitate. of the quartz tube. 10% H2 (rest N2) gas was passed through the
The obtained precipitate was washed four times with ethanol catalyst at a flow rate of 50 mL/min with a programmable PID
and dried for 6 h at 150  C, and then the sample was subjected controller at a ramping rate of 10  C/min up to 700  C. The
to calcination for 4 h at 700  C. consumption of H2 was monitored by using a thermal con-
ductivity detector, which was procured from Mayura analyt-
Catalyst synthesis by solution combustion method ical, India.
The stoichiometric composition of oxidizers Mg (NO3)2.6H2O
and Ni (NO3)2.6H2O to fuel (glycine) ratio was calculated by Temperature programming desorption with CO2 (CO2eTPD)
considering the reducing valences of components based on
the theory of propellant chemistry for solution combustion TPD studies were implemented for all the catalysts to
synthesis [29]. In a typical synthesis protocol, 6.4 g of Mg comprehend the adsorption rate of catalyst. In a characteristic
(NO3)2.6H2O, 2.90 g of Ni (NO3)2.6H2O, and 2.5 g of glycine were study, 25 mg of catalyst was filled between the glass wool
taken in a crystallizing dish (50  100 mm) and dissolved in the plugs inside a quartz tube. The samples were purged with
minimum amount of water, based on the solubility of pre- pure CO2 for 1 h at a flow rate of 50 mL/min. After passing CO2,
cursors. The prepared aqueous solution was stirred continu- the quartz tube was heated up to 500  C in the presence of
ously for 1 h to ensure proper solubility of components in helium as a carrier gas at a flow rate of 50 mL/min and a
distilled water. The aqueous solution was kept in a muffle ramping rate of 10  C/min. A thermal conductivity detector
furnace at 400 ± 10  C. The combustion was propagated within (Mayura analytical, India) was used to monitor the desorption
10 min of thermal exposure and resulted in the formation of of CO2.
dry nanomaterial with the evolution of a large volume of
fumes. The dried porous material was well-ground and sub- Catalytic CO2 methanation studies
jected to calcination at 700  C for 4 h.
The catalysts were pelletized using sieves of 60/80 mesh-size.
Catalyst synthesis of Co/Cu/Fe impregnation on NiOeMgO 100 mg of catalyst was filled between the ceramic wool plugs
inside a 4 mm internal diameter quartz reactor. Catalytic bed
In a typical wet-impregnation protocol, 7 mM of 50 mL solu- length of 1 cm was maintained by diluting the catalyst with
tion of copper or iron or cobalt nitrate was added dropwise to quartz sand of equivalent size. The catalyst loading was taken
NiOeMgO dispersion loading of 1 g in 100 mL with continuous in between 0 to 100 mg for the study of the apparent activation
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1 28719

energy estimation. The sample was pretreated at 120  C for 1 h patterns. Peak shift indicates that NiO and MgO phases are in
with the same reactant flow conditions. The reactants flow the same planes and having adequate dispersion. All the
rate composed of 2 vol% CO2, 16 vol% H2, and 82 vol% N2 was materials were primed by sonochemical synthesis with ni-
kept with a flow rate of 100 N mL/min (N ¼ NTP conditions) trates as raw precursors, which may generate impurities due
and the gas hourly space velocity (GHSV) of 47,760 h1 for all to nitrates. However, nitrate peaks and CoO, Fe2O3, and CuO
catalytic activity studies. A condenser was connected at the phases associated peaks are not witnessed because of the
exit of the reactor to remove the steam which may have aggregation of doped ions. From the Debye-Scherrer relation,
generated due to undesirable reactions and dry gases alone the crystallite size of the prepared catalysts was analyzed by
allowed to pass through online gas chromatograph to analyze taking the values full width half maxima (FWHM) of the three
the outlet gas composition. CO2 conversion and CH4 selec- most intense peaks from the data. In the reference, the
tivity are calculated using the formulae given below, exposure of plane (200) has almost the same d-spacing value,
and the remaining planes (111) and (220) are slightly low. All
F½CO2 in  F½CO2 Out
CO2 conversion ¼ (1) the physical parameters and surface areas are listed in Table
F½CO2 in
1.

F½CH4 Out Morphological studies

CH4 selectivity ¼ (2)
F½CH4 Out þ F½COOut

Here, F½CO2 in is inlet molar flowrate of CO2, F½CO2 Out is outlet SEM images of NiOeMgO nanocomposites prepared by
molar flowrate of CO2, F½CH4 Out is outlet molar flowrate of CH4 different synthesis protocols are shown in Fig. S2. It is clear to
and F½COOut is outlet molar flowrate of CO. notice narrow and homogenous particle size distribution with
sonochemical synthesis protocol. High local combustion,
adiabatic flame temperatures and pH of the solution could be
Results and discussion the prime reasons for high rate of nucleation with solution
combustion and co-precipitation routes, which ultimately
XRD studies resulted larger average particle sizes than that of sonochem-
ical synthesis.
The XRD patterns of NiOeMgO supports synthesized using co- As per the images shown in the Fig. 2, NiOeMgO support is
precipitation, and solution combustion methods are shown in merged with the dopant. As the support and dopant cluster
Fig. S1 of supporting information. All three methods resulted sizes and in equivalent ratios, the distinction between dopant
in pure phases of NiO and MgO. The XRD patterns of the and support was unclear. All catalysts showed no metal
synthesized catalysts with dopants are presented in Fig. 1, deformation and indicated definite XRD patterns as shown in
both the NiO and MgO phases were verified with JCPDS ref- Fig. 1. The pore volume of the catalysts was found to high for
erences 01-001-1239 and 01-001-1235. The NiOeMgO is the doped catalysts. From Fig. 2(a)e(c), the uniform particle
comprised of cubic NiO (a ¼ b ¼ c ¼ 4.1710
A, space group: Fm- size distribution is noticed with NiOeMgO, Cu/NiOeMgO and
3m) and cubic MgO (a ¼ b ¼ c ¼ 4.2030
A, space group: Fm-3m). Co/NiOeMgO catalysts. The flaky distribution was occurred
With the highest peak intensity, it is observed that the NiO with Fe doping over NiOeMgO support, which can be seen
and MgO are in the same phase (42 e43 ), and there is a small from Fig. 2(d). Due to its flaky morphology the pore volume
shift with the 2q values from comparing with the reference was found to be higher compared with the other doped (Co
and Cu) materials and NiOeMgO. Calcination temperature
also plays an important role in the formation of particle size.
Since the calcination was performed at a high temperature of
700  C the agglomeration of the particles is found to be more.

Table 1 e Textual and physical properties of the

synthesized catalysts.
Catalyst Average Specific surface Specific pore
crystallite size area (m2/g) volume (cm3/g)
(nm)
NiO 18 49 0.0883
eMgO
2%Co/ 17 68 0.0931
NiO
eMgO
2%Fe/ 15 68 0.1334
NiO
eMgO
2%Cu/ 19 57 0.1133
Fig. 1 e X-ray diffraction patterns of NiOeMgO and 2%Co/ NiO
eMgO
Cu/Fe deposited on NiOeMgO catalysts.
28720 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1

Fig. 2 e Scanning electron microscopic images of (a) NiOeMgO (b) 2% Co/NiOeMgO (c) 2% Cu/NiOeMgO (d) 2% Fe/NiOeMgO.

The mean particle size of the catalysts was estimated to be conversion and methane selectivity. From the obtained re-
65 ± 5 nm. The particle sizes for all materials prepared by the sults, the catalytic studies have been extended to other
sonochemical method were analyzed and shown in Fig. S3 of impregnated catalysts. Role of the synthesis methods on the
Supplementary Information. 2%Co/NiOeMgO showed less catalytic activity studies of NiOeMgO was shown in Fig. 4. CO2
particle size compared to other catalysts. In fact, it is proved methanation might be affected by the synthesis method of the
that sintered particles help in improving the catalytic activity catalyst through the dispersion of active sites. The prepara-
studies [30]. The sizes of the catalyst nanoparticles with tion method affected the maximum conversion temperatures
dopants were observed from the SEM images shown in Fig. 2. of CO2, which typically occur above 350  C. The catalytic ac-
From Fig. 3, the presence of Ni (111), (200) and (220) was tivity was enhanced by sonochemical modified catalyst
detected from the lattice fringes of the particles. (111), (200), compared with other conventional methods such as solution
(220) planes of MgO were confirmed by analyzing diffraction combustion and co-precipitation. The results showed that the
rings as well (Fig. 3 (c), (f), (i), and (l)). The dopants might be sonochemical method could advance reactivity of M/
oxidized by consuming bulk oxygen or oxygen vacancies in NiOeMgO catalysts. The impregnation method further
the support which will enhance the catalytic activity enhanced the overall surface area, which could increase the
[28,31,32]. The EDS mapping for all the catalysts from HRTEM number of active sites in the catalyst system. The catalyst
images confirms the presence of Cu, Co and Fe in the syn- developed with sonochemical method exhibited higher con-
thesized catalysts (shown in Fig. S5), In all the catalysts, cop- version rates. This could be due to high dispersion of redox
per presence is noticed in all samples because of drop casting active sites. It has been reported that the redox nature of
of catalyst over copper grids (300 mesh, 83 mm pitch). However, support can be influenced by a synthesis method [33].
for Cu/NiOeMgO, Cu atomic % is significant, that confirms the Therefore, CO2 methanation can be dependent on type of
doping of Cu. Fig. 3 (b), (e), (h) and (k) shows the HRTEM images preparation method and can be route to develop a most active
of NiOeMgO, 2% M/NiOeMgO (M ¼ Co, Cu and Fe) and the d e metal. Thus, sonochemically synthesized NiOeMgO as a
spacing of lattice fringes were observed as 2.10
A, 1.48

A and suitable support for CO2 methanation and the further modi-
2.43
A correspondingly. The d e spacing values are approxi- fications with Co, Cu, and Fe on it are discussed in later
mately the same for Ni (111) (200) and (220) planes. sections.
Fig. 5(a) and (b) depict CO2 conversions and CH4 selectiv-
Catalytic activity studies ities of the 2% M/NiOeMgO (M ¼ Co, Fe and Cu) catalysts.
There is precarious importance in catalytic efficiency found in
Primarily, the synthesis of NiOeMgO was done by using three its morphology, crystalline size, reducibility, and deactivation
conventional methods. The three modes of approach for the strength [34,35]. The reaction temperatures below 250  C,
catalyst synthesis were discussed in section Catalyst every catalyst showed low CO2 conversions (<30%). At tem-
synthesis by sonochemical method, Catalyst synthesis by perature above 250  C, CO2 conversions are found to be higher.
co-precipitation, Catalyst synthesis by solution combustion The maximum conversion of CO2 was achieved at 400  C for all
method . The synthesized catalysts were subjected to CO2 catalysts, which is 84%, 86%, 89%, and 90% for NiOeMgO and
methanation studies with similar reaction conditions for all M/NiOeMgO (M ¼ Cu, Fe and Co) catalysts respectively. After
the samples. The sonochemical route gave the best CO2 400  C, decrease in the conversion of CO2 was observed for all
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1 28721

Fig. 3 e Bright-field, high-resolution transmission electron microscope images and SAED patterns of (a, b and c) NiOeMgO,
(d, e, and f) 2% Co/NiOeMgO, (g, h and i) 2% Cu/NiOeMgO, and (j, k, and l) 2%Fe/NiOeMgO.

catalysts. Such reduction in conversion can be attributed to a between the adsorbed CO2 and surface H2 to form methane at
reverse water gas shift reaction, which is thermodynamically low temperature. Fe also has the same ability to adsorb CO2
ideal at high temperatures for turning CO2 into CO. By using but to reach higher rates of conversion it requires to form
the sonication process, the dispersion of Ni nanoparticles on FeeNi alloys [24,35]. However, alloy formation is improbable
Mg can be done in a homogenous way [36], which can influ- because of the substitution of Fe on NiOeMgO system is very
ence the CO2 methanation activities. The effect of adding low (~2%), which cannot be seen from XRD patterns.
materials like Cu, Fe, and Co on NiOeMgO nanocomposite Cu-promoted catalysts exhibited low-slung CO2 conver-
further controls the catalytic efficiency concerning to selec- sion compared to Co/Fe doped NiOeMgO samples (Fig. 5 (a)).
tivity and conversion. Whereas compared to Cu, the catalytic From 200 to 300  C, very less conversions were observed. The
efficiency has increased enormously with Co doping at low maximum conversion over Cu/NiOeMgO was about 45% at
temperatures. In the presence of Co, the reaction rates are 300  C. It is clear that the impregnation of Cu addition on
found to be high with respect to conversion due to the avail- NiOeMgO leads to lesser conversions compared to NiOeMgO.
ability of Co metallic sites [24]. Similarly, Guilin Zhou et al. also At low temperatures, Cu shows more tendency to reduce
stated the same observation, when the metal Co doping on the catalyst activity [38]. Another reason for the less activity of
surface it will enhance the catalytic activity [37]. Moreover, the CO2 methanation over Cu is its low hydrogen adsorption af-
presence of MgO as a promoter can allow the material to finity, which will make it a less active for hydrogen dissocia-
adsorb CO2 at higher rates providing the more interaction time tion [39]. At high temperatures, along with the reduction of
28722 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1

100 much further. This could be the possible reason for sudden
NiO-MgO-Sono decrease in the CO2 conversion and CH4 selectivity observed in
NiO-MgO-Solution Fig. 5. In literature it is reported that Cu based catalysts pro-
80 NiO-MgO-CP motes the formation of CO at higher temperatures [40,41], this
could be another possibility for the low selectivity of CH4
% CO2 Conversion

60 shown in Fig. 5(b).

Catalytic process sequences for T90% are as follows: 2%Co/
NiOeMgO > 2%Fe/NiOeMgO > 2%Cu/NiOeMgO > NiOeMgO.
40
Further, percentage yield of CH4 for all catalysts is showed in
Fig. S4. The main products of the reaction are methane with a
20 minor amount of carbon monoxide in the low-temperature
region (<350  C). Methane selectivity has been monitored
throughout the reaction time to understand the role of side
0
reactions. 100% of methane selectivity has been noticed below
350  C. The selectivity and yield decreased with increase in
150 200 250 300 350 400 450
temperature (>350  C) by favouring the side reactions. The
Temperature,°C formation of other by-products such as C2H6 and C3H8 has not
been observed even at higher temperatures, indicating that
Fig. 4 e Conversion of CO2 over NiOeMgO synthesized by
the material is completely inbound to the formation of
sonochemical, co-precipitation, and solution combustion
methane.
synthesis.
A thermodynamics investigation for the CO2 conversion
and selectivity of CH4 at equilibrium using RGIBBS reactor in
(a) ASPEN PLUS simulator in the temperature from range of
100 150 Ce450  C has been performed. Along with the main re-
T90% CO2:H2:N2: 2:16:82 vol%
action, CO2 methanation, other side reaction such as r-WGS is
80 also considered. The effect of both dry and steam reforming
% CO2 Conversion

steps on equilibrium are negligible. The equilibrium conver-

60 sion at 450  C without any side reactions is estimated at 99%,
T50% whereas with side reactions equilibrium conversion is 89.5%.
40 From Fig. 5(a) it is evident that 2%Co/NiOeMgO offered activity
towards the main reaction, and the role of r-WGS is negligible.
Equilibrium conversion line
The CO2 conversion at 450  C was found to be 93%, which is
20 NiO-MgO
2% Co/NiO-MgO
higher than the equilibrium CO2 conversion with the side re-
2% Cu/NiO-MgO action (r-WGS). Table 2 gives a comparison between the pre-
0
2% Fe/NiO-MgO sent study results with the existing literature along with the
optimum parameters and preparation methods. The results
150 200 250 300 350 400 450
obtained from the work are quite promising and indicating
Temperature, °C
sonochemically synthesized catalysts to be highly active for
(b) CO2 methanation.
100
Equilibrium selectivity
Apparent activation energy estimation under kinetic regime
2% Co/NiO-MgO
80
2% Cu/NiO-MgO
In Fig. 5, CO2 conversion into CH4 was started at 200  C, and
% CH4 Selectivity

NiO-MgO
60 2% Fe/NiO-MgO the transition completed by 350e375  C. It is apparent from
this study that methanation plays an indispensable role due
40 to the amplification of H2 [53]. For CO2 methanation, dissoci-
ation of H2 is required, and the decomposition of CO2 into CO
20
is a necessary step. If there is no dissociation of CO2 into CO,
then it does not aid the development of CH4 by the interface of
adsorbed CO2 molecules with H2 [54]. CO yield is an essential
0
aspect for understanding the methane selectivity and the
150 200 250 300 350 400 450 development of catalysts at low-temperature profiles. Me-
chanical and physical activities on the catalyst substrate also
Temperature, °C
reduce the oxidation of CO and upgrade the selectivity of CH4
Fig. 5 e (a) CO2 conversion and (b) CH4 selectivity of 2%M/ up to 350  C.
NiOeMgO (M ¼ Co, Cu, and Fe) catalysts. In the packed bed reactor, the catalyst loading was varied
from (0 mge100 mg) and performed CO2 methanation studies
over impregnated 2%M/NiOeMgO (M ¼ Co, Cu, and Fe) cata-
catalysts, Cu becomes inactive for H2 dissociation, which will
lysts to compute their activation energies. A packed bed cat-
deteriorate the catalyst performance for CO2 methanation
alytic reactor’s kinetic regime is known as the region with
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1 28723

Table 2 e Literature comparison for CO2 methanation studies.

Catalyst Method of synthesis Temperature, GHSV, % Conversion of % Selectivity of Reference

C h1 CO2 CH4 No
Ni0.8Mg0.2O@SiO2-R Surfactant assisted Co-precipitation 300 6700 87 100 [6]
NieZrO2eAl2O3 Precipitation- impregnation 360 8100 70 NA [42]
Ni-(Zr þ Ca) Pulverization 400 400 85 NA [43]
2%CeO2/NieAl2O3 Co-impregnation 300 15,000 71 99 [44]
Ni/MgAl2O4 Plasma decomposition 350 15,000 85 NA [45]
Ni0.1Mg0.9O_600 Co-precipitation 340 NA 70 85 [46]
NieAl Wet impregnation 400 75,000 71 98.1 [47]
NieCeO2/Al2O3 One-pot -evaporation induced self- 150 40,000 70 NA [48]
assembly
Ni/Mg0.1Ce0.5Ox Sol-gel 400 36,000 75 100 [49]
Ni/Ce0.85Zr0.15O2 Precipitation 400 20,000 70 100 [50]
7.5% Sr/NieAl2O3 Incipient wet impregnation 400 16,000 80 NA [51]
NieAl Precipitation 350 20,000 80 99 [52]
NiOeMgO Sonochemical 400 47,760 85 98 Present study
2%Co/NiOeMgO Impregnation-sonochemical 400 47,760 90 99 Present study
2%Cu/NiOeMgO Impregnation-sonochemical 400 47,760 86 94 Present study
2%Fe/NiOeMgO Impregnation-sonochemical 400 47,760 89 96 Present study

negligible convection and resistance to mass transfer/diffu- stream condition. 2%Co/NiOeMgO catalyst showed 90% CO2
sion. Reactions under this system are intensely pretentious by conversion even after 35 h, Fe and Cu showed 87% and 89%
resistances delivered by intermediate elementary reactions, conversions at the end of 50 h. Minor decrement in the
such as catalytic surface reaction [55]. Considering the above methane selectivity was observed after 35 h for all catalysts
aspect, experimental conversions were plotted as a function except 2%Co/NiOeMgO. The methane selectivity of all cata-
of catalytic loading to authenticate the activity of the kinetic lysts except Co catalyst decreased from 99% to nearly 85%. The
regime. The experimental data in the given conditions follows Co-based catalyst showed 99% methane selectivity
the Weisz e Prater correlation [56] for mass transfer limita- throughout the time of 50 h. Although, all the impregnated
tion, signifying the validity of the differential flow reactor composites have shown excellent stability, 2% Co/NiOeMgO
assumption. Thus, the reaction rates were calculated by, offered higher conversions and stability for 50 h.

XCO2
rCO2 ¼
(3) X-ray photoelectron spectroscopy
W FCO2

From Eq. (3), reaction rates were obtained from the slope of Fig. 8 shows the XPS spectra of NiOeMgO composite catalysts
XCO2 vs W=FCO2 Fig. 6(a)e(d) signifies the linear variation of with M doping (M ¼ Co, Cu, and Fe). O 1s spectra for NiOeMgO
fractional CO2 conversion with the catalyst loading in the (as shown in Fig. S6(b)) depicts the lattice and vacant oxygen.
reactor under given feed conditions, CO2:H2:N2 ¼ 2:16:82 vol%. The contribution of both found to be 22.8% and 60.5%. Fe was
The reaction rates are resulted based on the above mentioned found in only þ2 and þ 3 oxidation states and having binding
method for different temperatures for all catalysts. Apparent energies of 711.8 eV and 724.2 eV. Fig. 8(a) shows Co 2p spectra
activation energies of all the catalysts for CO2 methanation of the catalyst, the binding energies of core level Co 2p3/2, 2p1/2
are found by generating the Arrhenius plot. The apparent peaks are observed at 779.7 eV, 794.8 eV for Co3þ,781.4 eV,
activation energies for all catalysts are listed in Table 3. 796.5 eV for Co2þ, 780.1 eV for Co (0) which is in metallic state
Amongst catalysts, 2%Co/NiOeMgO showed the lowest acti- and the difference of Co 2p3/2 and Co 2p1/2 of Co3þ and Co2þ
vation energy of 43 ± 2 kJ mol1. The cause behind the Co was 15.1 eV [32,62e64]. Co 2p3/2 and Co 2p1/2 satellite peaks are
impregnated catalyst has lower activation energy the abridged observed at 782.9 eV and 798.6 eV. A peak corresponds to
form of Co can provide more active sites for improving CO2 789.1 eV in Fig. 8(a) is because of the CoO satellite. Deconvo-
methanation at lower temperatures with an outstanding luted spectra in Fig. 8(e) shows the presence of Fe3þ at 710.6 eV
selectivity of methane [57]. Table 3 lists the activation energies and 723.6 eV for 2p1/2 and 2p3/2 core shells and Fe3þ at 713.9 eV
comparison with the existing literature. and 726.9 eV for 2p1/2 and 2p3/2 [62,65,66]. Fig. 8(e) shows the
core level spectra of Cu 2p3/2, 2p1/2 peaks were observed at
Stability studies on the synthesized catalysts 933.4 eV, 929.8 eV for Cu2þ and Cu metal [67]. In Fig. S6 (c) and
(d), the core level spectra of Ni and Mg were at 854.8 eV,
All impregnated catalysts and NiOeMgO composites were 860.8 eV for NiO and Ni(OH)2 [68] and Fig. S6(f) 1303.8 eV and
subjected to stability studies at 350  C for the experimental 1302.4 eV for MgO and Mg metal [69]. After stability studies,
feed conditions mentioned in section Catalytic CO2 from Fig. S6(b), (d) and (f), no significant changes was observed
methanation studies. The outcome of catalytic activity was in binding energies before and after reactions, and the shift is
studied on all catalysts at a longer exposure time of 50 h. Fig. 7 limited to 0.3 eV. This further confirms the high stability of the
shows the catalytic activity of all catalysts over 50 h of time on catalysts.
28724 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1

Fig. 6 e Fractional CO2 conversion variation with a ratio of catalyst loading to constant molar flow rate (a), (b), (c) and (d) for
2%M/NiOeMgO (M ¼ Co, Cu, and Fe) catalysts under kinetic regime (e) Arrhenius plot for 2%M/NiOeMgO (M ¼ Co, Cu, and Fe)
catalysts.

H2-TPR analysis the temperature above 600  C, the broadened peaks are
noticeable, which can state the solid solution formation of
Altogether M/NiOeMgO (M ¼ Co, Fe and Cu) have a great NiOeMgO materialization and endorses the addition of Co, Fe,
decrease in distribution above a temperature range up to and Cu [70]. The wide reduction distribution over temperature
700  C, as shown in Fig. 9. The primary reduction peak was was observed with the impregnated catalysts as well. How-
detected at 362  C. However, another reduction peak was ever, the overall oxygen storage capacity was found to be
detected for the catalysts above 600  C, and that might be due lower compared with the 2% Co/NiOeMgO catalyst.
to the second phase transition peak of Ni (From NiO to Ni). At Commencing the literature, the Co has high oxygen storage
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1 28725

Table 3 e Apparent activation energies comparison with literature.

Catalyst % Maximum CO2 Apparent activation Temperature range and flow rate, Catalyst Reference

conversion energy, Ea kJ/mol C and mL/min loading, mg
Ni-CNT-A 70 29 100-800, 30 100 [58]
60% Raney Ni 100 90 200-450, 32-740 70 [59]
Rh75ePd25 6.5 80 50-200, 20 200 [60]
Ni0.1Mg0.9O_600 70 96 220-280, 60 NA [46]
Ni/ɣ-Al2O3 96 92 120-650, 300 500 [61]
NiOeMgO 85 67 ± 2 200-450, 100 100 Present study
2%Co/NiO 95 43 ± 2 200-450, 100 100 Present study
eMgO
2%Fe/NiO 86 58 ± 2 200-450, 100 100 Present study
eMgO
2%Cu/NiO 89 66 ± 3 200-450, 100 100 Present study
eMgO

capacity and Co easily reduces from Co3þ to Co2þat the low CO2-temperature programmed desorption, mechanism and
temperature range. kinetic studies

In the literature, studies previously discovered that the MgO

100 surface comprises of Lewis basic sites through diverse
(a) electron-pair donor (EPD) strength [71]. Adsorbed CO2 can
form uni-dentate, bidentate, and tridentate species, which are
80 the primary intermediates required for the formation of
NiO-MgO
methane as a product. From Fig. 10, the foremost desorption
% CO2 Conversion

2%Co/NiO-MgO
peaks of 2% M/NiOeMgO nanocomposites are at 200  C, 260  C,
60 2%Cu/NiO-MgO
267  C, and 360  C. These desorption peaks confirms the most
2%Fe/NiO-MgO
significant number of medium basic sites available in the re-
gion. Low and strong basic sites are also noticed in the range of
40
90e120  C and 500e530  C. The review on NiOeMgO system
indicates the maximum conversion of CO2 is at strong basic
20 sites [72] and however, T50% is detected at medium basic sites
on all the catalysts presented in this study. The temperature
desorption rate of 2% Fe/NiOeMgO is better because of having
0 a better surface area. There is a deleterious effect on MgO
0 10 20 30 40 50
basic sites because of NiO having acidic sites. These acidic
Time, h sites will affect the reaction partially at higher temperatures
by favouring the agglomeration due to sintering effect [72].
(b)
100 TPD studies signalled that the presence of the weak, medium,
and strong basic sites over M/NiO-MgO (M ¼ Cu, Co, and Fe)
catalysts, which shows the interface between the metallic
80 NiO-MgO
sites and basic sites, and the application is solidly based on the
2% Co/NiO-MgO
% CH4 Selectivity

2% Cu/NiO-MgO
impact of MgO basic sites [73].
60 2% Fe/NiO-MgO CO2 methanation mechanism is elaborately discussed in
two types in the literature. One is CO2 associative mechanism,
and another is the CO2 dissociation mechanism. Many of the
40 researchers acknowledged the dissociative mechanism as the
precise way of demonstrating the mechanism of CO2 metha-
20 nation [74e76]. In the literature, it is conceivable to form CO2
straightway separated to carbonyl and O as intermediates in
the methanation process. CO2 consequently hydrogenated
0 and dissociated to carbon monoxide and oxygen in the next
0 10 20 30 40 50
step [57]. The formed CO is the basis to generate methane in
Time, h the reaction. Initially, the methylidene radical will form and
Fig. 7 e (a) Stability of CO2 conversion and (b) CH4 using this intermediate, it will produce a methylene bridge by
selectivity of NiOeMgO, 2%Co/NiOeMgO, 2%Cu/NiOeMgO holding the hydrogen [67]. Later, it starts the development of
and 2%Fe/NiOeMgO catalysts at 350  C. (100 mg catalyst, stable methane. Available intermediates from literature and
100 mL/min, GHSV: 47,760 h¡1, Feed composition: 2 vol% experimental results from H2eTPR, CO2-TPD and kinetic
CO2, 16 vol% H2 and rest N2). studies have been used as a basis for the detailed mechanism,
28726 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1

Fig. 8 e Core levels spectra of (a), (b) Co-before and after reaction (c), (d) Cu-before and after reaction (e), (f) Fe-before and after
reaction.

and it is proposed in subsequent fundamental elementary

steps. 1 k3
M þ H2 ðgÞ % M  H (R3)
2 k3
k1
M þ CO2 ðgÞ % M  CO2 (R1)
k1
k4
M  CO / M  C þ O* (R4)
k2
M  CO2 þ * / M  CO þ O* (R2)
k5
M  C þ M  H / M  CH þ M (R5)
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1 28727

The overall reaction kinetics approach and mechanism has

been studied and listed in the supplementary information.
From the elementary steps, it is deduced that the CO2 gas
molecules were adsorbed on both support and dopants. The
reactions R1, R2, R4 and R5, are based on the adsorption of the
active sites of composites and dissociation of carbon dioxide
into active carbon. All these steps are assumed based on the
dissociation of CO2 [77]. The formed complex is a mono-
dentate methylene group which is directly attached to the
dopants surface. The dopants are the central reason for the
formation of oxygen vacancies, and which are less substantial
in the reaction and anticipated final rate of reaction with
respect to methane formation is given below,

1 1 !
P2H P2H
A
2
K3  2Ak5 2

Fig. 9 e H2-TPR profiles of 2% M/NiOeMgO (M ¼ Fe, Cu, and

Co) catalysts. Rate ¼ 0 1 (4)
 
B 1
C
@1 þ K1 PCO2 þ 1 þ 2Ak
1
4
K3 P2H2 A

 
where, A ¼ 1 þk17 þk18 , Ki represents equilibrium constant of

ith elementary step and kj represents rate constant of jth

elementary step.
Using the Eq. (4) as a generalized reaction rate expression,
the experimental data was fitted using a non-linear regression
procedure with Levenberg-Marquardt algorithm. The initial
guesses for kinetic parameters were taken by using a modified
expression. In this methodology, first, the second term is
neglected from Eq. (4) and reduced in reciprocal terms. Linear
1
regression of 1/Rate vs 1=P2H2 data provided the initial guesses
for the kinetic parameters in Eq. (4). The nature of the rate
expression indicates a gradually increasing trend without the
second term, however, the second term in the Eq. (4) controls
the rate with increasing concentrations of H2, indicating the
Fig. 10 e CO2-TPD profiles of 2% M/NiOeMgO (M ¼ Fe, Cu, Langmuir-Hinshelwood (LH) kinetics as shown in Fig. 11. In
and Co) catalysts. this mechanism, both the reactants are assumed to be
chemisorbed on the catalyst surface. Similar mechanism was
proposed by Huang et al. for NieMgO catalysts [78]. All the
catalysts followed the generalized reaction rate model with
k6
M  CH þ 3M  H / CH4 ðgÞ þ 4M (R6) high goodness of fit. The kinetic parameters are optimized
using sensitivity analysis and listed in Table S1.
k7 It is well known that the equilibrium constant decreases
M  H þ O* / OH* þ M (R7)
with the increasing temperatures. Similar trend was observed
with equilibrium constants corresponding to CO2 and H2
k8
OH * þ M  H!M þ * þ H2 OðgÞ (R8) adsorption and desorption steps (K1 and K3). Among all cata-
Here, M represents the active site and * represents the lysts, it is observed that Cu based catalysts offered low con-
lattice oxygen vacancy. From Fig. 5, both doped and undoped versions. This could be due to its poor affinity towards H2
catalysts showed reasonable catalytic activity, indicating the adsorption [39,40]. In this study, the equilibrium constant
possible active sites on undoped NiOeMgO as well. Thus, the corresponding to H2 is estimated to be small compared with
reaction mechanism is proposed by considering metallic the other catalysts, indicating poor catalytic performance of
active sites from doped and undoped catalysts as M. Oxygen Cu/NiOeMgO. The reaction rate expression is highly sensitive
vacancies are detected from H2-TPR study for all the catalysts to kinetic parameters k5 and K3. The trend for k5 parameter for
and these vacancies will play significant role in forming active doped catalysts is as follows, Fe > Cu > Co, whereas the trend
lattice oxygen and hydroxyl species as intermediates as for K3 parameter is Co > Fe > Cu. Interestingly, k5 parameter
shown in the mechanism. for all catalysts is estimated to be large (order of 1010),
28728 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1

Fig. 11 e Effect of the partial pressure of H2 on the reaction rate of methane formation at constant pressure ðPCO2 ¼ 2:43 kPaÞ
for (a) NiOeMgO (b), (c) and (d) 2%Co/Fe/CueNiOeMgO.

indicating the high rate of association of adsorbed C and H experimental data was validated, and kinetic parameters
atoms. Whereas, with respect to K3 parameter, the values are were optimized using the developed rate expression consid-
having wide range of distribution over the doped catalysts and ering association of adsorbed C and H as rate limiting step.
the order is as follows, order of 103 for Co, 104 for Fe and 108 This study showed that transition metal impregnated NiO-
for Cu. This indicates that a high catalytic activity is possible MgO are stable and robust catalysts for CO2 methanation.
with the largest K3 parameter. The activation energy and
enthalpy (E and H) values are listed in Table S1. The apparent
activation energies are in the vicinity of E5 for all catalysts, Declaration of competing interest
suggesting that all dopants (Co, Fe and Cu) impregnated on
NiOeMgO composite follow the association of adsorbed C and The authors declare that they have no known competing
adsorbed H atoms as rate limiting step. financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

Conclusions
Acknowledgements
Co, Fe, and Cu impregnated NiOeMgO catalysts are highly
active for CO2 methanation. Around 95% conversions were
Authors sincerely thank Dr. Srikanta Dinda (BITS-Pilani,
achieved at 400  C, and slow light-offs were observed. The
Hyderabad Campus, Head of Department, Chemical Engi-
activation energy of 2% Co/NiOeMgO is lowest compared to
neering) for extending TPR and TPD facilities and Mr. Pre-
other catalysts due to reducing nature of Co by which it can
mnath Murge for his assistance in conducting TPR and TPD
offer more active sites. Further, 2% Co/NiOeMgO surface is
studies. Dr. S.A. Singh thanks BITS-Pilani, Hyderabad campus,
more susceptible to main reaction (i.e., CO2 methanation)
India for providing financial support by Research Initiation
than the other possible side reactions (r-WGS and reforming).
Grant (RIG-733) and Additional Competitive Research Grant
Mechanism of CO2 methanation is elucidated in a compre-
(ACRG-906). Authors are grateful for the characterization fa-
hensive approach, and the reaction rate model is developed
cilities offered by Central Analytical Laboratory, BITS-Pilani,
from the surface species’ interaction with the composite. The
Hyderabad campus.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 5 ( 2 0 2 0 ) 2 8 7 1 6 e2 8 7 3 1 28729

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