Reaction Mechanism of CO2 Methanation

Subjects: Chemistry, Physical

Submitted by: Li Li

Definition
The combustion of fossil fuels has led to a large amount of carbon dioxide emissions and increased
greenhouse effect. Methanation of carbon dioxide can not only mitigate the greenhouse effect, but
also utilize the hydrogen generated by renewable electricity such as wind, solar, tidal energy, and
others, which could ameliorate the energy crisis to some extent. Highly efficient catalysts and
processes are important to make CO2 methanation practical. Although noble metal catalysts exhibit
higher catalytic activity and CH4 selectivity at low temperature, their large-scale industrial
applications are limited by the high costs. Ni-based catalysts have attracted extensive attention due
to their high activity, low cost, and abundance. At the same time, it is of great importance to study the
mechanism of CO2 methanation on Ni-based catalysts in designing high-activity and stability
catalysts.

1. Introduction
With the continuous advancement of social economy and the unceasing enhancement of human living
standards, the overuse of fossil fuels has resulted in an energy crisis while the excessive emission of CO2
has exacerbated the greenhouse effect, which has induced global climate problems [1][2][3][4][5]. As the
main component of industrial waste gas, CO2 could also be used as an abundant and cheap chemical
feedstock for renewable fuels [6]. Therefore, converting CO2 into value-added chemicals is considered to
be one of the most promising strategies to mitigate the energy crisis and reduce the greenhouse effect.
Several clean and renewable energy resources such as wind, solar, and tidal energy produce
discontinuous and unstable electricity, which cannot be used effectively. Hydrogen can be generated by
the electrolysis of water using this kind of unstable electricity [7][8][9][10][11]. With this low cost H2 supply,
CO2 could be hydrogenated to form methane[12][13][14][15], and methane, as the main component of
natural gas, can be effectively utilized as a fuel or chemical, thus forming a new carbon cycle. In light of
the importance of the CO2 methanation reaction, it has been widely investigated. This reaction was
proposed by Sabatier and Senderens in 1902, which was also called the Sabatier reaction (Equation
(1))[16][17]. The reaction is exothermic, and can be carried out at low temperature to achieve high CO2
conversion [18][19][20][21]. However, CO2 is the upmost oxidized state of carbon and the activation of the C–
O bond in CO2 faces many challenges. The hydrogenation of CO2 to methane is an eight-electron process
with high kinetic barrier that requires a catalyst to achieve acceptable rates and selectivity[22][23][24]. The
active metals usually affect the catalytic activity and selectivity of the catalysts. Many noble metals such
as Rh [2][25], Ru[26][27][28], and Pd [29][30] have been widely applied in CO2 methanation due to their
excellent activity and CH 4 selectivity at low temperature. However, their large-scale industrial
applications are limited due to the high costs. In addition to noble metal catalysts, some Ni-based
catalysts also exhibit high catalytic activity and CH4 selectivity. However, the precise elucidation of the
CO2 methanation mechanism is still a challenging task. It is crucially important to understand the key
intermediates and reaction mechanisms in depth when designing catalysts with excellent catalytic
[26]
performance .
CO2 + 4 H2 → CH4 + 2 H2O, ΔH298K = −165.4 kJ/mol, ΔG298K = −130.8 kJ/mol, (1)

2. The Reaction Mechanism of CO 2 Methanation

Many researchers have made efforts to elucidate the possible CO2 methanation mechanism by in situ
FTIR, mass spectrometry (transient-MS) techniques, and DFT calculations. Although there are many
arguments on the intermediates and different reaction pathways of CH4 formation, two widely accepted
pathways have been proposed: (1) the formate pathway where formate species are the main
intermediate products formed during CO2 methanation reaction, also called the CO2 associative
methanation: the chemisorbed *CO2 species can first be converted to bidentate formates (HCOO*) and
then to formic acid (HCOOH), then to CH 4, and (2) the CO pathway, also called the CO2 dissociative
methanation: the chemisorbed *CO2 species can dissociate into *CO and *O. The formed *CO species can
further dissociate into carbon species (*C), which can then be hydrogenated to CH4 by dissociated H2 still
on the metal particles, desorbing from the catalyst surface, whereas the *O species can react with
hydrogen to produce H2O [10][31][32][33][34][35][36].

The possible reaction pathways are illustrated in Figure 1. CO2 methanation on different catalysts occur
[10]
via two different pathways, which are affected by the nature of nickel active sites and the supports .

Figure 1. Two different CO2 methanation reaction routes: formate route and CO route.

2.1. The Formate Pathway

Many studies have reported that CO2 methanation follows the formate route on different nickel catalysts
such as Ni/MgO [37], Ni-Mn/Al@Al2O 3 [38], Ni/Y2O 3 [39], Ni/ZrO2 [35][40], Ni/ultra-stable Y (USY) zeolite [41],

[42] [35]
and Ni@C . For example, Xu and coworkers discussed the formation and evolution of CO2 adsorbed
species on Ni/c-ZrO2 by in situ FTIR and DFT calculations. CO2 methanation on Ni/c-ZrO2 was dominated
by the formate pathway as follows: CO2*→ HCOO* → H2COO* → H2COOH* → H2CO* → CH2*→ CH4*, which
is the same as that shown in Figure 1. CO was a by-product instead of a reaction intermediate, which
could not further form CH4, and the DFT calculations also confirmed the formate pathway, which was
highly consistent with the in situ FTIR results. Solis-Garcia et al. [40] also found that CO2 methanation
follows the formate pathway over Ni/ZrO2 and no CO species were observed during the reaction. The
possible reaction pathway of the CO2 methanation over Ni@C was also investigated by CO2-TPD
measurements and in situ FTIR characterization. All results demonstrated that CO2 methanation over
Ni@C catalyst proceeded via the formate route without involving CO as an intermediate [42]. Aldana et al.
[12]
also found that the main CO2 methanation mechanism on Ni-CZsol–gel was the formate pathway, which
does not require CO as reaction intermediate. They also found that H2 was dissociated on Ni0 sites while
CO2 was activated on the ceria–zirconia support to form carbonates and then further into CH4, suggesting
that a stable metal–support interface is beneficial for the adsorption of CO2.

[43]
In another study, Pan et al. found that the reaction pathway on Ni/γ-Al2O 3 and Ni/Ce0.5Zr 0.5O 2 all
followed the formate pathway, only differing in reactive basic sites. On the Ni/Ce0.5Zr 0.5O 2 catalyst, CO2
adsorption on medium basic sites formed bidentate formate, whereas CO2 adsorption on surface oxygen
resulted in the monodentate formate. Due to the faster hydrogenation of monodentate formate, it was
assumed to be the main reaction route on the Ni/Ce0.5Zr 0.5O 2 catalyst. For CO2 methanation on Ni/γ-
Al2O 3, hydrogenation of bidentate formate was the main reaction route as bidentate formate was the
main adsorption and intermediate species and CO2 adsorbed on strong basic sites of Ni/γ-Al2O 3 will not
participate in the CO2 methanation reaction. It was assumed that medium basic sites are responsible for
promoting the formation of monodentate formate species, thus enhancing CO2 methanation activity. CO2
methanation reaction pathways on Ni/Ce0.5Zr 0.5O 2 and Ni/γ-Al2O 3 are shown in Figure 2.
 Figure 2. CO2 methanation reaction route on (A) Ni/Ce0.5Zr 0.5O 2 and (B) Ni/γ-Al2O 3.

2.2. The CO Pathway

The CO pathway involves the dissociation of CO2 to CO prior to methanation, and in the subsequent
[44]
reaction, CO is converted to CH4 by reacting with H2 . Karelovic et al. showed the direct dissociation of
CO2. The reactions below summarize the reduction process (Equations (3) and (4)). The excess amount of
CO generated in the first reaction deposits on the catalyst, which produces coking effects. To avoid this
problem, the methanation of CO must proceed much faster than the CO production, and the CO2
methanation reaction must take place at low temperatures. Therefore, the direct dissociation of CO2 to
COads and Oads often occur over a variety of noble metal-based catalysts at low temperature [25][45][46]. In
addition, the formation of nickel carbonyls Ni(CO)4 would cause the deactivation of Ni-based catalysts [47].

CO2 + H2 → CO + H2O
(2)

CO + 3 H2 → CH4 + H2O
(3)

Therefore, CO2 methanation occurred via the CO pathway only over some Ni-based catalysts including
[48] [49] [50]
Ni/CeO2 , Ni/F-SBA-15 , and Ni-sepiolite . The CO pathway over Ni/CeO2 could be proven by in
situ FTIR. The FTIR adsorption bands at 2017 cm−1 were assigned to the CO adsorption state, and the
bands at 2120 and 2170 cm−1 were ascribed to gas phase CO, which indicated that CO2 molecules can be
converted to CO molecules on the surface of the Ni/CeO2 catalyst. Characterization results indicated that
CO species generated from the reduction of CO2 molecules by nickel active sites and surface oxygen
[48]
vacancies promoted CO2 methanation . Bukhari et al. found that Ni metals on Ni/F-SBA-15 (Fibrous
type SBA-15) contributed to the CO2 dissociation into CO and O species as well as the dissociation of H2
into atomic hydrogen species. The linear carbonyl group came from the dissociation of CO2, which was an
intermediate during CO2 methanation and could be seen at 2055 cm−1. Then, the adsorbed CO species
interacted with surface oxygen, producing bidentate and unidentate carbonate groups, thus CH4 [49].

[50]
Cerdá-Moreno et al. also found linearly and bridged bonded CO as intermediates during CO2
methanation over a Ni-sepiolite catalyst.

2.3. The Key Factors of CO2 Methanation Reaction Route

There are also many factors influencing the CO2 methanation mechanism. The addition of promoters
affects the formation of intermediates. Mg or Ca modified Ni/Al2O 3 catalysts promote the formation of the
carbonate species due to the increased basicity, while Sr or Ba modified catalysts promoted *CO and
[51]
H2CO* formation . The nature of nickel active sites also influence the CO2 methanation mechanism.
[52]
Zhou et al. found that CO2 methanation took the pathway of CO over the Ni/TiO2 catalyst with Ni (111)
as the principal exposing facet, while the catalyst with multi-facets followed the formate route, with which
nickel was only functional for hydrogen dissociation. The location of nickel active sites also affects the CO 2
[33]
methanation reaction pathways . Controlling nickel being on either the interior or the exterior of
adjacent siloxene nanosheets is achieved by employing different solvents in the preparation process,
 which determines the reaction intermediates and pathways for CO 2 methanation, as shown in Figure 3.
CO2 methanation occurred through the formate pathway over Ni@SiXNS-EtOH with nickel active sites
being on the interior of adjacent siloxene nanosheets while CO2 methanation followed the CO pathway
when nickel was at the exterior of adjacent siloxene nanosheets on Ni@SiXNS-H2O.

Figure 3. CO2 methanation pathways on (A) Ni@SiXNS-H2O and (B)Ni@SiXNS-EtOH.

The different preparation methods can also influence the reaction pathway of CO2 methanation. Jia et al.
[53]
used the operando DRIFT analyses to demonstrate the CO2 methanation pathway on Ni/ZrO2 obtained
via different preparation methods. CO2 methanation over the plasma decomposed catalyst follows the Co-
hydrogenation route. The exposed high-coordinate Ni (111) facets of the plasma decomposed catalyst
facilitate the decomposition of CO2 and formates into adsorbed CO. The subsequent hydrogenation of
adsorbed CO leads to the production of methane. However, the thermally decomposed catalyst with a
complex Ni crystal structure and more defects mainly takes the pathway of direct formate hydrogenation.

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Keywords

CO2;CH4;reaction mechanism;Ni-based catalysts;low temperature

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