Catalysis Today 356 (2020) 471–489

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

A review of recent catalyst advances in CO2 methanation processes T

Jangam Ashok, Subhasis Pati, Plaifa Hongmanorom, Zhang Tianxi, Chen Junmei,
Sibudjing Kawi*
Department of Chemical & Biomolecular Engineering, National University of Singapore, 117585, Singapore

A R T I C LE I N FO A B S T R A C T

Keywords: This review focuses on various catalytic CO2 hydrogenation approaches for converting CO2 to fuels such as CH4.
CO2 conversion The catalytic CO2 methanation using thermal, catalytic-membrane, photo and plasma energy assisted processes
Methanation were covered. The recent catalysts developments in thermo-catalytic systems for CO2 methanation in thermal
Membrane-catalysis process with respect to the nature of active catalytic centres and their performance were presented. Followed by
Plasma-catalysis
the technological development of catalytic-membrane process and its advantages in overcoming thermodynamic
Photo-catalysis
equilibrium activities were also discussed. Additionally, the catalytic CO2 hydrogenation process assisted with
plasma and photo energy were also covered with respect to the catalyst structures, CO2 conversion and se-
lectivity towards various products. Several highly emerging in situ characterization techniques such as operando
XAS and DRIFTS were used to understand the state of catalyst surface and reaction intermediates involved in
CO2 methanation reaction. Furthermore, parameters affecting the selectivity towards desired products and
methods to improve the performance are explained in greater details. Finally, a section for technological
challenges of CO2 methanation in various processes are summarized and an outlook for future directions of the
development of catalysts was provided to overcome the CO2 conversion and selectivity towards desired products
limitations to eradicate the problems associated with global warming.

1. Introduction
Fossil fuels including oil, coal and natural gas are non-renewable
resources, and when they are burned, they release carbon dioxide
which lead to global warming and climate change [1–3]. Over the past
several decades, great efforts have been devoted to the CO2 conversion
to reduce the greenhouse gas emission and hence the global warming.
Hence, in recent years, there has been wide amount of global interest in
finding sustainable ways to reverse the increasing CO2 concentration in
the atmosphere. Globally, treaties such as the Kyoto Protocol and the
Paris Agreement identify reduction in carbon emissions as vital in
preventing the potentially disastrous effects of further global warming
[4]. Therefore, recently, the global attention is moving towards Carbon
Capture and Utilization (CCU) concept. In CCU concept, carbon dioxide
is captured and separated from emission gases and then converted into
valuable products. Among various CCU routes, catalytic CO2 fixation
approaches can play a vital role, because CO2 can be artificially con-
verted into reusable fuel or commodity chemicals, and provide a much
wider-scale route for CO2 utilization [5–7]. Among the catalytic reac-
tions of CO2, hydrogenation of CO2, the so called methanation reaction,
is a suitable technique for the large-scale CO2 fixation. This technique
can be used to convert exhausted CO2 into synthetic natural gas (SNG,
methane (CH4)), which can be recycled for use as a fuel or a chemical as
well as by contributing to the reduction of CO2 emissions [8–12].
CO2 hydrogenation to methane is an exothermic reaction, which is
thermodynamically favoured at lower reaction temperature. However,
a proper catalyst is required to achieve appropriate rate. Being a stable
molecule, activating CO2 at thermodynamically favoured conditions is
challenging for any catalyst. Due to this, CO2 methanation is mainly
operated between 200−400 °C. At these reaction conditions in addition
to CO2 methanation (eq (1)) reaction, other side reactions such as
carbon formation (eq (2)) and reverse-water-gas-shift (eq (4), RWGS)
do exists. Especially, at high operating temperatures and Ni-based
catalysts, CO2 reforming with methane and reverse-Boudouard reac-
tions are also possible along with the CO2 methanation reaction. Thus,
in order to obtain high selectivity towards formation of methane, the
role of suitable catalyst and it’s stability at exothermic condition is pi-
votal.
CO2 + 4H2 ↔ CH4 + 2H2O(ΔH298K = −165 kJ mol−1) (1)
−1
CO2 + 2H2↔C + 2H2O(ΔH298K = −90.1 kJ mol ) (2)

⁎
Corresponding author.
E-mail address: chekawis@nus.edu.sg (S. Kawi).

https://doi.org/10.1016/j.cattod.2020.07.023
Received 25 November 2019; Received in revised form 15 May 2020; Accepted 17 July 2020
Available online 29 July 2020
0920-5861/ © 2020 Elsevier B.V. All rights reserved.
J. Ashok, et al.
CO2 + C↔2CO(ΔH298K =172.4 kJ mol−1) (3)
−1
CO2 + H2↔CO + H2O(ΔH298K =41.2 kJ mol ) (4)
−1
CO2 + CH4↔2CO + 2H2O(ΔH298K =247.3 kJ.mol ) (5)
Though CO2 methanation is possible to happen at atmospheric
pressure and low temperatures, the conversion of CO2 is technologically
challenging because of high stability of CO2 molecule compared to the
intended products. And more importantly the cost associated with
production of renewable hydrogen source and CO2 separation.
Therefore, the economy of CO2 hydrogenation to methane is greatly
influenced by the availability of H2 and CO2 sources. In the case of
available CO2 source, many industrial processes such as biomass/coal
power generation, refineries and cement manufacture intrinsically
produce CO2 and can be fitted with CO2 capture. The adsorption, ab-
sorption, chemical looping and membrane separation are few of recent
technologies, which can effectively separate CO2 from flue gas and can
be utilized for CO2 conversion technologies. Recently, many researchers
are interested towards simultaneous separation and conversion of CO2
into valuables from flue gas like sources. For instance, T Chen et al.
demonstrated the catalytic disk type dual phase membrane containing
ceramic phase of oxygen-ion conductor and molten carbonate phase for
CO3− conducting [13,14]. The La0.9Ce0.1NiO3-δ material was integrated
for simultaneous separation and conversion of CO2 into CO via reverse
water-gas-shift reaction. This module demonstrated to be stable for
more than 70 h above 750 °C in synthetic reaction mixture. However,
the stability of the system in real flue gas composition is unknown. This
is probable one area where further research/investigation is required.
Furthermore, the hydrogen required for CO2 hydrogenation processes
should be from renewable resources, such as biomass gasification, wind
power, or solar water-splitting [15,16]. There are significant techno-
logical advancements has been reported for H2 production from re-
newable sources [17]. For instance, though biomass is a cheap and
renewable source, separation of H2 from reformate gas mixture of
biomass gasification makes the whole process expensive. Researchers
are trying various options to make this whole process cheaper such as
enriching O2 in air by using selective membrane [18], using catalyst to
promote steam reforming of tar [19] and WGS reaction [20] for en-
riching H2 gas and integrating WGS reaction with Pd-coated membrane
for selective H2 separation. These studies seeming to be possible in lab-
scale but application in large scale is challenging. In the solar energy to
hydrogen process, the photo-voltaic (PV) energy splits the water mo-
lecule into hydrogen and oxygen. Another possible route is via geo-
thermal energy where the heat and electricity can be applied to gen-
erate hydrogen by hybrid cycles or electrolysis process. For the process,
wind to hydrogen (WTH) via water electrolysis produces surplus elec-
tricity in the form of hydrogen which can be transformed back to
electricity again when there is a low wind potential.
As highlighted before, the thermo-catalytic process of CO2 metha-
nation is a mature technology, the major research is happening in the
area of catalyst technology. To intensify the overall technology, re-
cently, there are few technological developments are happening such as
integrating catalyst with selective membrane in thermal process, re-
placing the thermal energy with either low-temperature plasma or
photo energy. The integration of membrane separation with a catalytic
reaction is termed as a membrane reactor and it is always of interest it
terms of process intensification [21,22]. The yield of a reversible re-
action can be enhanced over the thermodynamic equilibrium conver-
sion by in situ removal of one of the product from the reaction using a
membrane [23]. The selective separation of one of the product from the
reaction shifts the equilibrium in the forward direction according to the
Le Chattelier’s principle. The membrane reactors also can be used to
feed the reactants to the reaction from an impure stream and boost the
reactor performance. The reactant supply to a particular reaction is also
controlled by using a membrane which eventually affects the rate and
selectivity of the reaction [24]. Due to these advantages, recently there
472
Catalysis Today 356 (2020) 471–489
was significant work has been reporting on catalytic-membrane reactor
system for CO2 hydrogenation reaction. In the below section besides the
catalyst development, we will be covering the technological advance-
ment of catalytic membrane process for CO2 methanation reaction.
Besides, we will also be covering the CO2 hydrogenation in hybrid
catalyst-plasma process. One of the main advantages of this process is it
can be operated at lower temperatures and H2O can be a source of H2
for CO2 hydrogenation reaction [25]. Though the reaction is feasible at
mild reaction conditions, achieving the selectivity towards desired
products is the bottle neck for this process. Therefore, the role of sui-
table catalyst has vital role in plasma assisted catalyst CO2 hydro-
genation process. Similarly, in photo-catalytic CO2 methanation pro-
cess, the renewable energy can be utilized for activating CO2 and
various hydrogen containing components can be used as sources for H2.
The main drawback for this process is yield of the desired product is
limited and discontinuity of the energy source. To enhance the yield of
desired product, developing the suitable catalyst is required.
Due to the rapid advancement in the research activity in the CO2
hydrogenation to C1 valuables, there has been several reviews in the
recent past focusing on the technical challenges and the recent progress
in catalysis, process innovations, novel trends and lifecycle assessments
in these areas [26–30]. Jan Kopyscinski et al. reviewed the processes
developed between 1950 and 2009 for the production of SNG from coal
and dry biomass. The authors have highlighted that the process concept
of SNG from biomass have to consider the biomass logistics and in-
evitable ethylene content of few percent cause the deactivation of the
catalyst. It is necessary to convert the active ethylene to less active
hydrocarbons before methanation process [31]. K. Ghaiba and F.Z.B.
Faresb, and others reviewed the technology development of ‘power to
methane’ concept of converting electrical energy into chemical energy
using CO2 and H2O. Electrolysis of H2O is considered as the process for
H2 source [32,33]. Thenert et al. did a comprehensive review on dif-
ferent CO2 technologies including catalysis, challenges and current
status of technology and life-cycle assessments [28]. Song et al. re-
viewed a progress in heterogeneous catalysts for the production of
hydrocarbons including methane, methanol, olefins and higher hydro-
carbons by hydrogenation of CO2 [26]. Similarly, MAA Aziz et al.
summarized the catalysts development for thermal CO2 methanation
process and the catalyst with Ni as active component and supported
over high surface area materials would be the suitable contenders for
this reaction. In another work, Panpan Li et al. presented the applica-
tion of 2-D layer double hydroxide (LDH) derived catalysts for both CO2
methanation and CO2 methane reforming reactions [34]. M. Carmen
Bacariza et al. highlighted the tuning the zeolite properties for CO2
methanation activity [35]. The hydrophilicity of the zeolite structures
and fine tuning of acid base properties using dopents such as Cs+ is
crucial for CO2 methanation activity. J.C. Navarro et al. summarized
the policies that are motivated the transition to circular CO2 models and
the development of different reactions for CO2 valorization. Special
attention to the case of the Sabatier reaction and in the application of
structured reactors [36]. Several recent reviews also focus on chal-
lenges and recent progress in catalyst development for CO2 hydro-
genation to methane [37–41]. Furthermore, there are few works high-
lighting the possible reaction pathways over supported metal catalysts,
thermo-catalytically there are two main possible CO2 methanation re-
action pathways, it can be either direct conversion to methane (via
format species as an intermediate) or via CO as the main intermediate
species [42,43]. In some catalysts both routes have been observed [44].
The developmental trends in CO2 methanation catalysts for various
process such as electro-catalytic, thermos-catalytic and photo-catalytic
is summarized by I. Sreedhar et al. Similarly, Miao Liu et al. reviewed
the heterogeneous and plasma catalysis for CO2 hydrogenation to va-
luables [45]. In most of the above highlighted review articles, the au-
thors have mainly discussed the progressive development of CO2 me-
thanation technology in single process. Only few articles were discussed
multiple processes together in single article. Therefore, by considering
 Table 1
Summary of catalyst development for CO2 methanation.
Catalyst Preparation method Reaction condition CO2 conversion CH4 selectivity Remarks Ref.
J. Ashok, et al.

(%) (%)

2.5 wt%Ru/TiO2 (001) Solvothermal hydrolysis for TiO2 WHSV =6000 mL h−1 g−1, at 325 °C > 80 100 TiO2 exposing (001) facets possesses high surface energy and abundant oxygen [47]
synthesis, followed by mixing with and 1 bar vacancies, which could provide more active sites for CO2 activation and result
RuO2 in a strong metal-support interaction with Ru.
5 wt%Ru/r-TiO2 Wet impregnation method GHSV =75000 mL h−1 g−1, at 300 °C 65 ∼100 Ru and rutile-type TiO2 had strong metal-support interaction via Ru-O-Ti [54]
and 1 bar bond, exhibiting good Ru dispersion.
Ce0.95Ru0.05O2 Solution combustion At 450 °C and 1 bar 55 99 The Ru dopant facilitated the reduction of CeO2, and the methanation reaction [57]
took place on the reduce Ce0.95Ru0.05O2.
3wt%Ru/Al2O3 Commercial catalyst GHSV =55000 h−1, at 350 °C and 1 85 85 3% Ru/Al2O3 is very active in CO2 methanation, with low CO coproduction. [61]
bar CO selectivity increases by decreasing reactants partial pressure apparently
more than expected by thermodynamics.
3.7 wt%Ru/CeO2/r Hydrothermal process for CeO2, GHSV =72000 mL h−1 g−1, at 350 °C > 75 99 Ru/CeO2/r outperforms Ru/CeO2/o and Ru/CeO2/c due to highest [58]
followed by wet ness impregnation and 1 bar concentration of oxygen vacancies.
5 wt%Ru/CeO2 Single-step flame spray pyrolysis GHSV =7640 h−1, at 300 °C and 1 bar 83 99 CeO2 showed a moderate Ru-CO coverage, which ensured the presence of H2 [177]
dissociation sites, while the Ru-CO adsorption strength remained sufficiently
high.
Mesoporous Rh Wet chemical reduction GHSV =48000 mL h−1 g−1, at 550 °C 98.9 81.2 Highly activity and CH4 selectivity are achieved due to their controllable [70]
and 1 bar crystallinity, high porosity, high surface energy, and large number of atomic
steps distributions.
1 wt%Rh/γAl2O3 Wet impregnation CO2 = 0.0833 kmol/s, H2 = 0.0833 25 100 The amount of CH4 produced depended on the temperature, pressure, presence [145]
kmol/s and He = 0.83 kmol/s, at 25 °C or absence of gas promoters, like CO or O2, in the feed.
and 1 bar
6wt%Pd@UiO-66 Solvent-thermal method GHSV =15000 h−1, at °C and 40 bar 56 97.3 The high catalytic activity was attributed to the synergistic effect of Pd NPs [73]
and UiO-66. CO2 could be activated in UiO-66 via its Zr6O4(OH)4 nods.
−1
10wt%Ni/CeO2 Wet impregnation GHSV =10000 h , at 350 °C and 1 93 100 The excellent performance was attributed to large amounts of CO2 adsorption, [74]

473
bar enhancement of CO2 reduction to CO because of the oxygen vacancies and
prompt conversion of CO to CH4 over Ni/CeO2.
5 wt%Ni/ZrO2 Plasma decomposition GHSV =60000 h−1, at 350 °C and 1 79.1 76.5 The plasma decomposition improved Ni dispersion with principally exposed Ni [78]
bar (111) facet. Oxygen vacancies created with enhanced Ni-ZrO2 interaction
promotes CO2 adsorption.
10wt%Ni/CeO2-ZrO2 Ammonia evaporation (AE) GHSV =20000 mL h−1 g−1, at 275 °C 55 99.8 The excellent performance of Ni/CeO2-ZrO2 prepared by AE method was due [79]
and 1 bar to the ability to be activated at low temperature. It was also stable for nearly
70 h.
2wt%Ni@CeO2-ZrO2 Colloidal Ni nanoparticle dispersion GHSV =60000 mL h−1 g−1, at 350 °C 58 > 97.5 CeO2-ZrO2 shows a strong synergy with encapsulated Ni. Encapsulation also [80]
during sol-gel synthesis and 1 bar helps to prevent sintering of the Ni nanoparticles.
5 wt%Ni/MSN Wet impregnation GHSV =50000 mL h−1 g−1, at 300 °C 64.1 99.9 The existence of both intra- and inter-particle porosity in Ni/MSN led to high [81]
and 1 bar concentration of basic sites and large amount of oxygen vacancy. The Ni/MSN
catalyst performed with good stability and no deactivation up to 200 h.
20 wt%Ni-20 wt%CeO2/ Deposition precipitation GHSV =9000 mL h−1 g−1, at 380 °C 85.6 99.8 Due to synergetic effects, addition of CeO2 could improve Ni dispersion and [83]
MCM-41 and 1 bar increase CO2 adsorption sites. This catalyst could maintain its high reactivity
after 30 h.
10wt%Ni-1 wt%MgO/ Co-impregnation GHSV =15000 mL h−1 g−1, at 350 °C > 67 > 98 Addition of MgO could enhance CO2 adsorption capacity, accelerate CO2 [85]
SiO2 and 1 bar activation and suppress Ni sintering and oxidation. CO2 conversion still
maintained, while CH4 selectivity slightly decreased after 50 h.
10wt%Ni-La2O3/SBA- Citrate complex GHSV =6000 mL g−1 h−1, at 320 °C 90.7 99.5 Ni-La2O3/SBA-15 prepared using citrate complex shows high Ni dispersion. [178]
15(C) and 1 bar The interaction between La and Ni is also intensified due to LaNiO3 perovskite
structure.
10wt%Co/ZrO2 Wetness impregnation GHSV =3600 mL g−1 h−1, at 400 °C 92.5 99.9 The formation of a new Co-Zr phase at the Co-ZrO2 interface could provide the [88]
and 30 bar additional CO2 adsorption sites in CO2 methanation.
2wt%Co/ZrO2 Citric acid-assisted incipient wetness GHSV =7200 mL g−1 h−1, at 400 °C 85 99 Citric acid could form complex with Co precursor, leading to decreased Co [89]
impregnation and 30 bar particle size, increased Co dispersion and strengthened Co-ZrO2 interaction.
Co3O4 nanorods Co-precipitation GHSV =18000 h−1, at 230 °C and 10 70 ∼99 Co3O4 nanorods with exposed (110) surface facets exhibit considerably high [90]
bar catalytic activity and selectivity toward CH4.
(continued on next page)
Catalysis Today 356 (2020) 471–489
J. Ashok, et al. Catalysis Today 356 (2020) 471–489

recent and above studies on CO2 methanation and in order to have a

[92]
Ref.
better picture about CO2 methanation reaction in various processes, this
article aims to establish the recent works on thermos-catalytic, thermos-
can increase Co dispersion and facilitate the diffusion and transfer of gaseous
Large surface area and ordered bicontinuous mesoporous structure of KIT-6
catalytic-membrane, photo-catalytic and plasma-catalytic processes
together. Also, highlighted how they have completed each other in
order to achieve better performance. Furthermore, the recent catalyst
formulations for thermal process are also depicted in Table 1.

2. CO2 methanation catalysts under thermal condition

CO2 methanation is the reaction of one mole of carbon dioxide with

four moles of hydrogen in which one mole of methane is obtained as
represented in Eq. (1).
CO2 methanation is exothermic in nature and spontaneous at room
temperature, so high equilibrium conversion is predicted at low tem-
perature between 25 °C and 400 °C. Nevertheless, kinetic barrier is still
high although it is thermodynamically favourable, which retards the
industrial applications [38,46]. Thus, the fundamental studies on the
development of highly active and selective catalysts for CO2 methana-
tion is of great importance. Over the past decade, significant progress
has been made on the catalyst with respect to the nature of active metal
molecules.

components, supports and promoters. Here in this section we will be

Remarks

discussing the progress of catalyst development based on nature of

active components such as noble and non-noble metal catalysts. The
recent catalyst formulations for thermal process are summarized in
CH4 selectivity

Table 1.

2.1. Noble metal catalysts

100
(%)

2.1.1. Ruthenium (Ru)

Ru is one of the most active and selective catalysts for methanation
CO2 conversion

reactions, even being used at low metal loading and operated at low
temperature. Ru in its reduced state is highly effective for dissociation
of hydrogen, which further reacts with adsorbed CO2 on the catalyst
48.9
(%)

surface. Nevertheless, CO2 conversion and CH4 yield over Ru-based

catalysts are largely dependent on the amount of metal loading, size
GHSV =22000 mL h−1 g−1, at 280 °C

and dispersion of metal particles, nature of the support material and

interaction between the active metallic species and the support [47].
The impregnation of different Ru loading on alumina supported
catalysts was found to affect the catalytic activity in CO2 methanation
[48]. Increasing Ru loading from 1 to 5% neither changed Ru dispersion
Reaction condition

nor particle sizes of Ru in this work. Instead, higher Ru contents (op-

timal at 4%) could increase the surface basicity and form new CO2
adsorption sites, thus showing greater CO2 conversion. Theoretically,
and 1 bar

the sites corresponding to O2− (and OH- if applicable) linked to Ru

have low negative charge density. These sites could provide high ad-
sorption capacity of CO2, which is an acid gas with high negative charge
density.
The variation of Ru loading could also be controlled to prepare
different Ru structural configurations over Ru/Al2O3 catalysts, which
influenced the catalytic pathways towards either CO2 methanation or
RWGS reaction [49]. 1 % Ru/Al2O3 catalyst appreciably consisted of
Wetness impregnation
Preparation method

both Ru monolayers and multiple layers of 3D nanoclusters, whereas 2

% and 3 % Ru/Al2O3 catalysts consisted of 3D nanoclusters as the
dominant Ru sites. Focusing on methanation route, CH4 formation was
in favor of relatively larger 3D nanocluster sites of Ru as shown in
Fig. 1. Based on DFT calculations, the predicted energy barrier in the
dissociation step of H2COOH* species (the rate-limiting step of me-
thanation route) for the 3D nanocluster model was lower than that for
the monolayer model. The dependence of product selectivity on Ru
Table 1 (continued)

loading in the range of 0.1−5 wt% and cluster size was consistent with
20 wt%Co/KIT-6

previous findings by Kwak et al. [50]. 3D metal clusters preferably

formed on Ru/Al2O3 catalysts with Ru loadings at and above 1 wt%,
Catalyst

resulting in higher selectivity toward CH4 formation. It was also found

that apparent activation energy for CH4 formation was lower than that
for CO formation ∼20 kJ/mol, suggesting no involvement of CO as an

474
J. Ashok, et al. Catalysis Today 356 (2020) 471–489

Fig. 1. Schematic illustration of CO2 hydrogenation to form CO and CH4 over Ru/Al2O3 catalyst [49].

intermediate in the formation of CH4. In addition to Ru structural
configurations, size of Ru nanoparticles was also found to influence the
selectivity in CO2 catalytic reduction. The recent study by Cargnello
et al. [51] found that Ru nanoparticles (ca. 2.6 nm) on CeO2 pretreated
in H2 at 230 °C favored CH4 formation (CH4 selectivity > 90 %) via
methanation. In contrast, single-site RuOx/CeO2 pretreated subse-
quently in O2 and H2 both at 230 °C favored CO formation (CO se-
lectivity > 90 %) via RWGS. This substantial change in the reaction
pathway from selective methanation to dominant RWGS was attributed
to the redispersion of initial Ru nanoparticles into atomically dispersed
RuOx species during the oxidative pretreatment. These Ru single-site
species could bind CO more weakly than Ru nanoparticles, leading to
easier CO desorption and thus preferential CO production.
The relationship between CO2 methanation activity and different Ru
size regimes including single atoms, nanoclusters (ca. 1.2 nm) and large
nanoparticles (ca. 4 nm) was also systematically investigated over Ru/
CeO2 catalysts [52]. As shown in Fig. 2, Ru nanoclusters and large Ru
nanoparticles exhibited weaker SMSI than single Ru atoms, thus facil-
itating the activation of metal carbonyls. Conversely, single Ru atoms
and Ru nanoclusters exhibited weaker H-spillover effect than large Ru
nanoparticles, thus enhancing H2O removal from the support surfaces.
The balance between these two factors as well as optimal methanation
activity were achieved by CeO2-supported Ru nanoclusters. In another
systematic study, Abe et al. [53] investigated the dependencies of the
onset temperature of CH4 formation and the TONCH4 on the mean
particle diameter of Ru on TiO2 prepared by a polygonal barrel-sput-
tering method (Ru/TiO2(B) with different mean particles in the range of
ca. 2.5–6.4 nm) and a conventional wet method (Ru/TiO2(W) with the
mean particle of ca. 9.5 nm). The remarkable reduction in the onset
temperature and significant increase in TONCH4 were observed as the
particle diameter was decreased from 6 to 2.5 nm, whereas the onset
temperature and TONCH4 remained almost constant for nanoparticles
greater than 6 nm. It is also noteworthy that Ru/TiO2(B) with the mean
particle of 2.5 nm exhibited a reaction rate of 0.04 μmol min−1 g-1 even
at temperature as low as room temperature.
Ru catalysts have been supported on various oxide materials, in-
cluding both with oxygen vacancy (CeO2, ZrO2 and TiO2) and without
oxygen vacancy (Al2O3, SiO2). Among all Ru-based catalysts, Ru/TiO2
catalyst has been regarded as the most effective and selective in CO2
methanation [30]. The effect of crystalline phases of TiO2 on the
structure and performance of Ru nanoparticles in CO2 methanation was
revealed by Huang’s group [54]. Compared with anatase-type TiO2 (a-
TiO2), rutile-type TiO2 (r-TiO2) exhibited better Ru dispersion and less
aggregation of Ru species due to strong metal-support interaction via
Ru-O-Ti bond. Therefore, Ru/r-TiO2 catalyst displayed superior activity
and thermal stability than Ru/a-TiO2 catalyst in CO2 methanation. The
correlation between the structure and electronic properties of Ru/r-
TiO2 catalysts and their activities was also established by varying the

Fig. 2. The influence of different metal size regimes over highly active Ru/CeO2 catalysts on the methanation activities (left) and competitive SMSI and H-spillover
effect lead to competing CO activation and surface dehydration for CeO2-supported single Ru atoms, Ru nanoclusters, and large Ru nanoparticles (right) [52].

475
J. Ashok, et al.
pretreatment temperature in a follow-up study [55]. It was found that
the activity was dependent on encapsulation extent of Ru particles by
TiOx layers and the amount of hydroxyl groups on the TiOx surface.
The use of abundant oxygen vacancy on the surface of CeO2 support
was also explored in CO2 methanation. In brief, the dissociated hy-
drogen on metallic Ru could attack Ce-O bond on CeO2 surface and
generate Ce3+, surface hydroxyls and oxygen vacancy, which fa-
cilitated the CO2 chemisorption and activation. The detailed catalytic
roles of Ce3+, hydroxyl groups and oxygen vacancy for CO2 methana-
tion as well as the mechanistic insights were well described using op-
erando/in situ characterization methods and computational approach
[56,57]. In a recent study, the influence of the CeO2 morphology on Ru
catalysts for CO2 methanation was also investigated [58]. The CO2
methanation activity trend likely followed the oxygen vacancy con-
centration trend as follows: Ru/CeO2/r (rod) > Ru/CeO2/o (octa-
hedra) > Ru/CeO2/c (cube). This finding could suggest that the rate
limiting step is the reactive adsorption CO2 at oxygen vacancy.
Apart from reducible metal oxide supports, Al2O3 supported Ru
catalysts have been widely investigated in CO2 methanation due to their
high activity per gram and inexpensive price [59,60]. Besides, Ru/
Al2O3 catalysts are commercial catalysts for CO methanation at low
temperature applications [61]. The recent advance also shows that a
commercial 0.5 wt% Ru/Al2O3 catalyst is suitable to catalyze CO2
methanation (so-called Sabatier reaction) under process conditions re-
levant for Power-to-Gas applications [62]. The effect of process condi-
tions (feed composition, space velocity, temperature and pressure) and
influence of water on catalyst activity, selectivity and stability in CO2
methanation were extensively investigated to achieve high CO2 con-
version with high CH4 selectivity and confirm the potential of Ru/Al2O3
catalyst in Sabatier reaction for Power-to-Gas applications.
Recently, porous hexagonal boron nitride (pBN) material has also
been employed as a promising support to prepare low Ru loading (0.58
wt%) catalyst for CO2 methanation [63]. Atomic Ru could be im-
mobilized on pBN and restricted onto the defects via B and N co-
ordinations. These coordinations also reduced the valence state of
atomic Ru. By utilizing DFT simulation, this study revealed that atomic-
scale size and low oxidation state of Ru supported on pBN contributed
to a significant enhancement of CH4 production rate and a satisfactory
catalytic stability after 110 h.
2.1.2. Rhodium (Rh)
In addition to Ru, Rh is very active and selective in CO2 methana-
tion at low temperatures. Previous studies on Rh-based catalysts have
mainly established the effects of Rh particle size, support material and
chemical state of Rh on CO2 methanation activity and reaction me-
chanism.
The intrinsic activity of Rh/ γ -Al2O3 catalysts was found to be
dependent on Rh particle sizes in the range between 3.6 nm and 15.4
nm [64]. Especially at low temperature of 135−150 °C, larger particles
Fig. 3. Catalytic performance toward CO2 reduction over mesoporous Rh and nonporous Rh catalysts [70].
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Catalysis Today 356 (2020) 471–489
promoted the turnover frequency for CH4 formation due to their larger
proportion of lateral faces, which would favor the rate determining step
(the breaking of CeO bond) and hence lower overall activation en-
ergies. In contrast, catalytic performance was independent of Rh par-
ticle sizes at temperature between 185 and 200 °C. In their follow-up
study, the high sensitivity of apparent activation energy and H2 and
CO2 reaction orders to Rh cluster size over Rh/TiO2 catalysts was also
pronounced at low temperature between 85 and 165 °C [65]. Smaller
Ru clusters had less active sites and more strongly adsorbed CO inter-
mediates than larger Rh particles, resulting in lower reaction orders in
CO2 and higher apparent activation energies. It was noteworthy that
the activation energy for CO dissociation did not vary significantly with
Rh particle size. Smaller particles also exhibited higher reaction orders
in H2, indicating lower H2 coverage compared to larger ones. Overall,
increasing Rh particle sizes from 2 nm up to 7 nm enhanced the rate of
CH4 production per surface Rh atoms. No appreciable change could be
discerned beyond this particle size.
Regarding the choice of support, TiO2 is one of the most effective
supports for Rh catalysts. Rh/TiO2 catalyst exhibited the rate of CH4
formation one order of magnitude higher than Rh/Al2O3 and Rh/SiO2
catalysts. It was reported that electronic metal-support interaction or
interaction between Ti3+ ions located at the edge of TiO2 islands and
adsorbed CO on Rh could assist in the breaking of CeO bond [65,66].
Martin et al. have investigated Rh supported on various metal
oxides including SiO2, Al2O3 and CeO2 for CO2 methanation. Both Rh/
CeO2 (reducible oxide) catalyst and Rh/Al2O3 (nonreducible oxide)
catalyst exhibited high CO2 conversion towards CH4 [67]. Based on a
detailed DRIFTS study, the differences in their reaction mechanisms
were evident due to different nature of the support. Rh particles showed
high degree of electronic interaction with Al2O3, which could facilitate
the adsorption and dissociation of CO2. Under the reaction conditions,
the change in chemical state of Rh was observed for Rh/Al2O3 catalyst.
That is to say, dissociative adsorption of CO2 could generate linearly
adsorbed CO and O species on metallic Rh, and the latter species led to
RhOx species. The high activity over Rh/Al2O3 catalyst was associated
with the formation of the linear Rh-CO species and RhOx species re-
sulting from CO2 dissociation [68]. The interaction between Rh parti-
cles and the ceria phase was also strong. Ce3+ played a key role in
activating CO2 and forming formates likely at the metal-support inter-
face, which further dissociated to strongly bound CO and OH species
[69].
Recently, novel mesoporous Rh nanoparticles fabricated via facile
wet chemical reduction approach were used as a catalyst for CO2 me-
thanation [70]. The mesoporous Rh catalyst exhibited substantially
higher reaction rate than nonporous Rh catalyst, as shown in Fig. 3.
Highly catalytic activity was attributed to a large number of atomic
steps on the mesoporous Rh catalyst, which assisted in adsorption and
activation of CO2.
J. Ashok, et al. Catalysis Today 356 (2020) 471–489

2.1.3. Palladium (Pd)

Pd catalysts have been utilized in CO2 hydrogenation reaction due
to their ability to dissociate H2 and supply H atoms. Wang et al. in-
vestigated two Pd/ γ -Al2O3 catalysts with different Pd loadings (5 %
and 0.5 %) for CO2 hydrogenation and found that higher metal loading
could increase the concentration of H-species [71]. The abundant
supply of these H species was essential for high CH4 production. Ad-
ditionally, a larger fraction of terrace sites over 5% Pd/Al2O3 catalyst
could favor the formation of multibound and stable CO species, which
have less tendency to desorb as gaseous phase CO.
Crystallographic surface orientation and corresponding mean co-
ordination number of surface Pd atoms also contributed significantly to
the adsorption strength of reactants and CO intermediate species and
ultimately influenced the CH4 selectivity [72]. It was reported that low
mean coordination number of the surface sites including corners, edges
and steps, on impregnated Pd/SiO2 were more favorable to the for-
mation of CH4 than high-coordinated Pd(100) and Pd(111) facets on
shape-controlled Pd nanoparticles (cube and polyedra) embedded in
mesoporous silica catalysts, respectively.
A recent work by Jiang et al. revealed the high catalytic activity in
CO2 methanation through the synergistic effect between Pd nano- Fig. 5. A probable mechanism for Ni/MSN whereby spillover of atomic hy-
particles and UiO-66 [73]. As shown in Fig. 4, Zr6O4(OH)4 nods of UiO- drogen from Ni interacts with C(a) species and sequentially hydrogenates
66 could facilitate the adsorption and activation of CO2, while Pd na- carbon until the product methane desorbs [81].
noparticles could promote the dissociation of H2 into H atoms for
subsequent reaction with the activated CO2. The catalytic activity was
existence of both intra- and inter-particle porosity in Ni/MSN [81]. In
optimized with Pd loading of 6 wt% in this work. Beyond this metal
addition, these intra and interparticle pores consisting of basic oxygen
loading, unevenly dispersed and agglomerated Pd nanoparticles were
could provide high concentration of basic sites available for CO2 ad-
formed, leading to lower catalytic activity.
sorption. As illustrated in Fig. 5, defect sites or oxygen vacancies in
MSN was responsible for the formation of surface carbon species, which
2.2. Non-noble metal catalysts subsequently reacted with H atom dissociated on Ni sites to form CH4.
In case of Ni catalysts supported on non-reducible materials, alkali
2.2.1. Ni-based catalysts and rare earth oxides have been commonly employed as the promotor
Throughout the literature, Ni-based catalysts are the most widely [82]. One study has reported the increased CO2 adsorption sites due to
used for CO2 methanation due to their satisfactory catalytic perfor- the addition of CeO2 to Ni/MCM-41 catalyst [83]. Synergetic effect
mance, easy availability and low cost. However, Ni-based catalysts are among Ni active sites, CeO2 and MCM-41 could also improve metal-
active at higher temperature compared with noble metal-based cata- support interaction and Ni dispersion, resulting in high catalytic ac-
lysts. At that elevated temperature together with the exothermic nature tivity and good stability. The modification of Ni/SiC catalyst by La2O3
of methanation reaction, Ni particles are also prone to agglomeration also showed positive effect on catalytic performance and durability for
and sintering of Ni particles, leading to catalyst deactivation and loss of CO2 methanation [84]. It was found that La2O3 did not only strengthen
catalytic activity. A number of studies have been conducted to in- the interaction between NiO and SiC but also restrain the growth of NiO
vestigate the influence of (i) nature and properties of the support and nanoparticles. More interestingly, electron environment surrounding Ni
(ii) promoter addition on catalytic performance, aiming to develop atoms could be altered with the presence of La2O3; hence CO2 was more
more industrially promising Ni catalysts for CO2 methanation. easily activated on the Ni atoms. Likewise, the addition of MgO to Ni/
Since Ni has a main role in H2 dissociation to H atoms, the ability to SiO2 catalyst enhanced the capacity of CO2 adsorption and accelerated
adsorb large amounts of CO2 and active CO2 are then one of the criteria the activation of CO2 [85]. Synergistic effect of Ni and Mg species could
for choosing the catalyst support. Similar to noble metal catalysts, re- also inhibit the Ni sintering and oxidation. Nevertheless, amount of
ducible metal oxides have been extensively used due to the prevalence MgO loading needed to be tuned since the excessive addition may
of surface oxygen vacancies. Particularly, great number of oxygen va- provide too much basic sites and cause the blockage of Ni active sites,
cancies over Ni/CeO2 [74–77], Ni/ZrO2 [78] and Ni/CeO2-ZrO2 leading to a decrease in catalytic activity.
[79,80] catalysts could enable large amounts of CO2 adsorption and
facilitate CO2 activation. The defect sites or oxygen vacancies were also
present in mesostructured silica nanoparticles (MSN) due to the

Fig. 4. CO2 methanation over highly dispersed Pd@UiO-66 catalyst [73].

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Fig. 6. Reaction mechanism proposed over Ni/CZ-AE catalyst for CO2 methanation reaction [96].

2.2.2. Co-based catalysts price and less toxicological concern [94,95]. So far, however, there
Some studies have suggested that Co catalysts are the most active have been few studies and little scientific understanding of Fe-based
among the Group VIII metals for CO2 methanation [86,87]. On the catalysts for CO2 methanation. Lack of research on this topic may be
contrary, some studies have reported that only a few Co-based catalysts due to their low selectivity toward CH4. Thus, Fe-based catalysts have
exhibit high CO2 conversion, high CH4 selectivity and good stability at been mostly utilized in Fischer-Tropsch synthesis and ammonia synth-
the same time [88,89]. In reviewing the literature, morphologies and esis [38]. There is abundant room for further progress in determining
surface orientations [90], catalyst supports [88,91,92] and particle size the role of active Fe entities as well as understanding their phase
of metals [89,93] have been thought of as the key factors in the per- transformations, structural changes and participation of surface carbon
formance of Co catalysts in CO2 methanation. species during CO2 methanation [94,95].
The recent study by Lauterbach et al. [90] has noted the importance
of morphologies and surface orientations of Co catalysts in CO2 hy-
2.3. Reaction mechanisms
drogenation. Co3O4 nanorods with exposed (110) surface facets ex-
hibited considerably higher catalytic activity and selectivity toward
In situ or operando diffuse reflectance infrared Fourier transform
CH4 than Co3O4 nanoparticles with exposed (111) and (001) facets. In
spectroscopy (DRIFTS) has been the primary technique used to de-
another study [91], the same group has investigated Co nanorods
termine the mechanism experimentally as it can enable the researchers
(CoNR) with preferential (110) surface facets supported on SiO2, Al2O3
to probe the surface intermediates and track their transformation
or TiO2 for CO2 methanation. In the kinetically controlled regime
during the reaction. In reliance on DRIFTS analysis, mechanisms of CO2
(150−250 °C), CoNR/TiO2 exhibited much higher catalytic activity
methanation can be categorized into formate route and CO route in
than the other two catalysts, which could be attributed to the strong
general [26].
interaction between Co3O4 and TiO2. In the mass transfer controlled
In the formate pathway, formate species are the main intermediates
regime (> 300 °C), CoNR/Al2O3 showed markedly enhanced activity
without the involvement of carbonyl (COad) during the reaction. Ashok
due to the fact that Al2O3 has great thermal conductivity. In contrast to
et al. proposed a possible mechanism for CO2 methanation over Ni/
CoNR/TiO2 and CoNR/Al2O3, CoNR/SiO2 showed no change in cata-
CeO2-ZrO2 catalyst prepared via ammonia evaporation, in which the
lytic activity compared to pure CoNR.
main pathway went through formate species formation. In Fig. 6, CO2
One study by Zhou et al. [92] has focused on inert SiO2-supported
first linearly adsorbed onto catalyst support as mono- or bi- dentate
Co catalysts for CO2 methanation. A highly ordered cubic mesoporous
carbonate, which was then reacted with H atom dissociated on metallic
silica KIT-6 material was used to prepare highly dispersed Co/KIT-6
Ni to form hydrogenated carbonates. These hydrogenated carbonate
catalyst, which exhibited superior catalytic activity and higher CH4
species again reacted with H atom to form monodentate formates,
selectivity as compared with Co/meso-SiO2 catalyst. Better catalytic
which were later transformed to formaldehyde-like and methoxy spe-
activity can be certainly attributed to higher Co dispersion over the
cies, respectively, prior to being released as CH4.
large surface area of KIT-6. Additionally, the ordered bicontinuous
In another work by Wang et al., the formate route was also proposed
mesoporous structure of KIT-6 can enhance CH4 selectivity by facil-
for CO2 methanation over Ru/CeO2 catalyst; however, different inter-
itating the diffusion and transfer of CH4 product molecules.
mediate species and steps were involved in the reaction pathway [56].
Recently, Guo and Song groups [88] conducted the screening of
The conversion of Ce3+ to Ce4+ coincided with the conversion of CO2
various supports including ZrO2, Al2O3, SiO2, SiC, TiO2 and activated
to CO2δ− in step (1), which was hydrogenated to formate in step (2).
carbon for Co catalysts. Among these catalysts, Co/ZrO2 exhibited
The dissociation of formate to methanol took place in step (3), which
highest CH4 yield and high stability without deactivation after 300 h in
was identified as the rate-determining step and followed by hydro-
CO2 methanation. It was the first time that the formation of a new Co-Zr
genation of methanol to CH4 in step (4).
phase at the Co-ZrO2 interface was discerned by TEM. This phase could
It was noteworthy that change in structure of Ni/ZrO2 catalyst could
play a key role as the additional CO2 adsorption sites in CO2 metha-
alter the reaction mechanism route [78]. Ni/ZrO2-C catalyst prepared
nation. Their follow-up study then attempted to provide more Co-ZrO2
via conventional incipient wetness impregnation followed the formate
interface by decreasing Co particle size [89]. Specifically, citric acid
route due to no observation of carbonyl species in the DRIFTS spectra,
was used to form complex with Co precursor, which led to decreased Co
as presented in Fig. 7(b). On the contrary, Ni/ZrO2-P catalyst prepared
particle size, increased Co dispersion and strengthened Co-ZrO2 inter-
via plasma-assisted impregnation consisting of exposed Ni(111) facet
action. The suitable Co-ZrO2 interaction could induce more catalytically
involved the formation of COad as the intermediate species, so-called
reduced active sites and more oxygen vacancies, thus providing more
CO route, as shown in Fig. 7(a). Linear and bridge CO formed on the Ni
CO2 adsorption and high catalytic hydrogenation.
surface are visible in 2100−1950 cm−1 and 1950-1750 cm-1, respec-
Fe-based catalysts also exhibit a decent activity in CO2 methanation
tively. More stable bridge form seems to be dominant carbonyl species,
[86]. Compared to Ni catalysts, Fe catalysts benefit from their lower
which can migrate in the interfacial region and be hydrogenated to

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J. Ashok, et al. Catalysis Today 356 (2020) 471–489

Fig. 7. Operando DRIFTS spectra during temperature-programmed reaction of a gas mixture (40 mL min−1) containing 2.5 % H2, 0.5 %CO2 with Ar as carrier gas
over Ni/ZrO2-P (a) and Ni/ZrO2-C (b) [78].

CH4.
In a recent study, CO route was also postulated for CO2 methanation
over Ru/Al2O3 catalyst [97]. As sketched in Fig. 8, CO2 was adsorbed
on the catalyst support and converted bicarbonate species, which were
then reacted with H atoms dissociatively adsorbed on Ru sites to gen-
erate the formate species at the metal-support interface. Further reac-
tion of formates with H atoms could occur producing CO adsorbed on
Ru sites, which was stepwise hydrogenated to CH4.
The formation mechanism of COad as the intermediate species in the
CO route can be via the dissociation of CO2 to COad and Oad as well.
Sharma et al. revealed the mechanistic insights into CO2 methanation
over Ce0.95Ru0.05O2 catalyst, in which carbonates and CO were the in-
termediate species with no role of formates as follows [57]:

CO2 → CO → OCH2 → OCH3 → CH4

It is also possible that formate (*HCOO) species can be only a

spectator on Ru [98], Ni [99] and Co [90] catalysts. As can be seen in
Fig. 9, Lauterbach et al. [90] reported the formation of formate species Fig. 9. In situ DRIFTS spectra of CO2 hydrogenation on nanorods and nano-
(at 1600 and 1415 cm−1) as the site-blocking surface intermediates on particles at 250 °C [90].
Co nanoparticles (CoNP). Without the formation of inactive formate
species, Co nanorods (CoNR) exhibited superior activity through the
[101], however, proposed that CO* hydrogenation was the rate-de-
formation of active formyl (*HCO) species derived from initial dis-
termining step of CO2 methanation. CO* hydrogenation could form
sociation of CO2 to *CO.
HCO*, HCOH*, H2COH*, CH2*, CH3* and CH4* on the Ni(111) or (200)
The insights into the mechanisms of CO2 methanation could also be
surface. Recently, Huang et al. [102] took both studies by Ren et al.
disclosed by density functional theory (DFT). In the comparative study
[100] and Zhen et al. [101] into account and included CO2* C-terminal
by Ren et al. [100], CO route was found to be more energetically fa-
hydrogenation and OH* removal from HCOH* and H2COH*. The results
vorable for CO2 methanation over Ni(111) surface. Comparing between
revealed that formate pathway via the HCOOH* intermediate was the
HCOO → CO + OH and CO → C + O as the rate-determining step, the
optimal pathway over Ni(111) surface as follows:
path started with CO2 dissociation into CO and O exhibited lowest
maximum energy barriers. Therefore, CO2 → CO + O → C + O + 4H CO2* → HCOO* → HCOOH* → HCO* → HCOH* → CH* → CH2* →
→ CH2 + 2H → CH3 + H → CH4 was the optimal path. Zhen et al. CH3* → CH4* → CH4,

Fig. 8. Schematic representation of CO2 methanation reaction pathway and The evolution of the detected species over Ru/Al2O3 catalyst [97].

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J. Ashok, et al.
in which HCO* hydrogenation to HCOH* was the rate-determining
step.
Overall, the nature of the intermediate species and steps involved
during CO2 methanation mechanism can vary from one catalyst system
to another, strongly depending on the properties of the active metals,
supports and metal-support interaction. Although the exact mechanism
is still under debate, the researchers have made a significant progress in
fundamentally understanding the reaction mechanisms and providing a
new insight into the rational catalyst design for CO2 methanation by
utilizing in situ or operando DRIFTS and DFT calculations.
2.4. Catalyst deactivation
In CO2 methanation reaction catalyst deactivation is a big challenge.
There are many factors which cause deactivation during methanation
reaction, the major factors are metal sintering, carbon deposition and
catalyst structural changes.
Deactivation due to carbon accumulation and metal sintering were
considered as physical deactivation, which is most common for Ni-
based catalysts. Carbon deposition may be caused by either CO dis-
proportionation or incomplete CO hydrogenation reactions. At CO2
methanation reaction conditions, carbon deposition due to CH4 de-
composition is thermodynamically unfavourable. For Ni-based cata-
lysts, it has been reported that the deposition of carbon is depends on
the nature and size of the Ni particles [103]. In a study on Ni/YSZ
catalysts, Kesavana et al. observed that the catalyst prepared by im-
pregnation method has the formation of graphitic filaments on the flat
Ni° surfaces, whereas thin film of carbon was accumulated on spherical
Ni° particles [103]. Furthermore, the deposition of carbon can be
eliminated by introducing steam or increasing H2/CO2 ratio, because
H2 has the ability to hydrogenate the deposited carbon species at CO2
methanation conditions. Addition of steam has no influenceon oxi-
dizing the Ni° to Ni2+ species during methanation reaction, whereas for
Co based catalysts, steam can initiate the oxidation and mobility of Co
species during the course of reaction. Next, to minimize the metal
sintering, developing a catalyst with increasing metal dispersion by
strong interaction between metal and support [88], adding promoters
[104] and adopting advanced synthesis methods are the most common
strategies [105]. A core-shell structured NiO-MgO@SiO2 catalyst,
where SiO2 shell prevent Ni agglomeration by encapsulation and a
stable methanation activity for 100 h was reported by Li et al. [106], In
other work, MOF-derived Co-based porous carbon catalysts, in which
the Co species were separated by grahitic carbon species [107]. In other
works, the deactivation of Ni-based catalysts at low-temperature me-
thanation was due to the formation of mobile Ni-subcarbonyl (Ni(CO)x
with x = 2 or 3) species (at 2060 cm−1 as shown in Fig. 10), which
tends to migrate and causes Ni sintering [108,109].
Besides, the deactivation of CO2 methanation is also due to the
decrease in active sites caused by formation of spinel structure. In a
study between Co supported on ZrO2 and Al2O3 catalysts, Co/ZrO2 gave
stable methanation performance for nearly 300 h, whereas Co/Al2O3
showed rapid deactivation within same time on stream [88]. With
thermogravimetric analysis and hydrothermal treatment techniques, it
has been reported that the deactivation in Co/Al2O3 catalyst is due to
the formation of inactive CoAl2O4 spinel. The formation of CoAl2O4
spinel is accelerated by by-product steam in the reaction environment.
Though the carbon formation is one of the reasons for deactivation,
however, the main reason for deactivation in Co/Al2O3 is formation of
inactive CoAl2O4 spinel structure.
3. CO2 methanation in catalytic membrane reactor
The integration of membrane separation with a catalytic reaction is
termed as a membrane reactor and it is always of interest it terms of
process intensification [21,22]. The yield of a reversible reaction can be
enhanced over the thermodynamic equilibrium conversion by in situ
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Catalysis Today 356 (2020) 471–489
Fig. 10. In situ DRIFT spectra as a function of reaction time (in min) obtained
during the CO hydrogenation over Ni/SiO2 at 230 °C [108].
removal of one of the product from the reaction using a membrane
[23]. The selective separation of the product from the reaction shifts the
equilibrium in the forward direction according to the Le Chattelier’s
principle. The membrane reactors also can be used to feed the reactants
to the reaction from an impure stream and boost the reactor perfor-
mance. The reactant supply to a particular reaction is also controlled by
using a membrane which eventually affects the rate and selectivity of
the reaction [24].
CO2 methanation reaction or Sabatier reaction is an efficient way of
CO2 capture for production of SNG which, can be directly used in an
internal combustion engine. The reaction requires hydrogen as one of
the reactant and supply of pure hydrogen to the reaction makes the
process expensive. However, combining with H2 generation with CO2
methanation reaction using a hydrogen perm-selective membrane have
synergetic effect on the overall performance of the reaction [110].
Coupling the Sabatier reaction with hydrogen permeable membrane
decreases the additional cost and equipment required for pure hy-
drogen production. Further, the reaction produces H2O as one of the
products, removal of the product from the reaction using H2O perme-
able hydrophilic membrane can increase the product yield of the re-
action [111]. This is in accordance with surpassing the thermodynamic
equilibrium of the reaction towards more product formation by re-
moving one of the product from the reaction zone. Considering both the
two cases the type of membrane used are classified as (a) H2 permeable
membrane to feed hydrogen to the CO2 methanation reaction and (b)
H2O permeable membrane for removing the produced steam from the
reaction mixture. The schematic representation of both two types of
membranes are shown in Fig. 11.
3.1. Coupling with H2 permeable membrane to feed hydrogen as a reactant
Palladium based membranes are one of the most studied system for
hydrogen separation and recovery [112–114]. The membranes have
very good thermal and mechanical stability to be used under high
temperature and pressure reaction conditions [115–117]. Pd-alloy with
different transition metals have been utilized to recover H2 from reac-
tions like water gas shift reaction, steam methane reforming (SMR)
reaction etc. to overcome the equilibrium limitations of the reaction
[118]. However, integration of Pd membrane with different reactions to
feed H2 from an impure gas stream have also been studied. Many re-
actions like hydroxylation of methyl benzoate, conversion of benzene to
J. Ashok, et al.
Fig. 11. Schematic representation of CO2 methanation reaction in different
types of membrane reactor.
phenol, production of ammonia etc. have been studied previously using
Pd-alloy membrane to supply hydrogen to the reaction [119–122]. The
rate and conversion of the reactions have been enhanced by coupling
with the membrane reactor. The participation of the active H-atom near
the membrane surface helps to enhance the rate of reaction.
The combination of Pd membrane for coupling of CO2 methanation
and NH3 decomposition was studied by M. Miyamoto et al. (Fig. 12)
[24]. Ammonia decomposition reaction is an efficient way to store and
produce hydrogen. Pd membrane has been explored for ammonia de-
composition reaction to produce pure H2 [119,123]. Significant en-
hancement in the performance of both the Pd membrane and NH3 de-
composition reactions was reported after the integration of both
reactions [24].
They observed that the H2 permeation through the membrane was
increased after coupling with the CO2 methanation reaction compared
to sweep gas condition. The enhanced hydrogen permeation is ascribed
to lower H2 partial pressure in the permeate side due to continuous
Fig. 12. Coupling of CO2 methanation with NH3 decomposition [24].
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Catalysis Today 356 (2020) 471–489
Fig. 13. Enhancement of CH4 selectivity after combining with the membrane
[24].
consumption during the reaction. However, no improvement in the CO2
methanation reaction was observed except improvement in CH4 se-
lectivity. It is well known that hydrogen permeation through dense Pd-
based membranes follows a dissociative chemisorption route. The gas-
eous hydrogen molecule dissociates on the membrane surface to form
H-atom, and they diffuse through the interstitial sites of bulk membrane
via a quantum mechanical hooping mechanism. The atomised hydrogen
recombines on the permeate side of the membrane to form H2 molecule
and desorb from the surface [124,125]. According to the literature data
[24] due to hydrogen spill over mechanism the active dissociated hy-
drogen reacts with the adsorbed CO to form CH4 before it is desorbed
from the surface. The hydrogen spill over supress the formation of CO in
CO2 methanation reaction in a membrane reactor. The increased CH4
selectivity of CO2 methanation reaction in a membrane reactor is shown
in Fig. 13.
Recently, Pati et al. [110] studied the CO2 methanation reaction in a
H2 permeable Pd-Cu membrane reactor. They studied the feasibility of
coupling the exothermic CO2 methanation reaction and endothermic
propane dehydrogenation reaction in a single membrane reactor. The
authors claimed that the exothermicity of the CO2 methanation reaction
was decreased in a membrane reactor due to the homogenous supply of
hydrogen to the catalyst bed. The hot spot formation is a common
phenomenon for an exothermic reaction in a fixed bed reactor [126].
The reason of this is the localised heat accumulation and uneven mass
distribution throughout the catalyst bed. Using a membrane reactor,
hydrogen can be supplied homogenously over the catalyst bed and the
even distribution of the reactants reduces the hotspot formation in the
reactor bed. Hydrogen recovery was also reported to be increased by
coupling with CO2 methanation reaction (Fig. 14). Pd-membrane is
often susceptible to poisoning in presence of unsaturated hydrocarbons,
due to the stronger interaction of the vacant d-orbital of Pd with the pi-
electron cloud of the unsaturated compounds [127].
The study by Pati et al. [110] showed higher stability of Pd-Cu
membrane compared to Pd in presence of C3H6 and C3H8. The ob-
servation for this was ascribed to the filled d-orbital of Pd-Cu system
compared to pure Pd. The authors studied the absorption of C3H6 in the
two different membranes using in situ DRIFTS analysis shown in Fig. 15
and concluded that the Pd-Cu has a filled d-orbital compared to Pd,
which enables poor overlap between the PI-orbital of C3H6 and the
metallic d-orbital. The weaker adsorption of propylene resulted in in-
creased stability and less deactivation of H2 flux in a bimetallic Pd-Cu
membrane.
Therefore, they predicted that the membrane reactor is feasible for
propane dehydrogenation to produce C3H6, and the hydrogen can be
simultaneously separated through the membrane and utilized in the
J. Ashok, et al.
Fig. 14. Hydrogen recovery in membrane reactor, using sweep gas and cou-
pling with the membrane reactor.
Fig. 15. In situ DRIFTS spectra of C3H6 on Pd and Pd-Cu membrane.
CO2 methanation reaction. The combination of dual reactions helps to
increase the yield of propane dehydrogenation reaction and CO2 me-
thanation reaction. Further removing hydrogen from a reaction in situ
and using it for the CO2 capture reduces the supply of pure H2 cost for
CO2 methanation reaction.
The different studied results showed increased hydrogen recovery
after coupling with CO2 methanation reaction. The simultaneous con-
sumption of H2 in the permeate side creates a potential difference
across the membrane and the rate of H2 permeation increased. The
hydrogen spill over mechanism is also in important phenomena to in-
crease the selectivity and the rate of reaction. Mostly Pd-based mem-
branes have been explored for this applications, however, low cost
carbon or zeolite based membranes can also be utilized to reduce the
noble metal coast. Pd-membranes are susceptible to irreversible poi-
soned in presence of H2S which is present in the bio-hydrogen. Hence a
stable H2S resistance membrane which can be operated at lower tem-
peratures is imperative.
3.2. Integration of H2O permeable membranes to increase the conversion
Removal of H2O from the CO2 methanation reaction benefits in
terms of increased conversion in a membrane reactor. Hydrophilic
water permeable membranes have been explored to steam separation
from different gas mixtures [128,129]. The hydrophilic membranes,
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Catalysis Today 356 (2020) 471–489
due to the capillary condensation of water molecules inside the pores
decreases the flux of less hydrophilic molecules and increases the se-
lectivity of H2O. In the porous membranes, the permeation of different
non condensable gases such as H2, CO, CH4 shows Knudsen diffusion
mechanism. And the permeance show linear relationship with the re-
ciprocal of squire root of product of molecular weight (1/√M) whereas
the condensable H2O follow surface diffusion mechanism. Based on
these results, H. Ohya et al. [111] studied the CO2 methanation reaction
in a H2O permeable membrane reactor using 0.5 %Ru/Al2O3 catalyst.
They used microporous glass deposited over a ceramic support as a H2O
perm selective membrane. They observed higher selectivity of mem-
brane towards H2O compared to other gases H2, CO2 and CH4. When
coupled with reaction, the yield of reaction increased about 18 % than
without membrane. However, their result showed that the conversion
with the membrane reactor is below the equilibrium conversion at
lower temperatures and temperature above ∼400 °C the conversion go
across the equilibrium conversion.
An economic analysis for utilization of the H2O perm selective
membrane reactor for CO2 methanation reaction was analysed by B. Lee
et al. The authors studied the techno economic analysis and the feasi-
bility study to analyse the remunerations after integrating the catalytic
reaction in a membrane reactor. The economic analysis showed that the
production cost of the SNG reduced from 1.82 $ kg in a fixed bed re-
actor to 1.67 $ kg in a membrane reactor.
The combination of the H2O permeable membranes for several gas
phase reactions are limited due to the poor selectivity of H2O compared
to other gaseous molecules. This is because of the comparable kinetic
diameter of the diffusing molecules through the membrane pores. The
selectivity of the membranes for H2O purification in presence of gas-
eous mixtures like H2 and CO2 decreases with increased temperature
and pressure, which affects the performance of the membrane reactor.
Another important parameter is the rate of H2O permeation through the
membrane, which should match with the rate of moisture production in
the reaction. Thus a defect free membrane with high H2O flux is also
desirable parameter. This can be achieved by choosing a suitable
synthesis method to prepare ultrathin and defect free membrane.
Integration of H2O permeable membranes to CO2 hydrogenation to
methanol and other higher hydrocarbons is also another potential and
high emerging area to increase the reaction yield. Thus further devel-
opments in the water permeable membranes is required for its appli-
cation under high temperature and pressure. Several mixed matrix
membranes can be developed with high hydrophilicity to enhance the
H2O flux and maintain a good selectivity.
4. CO2 hydrogenation under plasma process
Since CO2 is highly stable, a high temperature is always required in
the catalytic process. The high energy input for CO2 activation has been
one of the major challenges in CO2 conversion and utilization
[130–133]. Recently, Non-thermal plasma (NTP) assisted conversion
technique has drawn increasing attention and been regarded as a pro-
mising strategy for CO2 hydrogenation under mild conditions
[134–137]. A NTP is featured by the high energy species such as ions,
free radicals, electrons, etc. which can activate CO2 and other molecular
species without any external heating input [138,139]. Various types of
plasma reactors (microwave discharge reactor, dielectric barrier dis-
charges (DBD) reactor, gliding arc discharges reactor and glow dis-
charge reactor) are being investigated now. Among these reactors, DBD
reactors have been most used and widely investigated in CO2 conver-
sion for their simple operation and low cost [140–142].
Fig. 16a shows a one-dimensional fluid model of DBD for NTP-as-
sisted CO2 hydrogenation [143]. When applying a potential difference
between the coaxial electrodes, the CO2/H2 mixture is excited under the
collisions with high energy species in the reactor thus creating excited
molecules, and finally new compounds. In most cases, the final products
include CO, CH4, CH3OH, CH2O etc (Fig. 16b) and hence a catalyst
J. Ashok, et al.
Fig. 16. a) The illustration of DBD plasma reactor, b) Dominant reaction pathways for the conversion of CO2 and H2 into various products, in a 50/50 CO2/H2 gas
mixture. The thickness of the arrow line is proportional to the rates of the net reactions. The stable molecules are indicated with black rectangles [143].
should be involved for selectivity enhancement.
4.1. Catalytic CO2 methanation
CH4 is a fuel and commodity gas that widely applied in industry and
civil use. It is a source for a wide range of important chemical raw
materials, such as ethyne, hydrogen, and ammonia, etc. One of the ways
to produce CH4 is through the CO2 methanation with H2, which is
thermodynamically exothermic and favourable at ambient temperature.
However, to achieve acceptable methane yield, this conversion needs to
be conducted with a catalyst at high temperatures (> 350 °C)
[144,145], which is contrary to the favorable temperature.To solve the
problem mentioned above, the association of a catalyst with a plasma
has been reported and which shows great potential in boosting CO2
methanation under mild conditions [146,147]. For this methanation
reaction, numerous catalytic systems, especially those based on tran-
sitional metals have been developed [148–150]. Nickel-based catalysts
have been mostly proposed and investigated in the methanation from
H2 and CO2.
Compared with those noble metals, i.e. Ru, Pt, the relatively low
cost of Ni can allow a much higher metal-loading, In another word, the
good compromise between high activity and low price promote the
constant development and investigation in Ni-based catalysts
[151–153].
The catalysts are usually supported on various porous materials,
such as Al2O3, SiO2, zeolites and oxides (NBTI), whose interaction be-
tween the metal may also be of great significance to catalyst perfor-
mance [154–156]. The effects of these supports on catalytic perfor-
mance has been studied extensively by many researchers. C. Henriques
et al. proved that the hydrophobicity of the catalyst plays an important
role in the performance of the reaction. When the ratio of Si/Al in Ni/γ-
Al2O3 catalyst is higher, a better performance could be obtained since it
will decrease its affinity to H2O, and thus to a decrease in the inhibitory
role of this compound in CO2 methanation process. [156]. The benefits
of introducing CeO2 to the commercial Ni/Al2O3 catalysts has been
presented by T. Andreu et. al. [157]. In the synthesized Ni-CeO2/Al2O3
catalyst, Ni and Ce would corporately catalyse the methanation reac-
tion, hence enhancing the reaction performance in both thermal and
plasma process. Nevertheless, the experimental results shown that a
significantly lower content of CeO2 was more active under plasma
process with respect to the thermal process. This is due to the formation
of CO intermediate (Fig. 17), and which also shown a significant role in
CO2 methanation. This result suggested that the by-products as reactant
for the optimization of catalysts composition should be considered in
plasma-catalysis process.
Except for Ni-based materials, other materials have also been ex-
plored as the catalyst for CO2 methanation. Tu et al. used Cu or Mn on
alumina to catalyse the methanation with a DBD plasma at low tem-
perature and atmospheric pressure [158]. The effect of different γ
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Catalysis Today 356 (2020) 471–489
-Al2O3 supported metal catalysts (Cu/γ -Al2O3, Mn/γ -Al2O3, and
Cu–Mn/γ -Al2O3) on the performance of the CO2 hydrogenation has
been investigated. The results shown that addition of Mn into the cat-
alyst could both promote the conversion of CO2 (∼36 %) and improve
the selectivity of CH4 (45 %).
4.2. CO2 conversion into methanol
Another important route for CO2 conversion is CO2 hydrogenation
to CH3OH. CH3OH is regarded as a valuable fuel substitute and additive
in energy industry. It is clean burning and highly biodegradable and is
also a key feedstock for some higher value downstream products, for
example, formaldehyde, acetic acid and methyl ethers, etc. What is
more, methanol is considered as a promising energy carrier, especially
for hydrogen, because as a liquid, it is easier to be stored and trans-
ported.
Though the CO2 conversion into CH3OH has attracted constant in-
terests, fundamental works in this field is still lacking today. In 1998,
Zhou et al. investigated the NTP-assisted CO2 hydrogenation to CH3OH
with and without catalysts [160]. When no catalyst was packed in the
reactor, the methanol yield was only 0.2 % at the atmospheric pressure
(1 bar) and low temperature (50 °C). To improve the CH3OH produc-
tion, a catalyst was introduced to this system, as well as an increase in
the reaction pressure (8 bar) and temperature (100 °C). However, the
methanol yields still stay at a low level (< 1%). Satoru and his co-
workers also reported the formation of CH3OH by using a radio fre-
quency (RF) impulse discharge [161]. By adjusting the discharge
parameters, such as voltage, gas flow rate, gas mixing ratio, and gas
residence time, the author found that the methanol production would
be maximized with a ratio of 1:6 in CO2/H2 mixture, although the
desired product was still obtained with a low yield, accounting for only
about 4 % among the products containing carbon from CO2. Tu et al.
successfully achieved a higher production of methanol through CO2
hydrogenation at room temperature (∼30 °C) and atmospheric pressure
by using a DBD plasma (Fig. 18a) [159]. In this work, the authors de-
monstrated that the methanol production depended strongly on the
plasma reactor setup. As shown in Fig. 18b-c, the reactor Ⅲ with a
unique water electrode design shows the highest production of me-
thanol among the three kinds of plasma reactors. Besides, the perfor-
mance of the plasma process with and without catalyst have also been
investigated. By comparison, plasma process packed with catalyst
shows higher selectivity and yield of methanol, and the Cu/γ-Al2O3
catalyst showed a better activity toward the conversion of CO2 than Pt/
γ-Al2O3 catalyst. The optimal methanol yield of 11.3 % and methanol
selectivity of 53. 7 % were achieved over the Cu/γ- Al2O3 catalyst when
using reactor III. This part of the review has largely demonstrated the
potential of plasma-assisted catalysis in converting CO2 into high value-
added products, especially CH4 and CH3OH. However, up to now, the
investigations about plasma-assisted CO2 hydrogenation are still scarce
J. Ashok, et al.
Fig. 17. Proposed reaction mechanism. a) methanation of CO2 by thermal activation in NiCe catalyst, b) Plasma left: low CeO2 content catalysts, c) Plasma right: high
CeO2 content catalysts [157].
and more researches about this field should be done to further exploit
the potential of plasma catalysis. On the one hand, more focuses should
be put on the design of specific catalysts to improve the products se-
lectivity and energy efficiency. On the other hand, the design of the
plasma setup to form the unique products is also needed. Furthermore,
revealing the reaction mechanism, like the interaction of various ex-
cited states with the catalyst surface and their prominent role in the
products formation, is also quite necessary. Based on the three aspects
as mentioned above, the development of plasma-catalysis will be sig-
nificantly promoted.
5. Photo-catalytic CO2 hydrogenation
Photocatalytic technology, which utilizes the abundantly available
solar energy and economical reactant (water) to reduce CO2 into solar
fuels, has attracted much attention recently. Generally, photocatalysts
were based on the nature of semiconductor materials in which the
electrons will move to conduction band (CB) from valence band (VB) if
the solar irradiation energy is higher than the semiconductor’s band gap
energy [162]. Then the electrons in the CB can reduce CO2 into dif-
ferent products, including CH4, CO, methanol, formic acid and for-
maldehyde, and the holes left in the VB can carry out the oxidation
reaction. However, the electrons and holes are always not instantly
exhausted, resulting in the combination of them. In addition, the charge
consumption during the reaction and light utilization are very low,
which limits the application of photocatalytic CO2 reduction [163,164].
To this end, various highly efficient photocatalysts with high electron-
hole separation, fast charge consumption and good light utilization
were prepared to improve the photocatalytic CO2 reduction perfor-
mance.
Among all the photocatalysts, TiO2 is widely employed photo-
catalyst due to its good activity under UV irradiation, high chemical
stability and non-toxicity [165]. Nevertheless, TiO2 shows light ab-
sorption only under UV region and suffers from serious charge-holes
Fig. 18. a) Scheme of CO2 Hydrogenation to Methanol, b) Images of H2/CO2 discharge generated in different DBD reactors (I, II, and III) without a catalyst, c)
methanol yield and CO2 conversion (reaction pressure 1 atm, H2/CO2 molar ratio 3:1) [159].
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Catalysis Today 356 (2020) 471–489
recombination problem. Several methods, for example, morphologies,
surface modification, heterojunction, have been adopted to improve the
performance of TiO2-based photocatalysts. Fang et al. developed TiO2
microspheres with hierarchical porosity made of larger mesopores (ca.
12.4 nm) and smaller mesopores (ca. 2.3 nm) [166]. Comparing to
commercial Degussa P25 TiO2, the as-prepared TiO2 microsphere cat-
alyst has significant enhancement in photodriven conversion of CO2
into CH4. As is shown in Fig. 19, different morphologies (nanoparticle,
microsphere, nanosheets, nanorods, nanowires, nanotubes) of TiO2
photocatalysts can be controlled, which will affect the surface area,
electrons transport and the route of mass transfer and influence the
photocatalytic efficiency. Surface functional groups are also playing an
important role in the interface between reacants molecules and cata-
lysts. Functional groups provide the basic active sites to attract CO2 and
absorb CO2, which leads to higher reaction rates of CO2 reduction. Liu
et al. found the organic amine, diethylenetriamine, was crucial for the
functionalization of titanate nanosheets and resulted in high CO2 ad-
sorption capacity, and achieved efficient photocatalytic CO2 reduction
toward solar fuels [167]. Some other methods, such as metal, non-metal
doping, cocatalysts, can also boost the performance of photocatalytic
CO2 reduction [168,169].
g-C3N4, another photocatalyst shows great prospects for advance-
ment of photocatalytic CO2 reduction [170]. Although g-C3N4 is an
ideal photocatalyst with an estimated bandgap of 2.7 eV, its application
is still limited by its fast recombination of photo-generated electrons
and holes and limited absorption of visible light. So combining g-C3N4
with another semiconductor to form heterojunctions, elemental doping,
co-catalyst deposition and surface functionalization, etc. are widely
used to improve the photocatalytic performance of g-C3N4 [171]. Cao
et al. reported In2O3/g-C3N4 hybrid photocatalysts with enhanced pho-
tocatalytic CO2 reduction efficiency [172]. Because of the effective
charge separation between g-C3N4 and In2O3, their photocatalytic CO2
reduction was obviously higher for CH4 production. Raziq et al. showed
SnO2-coupled boron and phosphorus co-doped g-C3N4 exhibited
J. Ashok, et al.
Fig. 19. Different morphologies of TiO2 (a) Microsphere (b) Nanoparticles (c) Nanosheets (d) Nanowire (e) Nanotubes and (f) Nanorods [162].
enhanced visible-light activities for CO2 conversion to CH4, compared
to the bare CN nanosheets [173]. Besides, there are also other kinds of
materials, including some metal oxides, metal-organic frameworks,
graphene-based materials, employed in the photocatalytic CO2 con-
version [163,174–176].
Although some advancements have already been made about the
photocatalytic CO2 reduction to CH4, its yield and selectivity are still
very low because of the limited utilization of light and separation of
charges and holes. Up to now, there are still a lot of challenges to get
more efficient and durable photocatalysts. In addition, the mechanism
of photocatalysis is still not clear and some in-situ technologies such as
FTIR, EPR can be employed to look insight into the mechanism of
photocatalysis. Electrocatalysis and thermocatalysis can also be com-
bined with photocatalysis to improve the performance of CO2 conver-
sion to CH4.
6. Conclusions and outlook
In this review, we have summarized various CO2 hydrogenation to
methane processes. Among the discussed processes thermos-catalytic
conversion of CO2 into methane is a mature technology. Most of the
research is happening with respect to catalyst technology. For this
process, recent developments are mainly focused on the catalysts ac-
tivity at low-temperature region due to thermodynamic favor. Ni and
Ru are much explored active components for CO2 methanation reaction
with the utilization of reducible support materials. Ru based materials
gave better activity at lower reaction temperatures, however due to
kinetic limitations at lower temperature, Ni-based catalysts are seeming
to be much suitable candidate for high temperature region. Apart from
active metal sites, designing support and addition of promoters play a
crucial role in activating H2 and CO2 molecules at mild conditions. The
reducible nature of the support materials such as CeO2 and recently,
nano-structured zeolites materials found to be promising as catalyst
support materials. Due to the exothermic nature of the reaction, con-
stant removal of heat is required to avoid possible hot spots during the
reaction. The fixed-bed reactors are the most widely used systems for
the CO2 methanation. Fluidized-bed reactors have proven highly reli-
able for the CO methanation, and other types of reactor are still under
development.
For intensifying the thermo-catalytic CO2 methanation process,
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Catalysis Today 356 (2020) 471–489
integrating with selective membrane is one of the options. The H2 se-
lective permeable Pd-alloy coated ceramic membrane helps to supply
purified H2 reactant to CO2 methanation process from H2 rich syngas
mixture produced from reforming reactions like biomass and coal ga-
sification process. Also when the CO2 methanation is coupled with H2O
permeable zeolite materials coated membrane, helps to overcome the
thermodynamic limitations at high temperature conditions. However,
the compatibility and long term stability of hollow fiber membrane in
the actual reaction conditions is little known.
Recently, plasma-assisted CO2 hydrogenation draws interest for
many researchers as it is considered as energy efficient compared to
conventional thermal catalysis. However, it is limited by the ability of
product selectivity. Another added advantage for this processes is wide
range of H-containing feeds can be used as H2 source for CO2 hydro-
genation reaction. To enhance the selectivity towards methane forma-
tion, the catalyst role is crucial. Generally, most of the heterogeneous
CO2 hydrogenation catalysts required certain temperature condition to
be active for selective methanation reaction. Therefore, to full use of
catalytic property of a catalyst, plasma-catalyst process should be op-
erated at mild reaction temperatures. By this way the yields of desired
products via CO2 hydrogenation reaction will be improved sig-
nificantly.
Similarly, for photo-catalytic CO2 methanation process, aalthough
some advancements have already been made, its yield and selectivity
towards CH4 formation is still very limited. It is due to the limited
utilization of available light and separation of charges and holes. Up to
now, there are still a lot of challenges to get more efficient and durable
photo-catalysts. One recommended advancement to overcome these
issues is to couple the photo-catalysis with mild thermal energy. As
highlighted before, in thermal-photo catalysis the selectivity and over
all yield of the desired product can be significantly improved.
In view of technology readiness level for various CO2 methanation
processes, the thermal CO2 methanation process is mature enough to be
commercialized. The catalyst technology available so far can reach near
equilibrium CO2 conversions and > 99 % of selectivity towards me-
thane formation. However, for non-noble metal based catalysts there is
a need in further development to achieve high conversion at lower
reaction temperature (< 200 °C) to obtain near 100 % CO2 conversion.
With respect to reactor technology, there are many kinds of commercial
scale reactor are available to carryout CO2 methanation reaction.
J. Ashok, et al.
However, the main drawback for commercialization of this technology
the availability of cheap and renewable H2 and CO2 source. In contrast,
catalytic membrane process is less mature, the concept of membrane
assisted catalytic CO2 reforming process is demonstrated in lab en-
vironment. The testing in the relevant atmosphere need further re-
search. In this process, the membrane technology for pure gas separa-
tions is commercially viable for limited applications. For instance, Pd-
alloy based membranes can be used to separate H2 from a syngas
mixture, however, high concentration of CO can poison the Pd metal of
the membrane, which reduces the separation efficiency of membrane.
Furthermore, selective separation of gases at moderate temperatures
and presence of poisonous gases is challenging for this technology. For
Plasma assisted and photo assisted processes, the technology available
so far with respect to catalyst and reactor are much inferior than
thermal process for CO2 hydrogenation reaction. Much research is re-
quired for these technologies to achieve high selectivity with reason-
able conversions.
In general, the research and commercial perspectives of CO2 me-
thanation technologies are proposed as follows:
• With respect the catalyst development, further research is required
to develop new materials which can be able to perform CO2 me-
thanation reaction at lower temperature.
• To obtain high methanation activity at lower reaction temperature,
activation of CO2 molecule is crucial, oxygen mobility and basic
properties of a support helps to activate CO2 at milder condition.
• In commercial point off view, this process is viable if CO2 and H2
were generated from renewable or wasted energy. For instance, CO2
can be collected from power plants and H2 can be generated from
biomass gasification or water splitting using renewable energy.
Moreover, the cheaper way of continuous separation of these gases
from a gaseous mixture is challenging. Further research is required
in gas separation technologies to selectively separate CO2 and H2
from diluted resources at much flexible atmospheres.
• For catalytic membrane process, further research is required to in-
vestigate the stability of membranes in the presence of poisonous
compounds such as H2S and so on. Another area of development is
required for scaling up the overall catalytic membrane process to
suit for industrial scale.
• For plasma assisted process, selectivity of desired product is chal-
lenging. Further research is required to understand the CO2 and H2
activation mechanisms and possible intermediate formations in the
presence of plasma energy and thermally best catalysts is required.
The understanding of detailed reaction mechanism helps to fine tune
operating conditions and catalyst development is possible for se-
lective CO2 methanation reaction.
In brief, the conversion of CO2 to synthetic natural gas has a tre-
mendous potential to be commercialized on a large scale. These pro-
cesses require a practical design of the catalyst system and an energy
efficient reactor design to improve the performance regarding activity,
selectivity, and stability. Finally, CO2 methanation process is techno-
logically matured and can become economically viable, if the costs
associated with CO2 and hydrogen production is mitigated.
CRediT authorship contribution statement
Jangam Ashok: Conceptualization, Writing - review & editing.
Subhasis Pati: Conceptualization, Writing - review & editing. Plaifa
Hongmanorom: Conceptualization, Writing - review & editing. Zhang
Tianxi: Writing - review & editing. Chen Junmei: Writing - review &
editing. Sibudjing Kawi: Conceptualization, Supervision, Funding ac-
quisition.
486
Catalysis Today 356 (2020) 471–489
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors gratefully thank the financial support from National
University of Singapore, National Research Foundation, Prime
Minister's Office, Singapore, the National Environment Agency under
the Waste-to-Energy Competitive Research Program (WTE CRP 1501
103, WBS No. R-279-000-491-279), Agency for Science, Technology
and Research (AME-IRG A1783c0016, WBS No. R-279-000-509-305)
and Ministry of Education(MOE2017-T2-2-130, WBS No. R-279-000-
544-112)
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