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Review

Research Progress and Reaction Mechanism of CO2 Methanation over Ni-Based Catalysts at Low Temperature: A Review

by
Li Li
1,
Wenqing Zeng
2,
Mouxiao Song
1,
Xueshuang Wu
1,
Guiying Li
1 and
Changwei Hu
1,2,*
1
Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China
2
College of Chemical Engineering, Sichuan University, Chengdu 610064, China
*
Author to whom correspondence should be addressed.
Catalysts 2022, 12(2), 244; https://doi.org/10.3390/catal12020244
Submission received: 22 January 2022 / Revised: 13 February 2022 / Accepted: 17 February 2022 / Published: 21 February 2022
(This article belongs to the Special Issue Carbon Dioxide Utilization: From Homogeneous to Heterogeneous Catalysis)
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Abstract

:
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. Herein, the present review focused on the recent progress of CO2 methanation and the key parameters of catalysts including the essential nature of nickel active sites, supports, promoters, and preparation methods, and elucidated the reaction mechanism on Ni-based catalysts. The design and preparation of catalysts with high activity and stability at low temperature as well as the investigation of the reaction mechanism are important areas that deserve further study.

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]. One of the most effective strategies is to replace fossil fuels with clean, renewable, carbon-neutral alternatives. Photocatalytic hydrogen production by solar energy has attracted the extensive attention of researchers, which was considered to be one of the most promising ways of utilizing solar energy because the combustion of H2 would release a large quantity of energy and the product would not pollute the environment [6,7,8,9]. However, it is impossible to achieve an industrial application due to the cost and operational limitations of this technology at present. Moreover, capture and geological sequestration strategies have also been used to remove excessive CO2 in the atmosphere [10,11,12]. However, several issues such as energy consumption, unsustainability, and leakage risks prevent these two methods from a large-scale application [13,14]. As the main component of industrial waste gas, CO2 could also be used as an abundant and cheap chemical feedstock for renewable fuels [15]. 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. CO2 reform of methane (DRM) is becoming an interesting strategy to convert the two greenhouse gases into syngas, which can be further converted to value-added products such as methanol or fuels through Fisher−Tropsch synthesis to replace traditional fossil fuels [16,17,18,19,20]. Many studies have also reported the steam methane reforming reaction to produce H2 as an alternative energy for fossil fuels [21,22,23,24].
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 [25,26,27,28,29]. With this low cost H2 supply, CO2 could be hydrogenated to form a variety of products including methanol [30,31,32,33,34,35], ethanol [36,37,38,39], olefins [40], methane [41,42,43,44], and other hydrocarbons [45,46]. At the same time, clean and renewable energy can also be effectively utilized [47]. Compared with the conversion of CO2 to other value-added chemicals, the CO2 methanation reaction rate is faster, the reaction conditions are milder, and can be carried out under atmospheric pressure. The hydrogenated product, methane, as the main component of natural gas, can be effectively utilized as a fuel or chemical, thus forming a new carbon cycle. The CO2 methanation reaction can alleviate the greenhouse effect, solve the problem of natural gas shortage, and reduce humanity’s dependence on fossil energy [48,49,50,51]. Throughout the years, the CO2 methanation reaction has been carried out via different methods such as thermo-catalysis [47,52], photo-catalysis [53,54,55,56,57,58,59,60,61,62], electro-catalysis [63,64], bio-catalysis [63,65,66,67], plasma-catalysis [68,69,70], etc. Figure 1 presents the CO2 hydrogenation to produce CH4 through different catalysis methods. Among these CO2 methanation processes, CO2 can be hydrogenated to produce CH4 by photo-catalysis, electro-catalysis, and plasma-catalysis at low temperature. However, there are still some challenges including the low CH4 selectivity and low efficiency. Thermo-catalysis is one of the most common forms of catalysis, which is mainly attributed to its high efficiency and applicability for large scale processes. As thermal CO2 methanation is mature enough to be commercialized, this paper focused on thermal catalytic CO2 methanation [71].
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)) [72,73]. The reaction is exothermic, and can be carried out at low temperature to achieve high CO2 conversion [74,75,76,77]. 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 [78,79,80]. More and more researchers are interested in designing a CO2 methanation catalyst. As reported, the sintering of metal particles and carbon deposition would result in the deactivation of catalysts at high temperature. At the same time, the reverse water–gas shift reaction (RWGS) (Equation (2)) would also occur at high temperature, and produce CO as a by-product [46]. The presence of CO might induce the Boudouard reaction, resulting in the formation of coke. Furthermore, the Tammann temperature of nickel is about 590 °C, so the sintering would occur at high temperature. Therefore, sintering-resistant and coke-resistant characteristics would be facilitated at low temperature (below 300 °C), where the life of the catalysts could also be prolonged [77]. The active metals usually affect the catalytic activity and selectivity of the catalysts. Many noble metals such as Rh [2,49], Ru [81,82,83], and Pd [84,85] have been widely applied in CO2 methanation due to their excellent activity and CH4 selectivity at low temperature. The catalytic performance of some noble metal catalysts on CO2 methanation is summarized in Table 1. It can be seen that noble metal catalysts with low metal loading exhibited high catalytic activity, especially excellent CH4 selectivity at low temperature. However, their large-scale industrial applications are limited due to the high costs.
In addition to noble metal catalysts, many non-noble metals such as Co and Ni have also been widely used in CO2 methanation due to their low cost. Co-based catalysts exhibit excellent low temperature catalytic performance and could effectively avoid catalyst sintering deactivation. However, the CH4 selectivity of the catalysts is generally low. Among the results reported thus far, only a few Co-based catalysts could achieve high CO2 conversion and high CH4 selectivity [61,97,98,99]. Therefore, many researchers have turned their attention to Ni-based catalysts with relatively high activity in this reaction because of their comparable price and abundance [75,79,100,101,102]. Some Ni-based catalysts also exhibit high catalytic activity and CH4 selectivity. Zhou et al. [103] prepared Ni/CeO2 catalyst by using the hard template method and the catalyst exhibited high CO2 methanation activity with 91.1% CO2 conversion and 100% CH4 selectivity at 340 °C, atmospheric pressure. However, Ni-based catalysts still face several challenges in the application of CO2 methanation at present. First, the activity of Ni-based catalysts at low temperature needs to be improved. Second, the sintering of nickel particles due to the exothermic methanation reaction and the formation of carbon deposition could all result in deactivation of the catalyst during the reaction process [104]. Third, the precise elucidation of the CO2 methanation mechanism is still a challenging task.
CO2 + 4 H2 → CH4 + 2 H2O, ΔH298K = −165.4 kJ/mol, ΔG298K = −130.8 kJ/mol,
CO2 + H2 → CO + H2O, ΔH298K = 41.17 kJ/mol, ΔG298K = −28.6 kJ/mol,
Many papers have reviewed the progress of the CO2 methanation reaction. Fan et al. [46] mainly reviewed various active metals and heterogeneous catalyst supports used for the thermal hydrogenation of CO2 to methane. Lee et al. [105] mainly focused on the recent work around low temperature CO2 methanation on a wide range of catalysts including reaction thermodynamics and kinetics, catalyst materials including supports and promoters, and suitable reactor technologies. Ashok et al. [51] mainly reviewed the research progress of three kinds of CO2 methanation reaction systems including thermo-catalytic systems, CO2 methanation in a catalytic membrane reactor, and the CO2 hydrogenation under plasma process in detail. Insightful guidance was provided in these review papers. The present work highlighted, in particular, CO2 methanation on Ni-based catalysts and elaborated the CO2 methanation mechanism, which was focused on discussing the research progress and present status of CO2 methanation with an emphasis on designing catalysts with high activity and stability at low temperature. We summarized the recent development of Ni-based catalysts used in CO2 methanation including the effects of nickel active sites, supports, promoters, and preparation methods on CO2 methanation as well as the two kinds of reaction mechanisms. Several suggestions for the future development of Ni-based catalysts for CO2 methanation at low temperature are also proposed.

2. CO2 Methanation at Low Temperature

As reported, Ni-based catalysts have been widely studied in CO2 methanation. Many key parameters including the essential nature of nickel active sites, supports, promoters, and preparation methods could influence the catalytic performance of Ni-based catalysts for CO2 methanation [106].
We summarized the catalytic activity and selectivity of most of the previously reported Ni-based catalysts for CO2 methanation with different reaction conditions, as listed in Table 2 and Table 3. Many studies added the balance gas in the reaction mixture such as Ar, N2, and He, which could improve heat and mass transfer during the reaction process, thus improving the CO2 conversion. Table 2 and Table 3 summarize the catalytic performance of different Ni-based catalysts for CO2 methanation without the balance gas and with balance gas, respectively. Here, we also review the recent research progress of CO2 methanation and discuss the effect of different factors through some detailed representative examples.

2.1. The Nature of Active Sites on CO2 Methanation

The catalytic performance of Ni-based catalysts can be influenced by characteristics of Ni active sites including the content of Ni [142,143], the size of Ni [125,144,145,146,147], the structure and chemical state of Ni [127,148,149,150,151], the different nickel precursor salts [152], and the location of Ni active sites [153].
Vita et al. [142] designed Ni/GDC (gadolinium-doped-ceria) catalysts containing different contents (15–50 wt%) of Ni. They found that the catalytic activity increased with an increase in Ni content because of the enhanced Ni–support interaction, basicity, and oxygen vacancies. However, some Ni-based catalysts with low metal loading also exhibited excellent catalytic performance, which are summarized in Table 4. For example, the CO2 conversion of the 2 wt %Ni/CeZrO4 catalyst was 63%, and the CH4 selectivity could reach 100% at 350 °C [154]. Both the catalytic activity and CH4 selectivity were proposed to also be related to the size of the Ni particles, and Ni-based catalysts can be prepared by controlling the nickel size to achieve higher catalytic performance [144,145,155,156]. Many researchers have devoted themselves to exploring the role of nickel size in CO2 methanation when designing catalysts with high activity. Citric acid was added during the preparation of the Ni/Y2O3 catalyst, which could affect the nickel particle size and the Ni–support interaction [125]. Ni/CeO2 with different sized Ni particles (2, 4 and 8 nm) were prepared to explore the size effect on CO2 methanation performance, and Ni/CeO2 with 8 nm nickel particles exhibited the highest catalytic activity. According to DRIFTS study, the larger Ni over CeO2 efficiently promoted the hydrogenation of the formate intermediates, which accounted for the excellent CO2 methanation performance [146]. Hao et al. [147] also explored Ni particle size in CO2 methanation over Ni/CeO2 catalyst. Through TGA measurements, the small Ni nanoparticles suffered a temporary loss of activity due to the carbon deposition.
Ni-based catalysts with special structure and chemical state also affect the performance of the catalyst [148]. Sponge Ni exhibited excellent CO2 methanation performance, and the CO2 conversion could achieve 83% under a high space velocity (0.11 molCO2 gcat−1 h−1) at 250 °C [149]. Hongmanorom et al. [127] designed Ni nanoparticles encapsulated in mpCeO2 using strong electrostatic adsorption with 0.183 s−1 TOF, but the TOF of the conventional Ni/CeO2 catalyst was only 0.057 s−1. The higher activity resulted from more oxygen vacancies provided by the encapsulated structure on the Ni–CeO2 surface. The Ni@HZSM-5 catalyst was synthesized by the hydrothermal method with a special embedment structure that showed high activity and stability in CO2 methanation, and Ni@HZSM-5 could retain a structure and content of nickel similar to that of the fresh catalyst due to its special structure, while the conventional Ni/SiO2 and Ni/HZSM-5 catalysts changed after a long period of reaction [150]. Hu et al. [151] discovered three distinct nickel active phases on Ni/Al2O3 obtained by reduction at different temperatures, that is, the catalysts reduced at different temperatures (535, 573, and 673 K, respectively) exhibited different CO2 conversion and CH4 yield.
Ni-based catalysts prepared by different nickel salt precursors exhibited different catalytic performance. The Ni–AA catalyst (nickel acetylacetonate precursor) with special coordinating anion showed the best catalytic performance, but the Ni–S catalyst (nickel sulfate precursor) deactivated rapidly due to the presence of Ni3S2 after the reduction pretreatment [152]. In addition, Yan et al. [153] found that the promising catalytic performance was also associated with the location of the nickel. They controlled the location of the nickel by employing the terminal groups of siloxene and varying the solvent used. When nickel was on the interior of adjacent siloxane nanosheets, the activity of Ni@Siloxene was higher, with above 90% CH4 selectivity. When the location of the nickel was different, there were two disparate reaction pathways accordingly.

2.2. The Support on CO2 Methanation

The nature of supports plays a critical role in the catalytic process by influencing the morphology, dispersion, stability, and reducibility of the active sites [160,161]. The nickel–support interaction can potentially modify the electronic state of active sites and suppress nickel sintering, which is important in promoting CO2 methanation at low temperature [82,111,162]. Therefore, synthesis of highly efficient supported Ni catalysts is one of the major directions of CO2 methanation. According to the reported study, we divided the supports of Ni-based catalysts into single supports, composite oxide supports, and other supports (MOF, zeolite, and activated biochar), as shown in Figure 2.

2.2.1. Ni-Based Catalysts Supported on Single Oxide Supports

Various oxides such as Al2O3 [143,163,164,165], TiO2 [158,166], ZrO2 [110,167], CeO2 [145,168], and SiO2 [25,101] have been explored for Ni-based CO2 methanation catalysts. Muroyama and co-workers [124] compared the catalytic activity of different metal oxide supported Ni catalysts and found that Ni/Y2O3 exhibited the highest catalytic activity with 80% CH4 yield at 300 °C. Italiano et al. [162] also found that Ni/Y2O3 exhibited the highest activity and no deactivation was observed after 200 h of testing, resulting from its good anti-coking and anti-sintering ability among Ni/CeO2, Ni/Al2O3, and Ni/Y2O3 catalysts. As reported, the oxygen vacancies on the support played a significant role in the adsorption/activation of CO2 species. CeO2 supported Ni-based catalysts have been widely used in CO2 methanation due to the high concentration of oxygen vacancies on the surface [103]. Le et al. [169] reported that Ni/CeO2 was the most active for CO2 methanation due to the smallest Ni particle size among Ni-based catalysts on different supports. The Ni/ZrO2 catalyst is also one of the most active systems for CO2 methanation, and ZrO2 is very relevant for the generation of active sites of the methanation reaction, and the high concentration of oxygen vacancies on ZrO2 also play an essential role in CO2 methanation [110,170,171]. Therefore, ZrO2 has also received extensive attention in CO2 methanation because of its high mechanical and thermal stability [172]. Martínez et al. [76] reported the outstanding catalytic performance of Ni/ZrO2, where the conversion of CO2 was close to 60% and CH4 selectivity was 100% at 500 °C, with high stability after a 250 h reaction.

2.2.2. Ni-Based Catalysts Supported on Composite Oxide Supports

Composite supports could modify Ni–support interaction more easily and exhibited better properties compared with single oxide support. Zhu et al. [129] prepared a Y2O3-promoted NiO–CeO2 catalyst and compared the catalytic activity of NiO–CeO2 and NiO–CeO2–Y2O3 catalysts. They found that the introduction of Y2O3 to CeO2 greatly facilitated the generation of surface oxygen vacancies during the reaction, which promoted the dissociation of CO2 and thus improved the catalytic activity. Siakavelas et al. [107] also reported binary CeO2-based oxides Sm2O3–CeO2, Pr2O3–CeO2, and MgO–CeO2 supported Ni catalysts used in CO2 methanation. The addition of Sm3+ and Pr3+ increased the amount of oxygen vacancies of the catalysts, which improved CO2 methanation activity. The strong nickel–support interaction on the Ni/MgO-CeO2 increased the anti-sintering ability of the catalyst. The oxygen vacancies and coordinatively unsaturated sites formed cation pairs on the Ca doped Ni/ZrO2. The number of these pairs on Ni/CaZrO2 was higher than the Ni/ZrO2 catalyst, which increased the CO2 methanation rate [110].
Although Al2O3 supported Ni-based catalysts exhibited relatively high catalytic activity because of their high surface area and excellent hydrothermal stability, it needed further improvement [112]. Much research has been conducted on the modification of the Al2O3 support by the employment of rare-earth oxides [74]. Furthermore, La3+ doping could also enhance the surface basicity of the catalysts [173]. A variable amount of La-doped Ni/γ-Al2O3 catalysts [164] was used in CO2 methanation, and the activity and selectivity of Ni/La-γ-Al2O3 increased compared with Ni/γ-Al2O3. The basicity of the support increased because of the addition of La, which enhanced the adsorption of CO2. ZrO2, as a promoter, is also widely used in CO2 methanation catalysts because of its excellent hydrothermal stability and high oxygen defects. Lin et al. [119] designed a Ni/Al2O3-ZrO2 catalyst with CH4 selectivity of about 100%, CO2 conversion of 77% at a lower temperature of 300 °C. The formed Al2O3–ZrO2 solid solution could promote the reduction and dispersion of NiO, and increase the number of nickel active sites and oxygen vacancies because of the higher Zr loading, which results in significant improvement of the catalytic activity at low temperature.

2.2.3. Ni-Based Catalysts Supported on Other Supports

In addition to various oxide carriers, there are many other materials such as zeolite [108,113,131,174], MOF [101,175], and activated biochar [176] supported Ni catalysts, which have also been used in CO2 methanation. Sholeha and co-workers [108] synthesized zeolite NaY from dealuminated metakaolin and used as a support of the Ni catalyst. The prepared Ni/NaY exhibited significant CO2 conversion (67%) and CH4 selectivity (94%) in CO2 methanation, which could be attributed to the combination of well-defined crystalline structures and the large surface area of NaY. The Ni catalyst with porous zirconia obtained from a Zr-based metal-organic framework with UiO-66 as the support exhibited a turnover frequency of 345 h−1 space−time yield of 5851 mmol·gNi−1·h−1 with CH4 selectivity of over 99%, showing only a 4% decrease in activity after testing for 100 h on stream [175]. Ni/zeolite X [131] derived from fly ash was also applied in CO2 methanation, where around 50% CO2 conversion could be obtained at 450 °C. Wang et al. prepared a Ni/Ce-ABC (where ABC refers to activated bio-char) catalyst using biomass as the raw material, and the bio-char was modified by highly dispersed CeO2 [176]. This catalyst showed fantastic catalytic performance in CO2 methanation, achieving 88.6% CO2 conversion and 92.3% CH4 selectivity at 360 °C.

2.3. Promoter Effect on CO2 Methanation

To obtain satisfactory catalytic performance, doping a second metal into Ni-based catalysts as promoters is also a good idea. The second metal and nickel might form an alloy structure, which tends to modify the geometric and electronic structure of Ni-based catalysts. Based on the literature, these promoters contain alkaline earth oxides [109,126,174,177,178], noble metals [120,137], rare-earth metals [121,130,134,136,163,179,180,181,182,183], and some other typical transition metals and non-metallic elements [3,13,75,80,118,157,166,184,185,186], as displayed in Figure 3. These promoters could affect the dispersion of nickel active sites, the acid–base properties of the support, the nickel–support interaction, and thus to the catalytic activity and stability of the catalyst.

2.3.1. Alkaline Earth Oxides Promoted Ni-Based Catalysts

Various studies have been conducted where alkaline-earth oxides have been widely used in CO2 methanation catalysts as promoters. As alkaline-earth oxides are cheap, abundant, and can improve the basicity of the catalysts, they can promote the adsorption, activation, and reduction of CO2 [61,74,130,177]. Ca-doped Ni-based catalysts have shown great potential in CO2 methanation. The influence of alkaline-earth oxides (Ca, Mg, Sr, and Ba) as promoters on Ni/γ-Al2O3 has also been investigated [126], where Ni and promoters were found to be uniformly dispersed into the pore structure of the support, and the Ca-promoted Ni/Al2O3 catalyst exhibited the highest catalytic activity, which could be attributed to the enhanced CO2 adsorption and the reducibility of Ni active sites. Do et al. [109] applied Ca-inserted NiTiO3 in CO2 methanation and found that the addition of Ca generated oxygen vacancies on the catalyst, and 84.73% CO2 conversion and 99.95% CH4 selectivity were observed. Xu and co-workers [178] reported that the Ca promoter increased the surface basicity of Ni–Al composite oxide catalysts, which enhanced the adsorption and activation of CO2. Bacariza et al. [174] prepared a Mg-promoted Ni/USY zeolite catalyst using different incorporation methods. They found that lower contents of Mg could enhance the catalytic performance because of the increase in nickel dispersion, while a higher amount of Mg would decrease CO2 conversion due to the formation of a NiO−MgO solid solution, and the dispersion and stability of nickel on the Ni/USY zeolite catalyst obtained by ion exchange were higher than that of the impregnated catalysts.

2.3.2. Noble Metals Promoted Ni-Based Catalysts

Bimetallic methanation catalysts were prepared by adding small amounts of noble metals into Ni-based catalysts, which showed a significantly enhanced catalytic performance at low temperature. Shang et al. [120] prepared different Ru content doped 30 wt% Ni/CexZr1−xO2 catalysts and explored the effects of Ru content on catalytic performance as well as the Ce/Zr molar ratios. 3Ru-30Ni/Ce0.9Zr0.1O2 exhibited the best catalytic performance with 98.2% CO2 conversion and 100% CH4 selectivity at a low reaction temperature (230 °C). The addition of Ru can improve the Ni dispersion and the basicity of the surface of the catalysts. Noble metals as promoters could enhance the reducibility, the dispersion of nickel, and H2 chemisorption capacity, thus improving the catalytic performance. Mihet et al. [137] also explored the effect of Pt, Pd, or Rh on the Ni/γ-Al2O3 catalyst, and found that Ni-Pd/γ-Al2O3 exhibited the highest activity with 74.6% CO2 conversion and 96.6% CH4 selectivity at 250 °C.

2.3.3. Rare-Earth Metal Promoted Ni-Based Catalysts

Rare-earth elements, mainly, La, Ce, and Y, have been used as promoters to increase the catalytic activity at low temperature because they can enhance the basicity of catalysts, Ni reducibility, and smaller Ni particles. Wang et al. [179] explored different rare-earth metals including La, Y, Ce and Ge promoted Ni/γ-Al2O3 catalyst. They found that the Y promoted Ni/γ-Al2O3 catalyst exhibited the highest catalytic activity, followed by the promoters of Ce, Gd, and La, which could be attributed to the differences in atomic radius, electron layer structure, and oxide basicity of each promoter. Mikhail et al. [173] also found that 4 wt% Gd promoted Ni/CeZrOx exhibited the highest activity with 85% CO2 conversion and 100% CH4 selectivity due to its high metal dispersion and the high percentage of medium basic sites. Many studies have reported that the addition of La could enhance the surface basicity and the adsorption of CO2, resulting in a significant increase in CO2 conversion and CH4 selectivity [136,182]. The effect of La on the catalytic activity was investigated and compared with that of Y and Ce [130]. The highest space velocity (480 L g−1 h−1) and CH4 productivity (101 LCH4 gNi−1h−1) were obtained on the La-promoted catalyst, which was related to more reduced, highly dispersed Ni nanoparticles and basic sites in the La2O3–Al2O3 matrix. Zhang et al. [134] also explored La as a promoter on CO2 methanation. The NiLa5/Mg–Al catalyst showed the best catalytic performance, obtaining 61% CO2 conversion and nearly 100% CH4 selectivity with a WHSV of 45,000 mL g−1 h−1 at 250 °C, 0.1 MPa. Characterization results showed that La effectively increased Ni dispersion and decreased Ni particle size. In addition, La could significantly increase the amount of moderate basic sites, which could contribute to enhanced CO2 adsorption capacity.
Ce as a promoter could increase the basicity of the catalyst, thus improving the adsorption and activation of CO2. In addition, the rapid reduction of Ce4+ to Ce3+ could form oxygen vacancies, which is of great importance for the catalytic activity [163]. Li et al. [180] prepared a Ce-promoted Ni-La2O3/ZrO2 catalyst with high Ni dispersion and excellent resistance to sintering, leading to high activity and stability. Daroughegi et al. [163] found that the Ce promoted Ni–Al2O3 catalyst exhibited the highest activity and stability with 76.4% CO2 conversion and 99.1% CH4 selectivity at 350 °C. Alarcón et al. [26] also reported a Ce promoted Ni-Al2O3 catalyst with high loading CeO2 (25 wt%), which was highly stable for 120 h.

2.3.4. Other Transition Metals and Non-Metallic Elements Promoted Ni-Based Catalysts

In addition, other typical transition metals such as Fe [3,13,184], Co [80,185], Mn [3,118,166], and non-metallic elements such as Si [75] promoted Ni-based catalysts can also be used in CO2 methanation.
Serrer et al. [184] reported that the Ni–Fe catalyst exhibited high activity and long-term stability. They found a synergistic effect between nickel and iron on a bimetallic Ni–Fe catalyst that led to higher fractions of reduced nickel compared to a monometallic Ni-based catalyst. The Fe0 ⇌ Fe2+ ⇌ Fe3+ redox mechanism could be observed at the interface of these FeOx clusters, which could promote CO2 dissociation. Mn was introduced into Ni/bentonite, and the conversion of CO2 on 2 wt% Mn-Ni/bentonite was 85.2% with 99.8% CH4 selectivity at 270 °C. On the other hand, CO2 conversion on Ni/bentonite needed 300 °C to obtain 84.7% CO2 conversion. The addition of Mn enhanced the nickel–support interaction and the dispersion of nickel, and increased the amount of oxygen vacancies on the catalyst surface, which promoted the CO2 methanation reaction [118]. Li et al. [75] prepared a series of Ni-xSi/ZrO2 catalysts and found that the appropriate amount of Si promoter increased the dispersion of nickel, Ni–support interaction, and the number of active sites. The Ni-0.1Si/ZrO2 catalyst exhibited the highest catalytic activity with 72.5% CO2 conversion and 72.2% CH4 yield at 250 °C.

2.4. The Effect of Preparation Methods on CO2 Methanation

Diverse methods are applied in the preparation of Ni-based catalysts including the impregnation method (IM), precipitation method (PM), sol–gel method (SGM) as well as other methods. Table 5 summarizes the synthesis methods of different Ni-based catalysts. From Table 5, it can be observed that most catalysts were synthesized by the traditional impregnation method and precipitation method. In addition, a small number of catalysts were prepared by other methods including sol–gel, solution combustion, ammonia evaporation (AE), and the mechanochemical ball-milling method. Furthermore, catalysts prepared by different methods also exhibited different structures and properties as well as catalytic activity [128,187].
Zhang et al. [134] found that the urea hydrolysis method was a more efficient approach compared to the coprecipitation method in the preparation of Ni-based catalysts and obtained a Ni-based catalyst with higher Ni dispersion, larger CO2 adsorption capacity, and therefore better catalytic performance. The Ni/CeO2 catalyst prepared via decomposition of the nickel precursor by gas discharge plasma exhibited above 99% CH4 selectivity at reaction temperatures lower than 300 °C, and more active sites were exposed to the CeO2 surface, which promoted the splitting of H2 and the activation of CO2, thus significantly improving the catalytic activity at low temperature [133]. Bukhari et al. [194] prepared Ni/SBA-15 catalysts using three kinds of hydrothermal treatment techniques (Reflux (R) and Teflon (T)) and without the hydrothermal technique (W), and applied them to CO2 methanation. The catalytic activity sequence was as follows Ni/SBA-15(R) > Ni/SBA-15(T) > Ni/SBA-15(W). Characterization results showed that Ni/SBA-15(R) possessed excellent catalytic properties due to its high surface area and pore diameter, finest metal particles, strongest metal–support interaction, and highest concentration of basic sites. In addition, Gnanakumar et al. [115] studied the influence of pretreatment method on the catalytic performance of Ni/Nb2O5 by calcining the Nb2O5 support at different temperatures. Ni/Nb2O5 calcined at 700 °C provided higher methanation activity and CH4 selectivity with good stability in a stream study for 50 h.

3. The Reaction Mechanism of CO2 Methanation

It is crucially important to understand the key intermediates and reaction mechanisms in depth when designing catalysts with excellent catalytic performance [81]. 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 CH4, 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 [28,51,128,153,195,196,197].
The possible reaction pathways are illustrated in Figure 4. CO2 methanation on different catalysts occur via two different pathways, which are affected by the nature of nickel active sites and the supports [28].

3.1. The Formate Pathway

Many studies have reported that CO2 methanation follows the formate route on different nickel catalysts such as Ni/MgO [198], Ni-Mn/Al@Al2O3 [199], Ni/Y2O3 [200], Ni/ZrO2 [196,201], Ni/ultra-stable Y (USY) zeolite [139], and Ni@C [102]. For example, Xu and coworkers [196] 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 4. 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. [201] 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 [102]. Aldana et al. [41] 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.
In another study, Pan et al. [202] found that the reaction pathway on Ni/γ-Al2O3 and Ni/Ce0.5Zr0.5O2 all followed the formate pathway, only differing in reactive basic sites. On the Ni/Ce0.5Zr0.5O2 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/Ce0.5Zr0.5O2 catalyst. For CO2 methanation on Ni/γ-Al2O3, 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-Al2O3 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/Ce0.5Zr0.5O2 and Ni/γ-Al2O3 are shown in Figure 5.

3.2. The CO Pathway

The CO pathway involves the dissociation of CO2 to CO prior to methanation, and in the subsequent reaction, CO is converted to CH4 by reacting with H2 [203]. 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 [49,204,205]. In addition, the formation of nickel carbonyls Ni(CO)4 would cause the deactivation of Ni-based catalysts [162].
CO2 + H2 → CO + H2O
CO + 3 H2 → CH4 + H2O
Therefore, CO2 methanation occurred via the CO pathway only over some Ni-based catalysts including Ni/CeO2 [103], Ni/F-SBA-15 [113], and Ni-sepiolite [206]. 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 vacancies promoted CO2 methanation [103]. 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 [113]. Cerdá-Moreno et al. [206] also found linearly and bridged bonded CO as intermediates during CO2 methanation over a Ni-sepiolite catalyst.

3.3. 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/Al2O3 catalysts promote the formation of the carbonate species due to the increased basicity, while Sr or Ba modified catalysts promoted *CO and H2CO* formation [177]. The nature of nickel active sites also influence the CO2 methanation mechanism. Zhou et al. [158] 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 CO2 methanation reaction pathways [153]. 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 CO2 methanation, as shown in Figure 6. 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.
The different preparation methods can also influence the reaction pathway of CO2 methanation. Jia et al. [135] 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.
Although some researchers have reported on the mechanism of CO2 methanation, it is still hotly debated. Some of the problems are as follows: (1) Why are there two different CO2 methanation mechanisms on Ni-based catalysts with the same Ni element as the active component? (2) What are the influencing factors of reaction pathways? (3) Are the adsorbed CO2 species on different Ni-based catalysts are the same? (4) What is the approach and process of the adsorbed CO2 species evolution on the catalysts? (5) What is the effect of Ni on the activation and dissociation of CO2? (6) Ni-based catalysts are also used in CO methanation, so why is CO only a by-product and does not react further to form CH4 on some catalysts? and (7) What is the role of CO across the whole CO2 methanation reaction process? Regarding these problems, no consensus has been reached. Establishing a reaction network to understand the CO2 methanation mechanism at the molecular-level is extremely important. These mechanistic insights will have great potential to guide the rational design of catalysts with high activity and CH4 selectivity.

4. Summary and Perspective

This review encompassed the recent development of Ni-based catalysts used in CO2 methanation including the effects of nickel active sites, supports, promoters, and preparation methods on CO2 methanation as well as the two kinds of reaction mechanism, with emphasis on designing catalysts with high activity and stability at low temperature. By discussing the research progress and present status of CO2 methanation over Ni-based catalysts, some conclusions could be obtained. First, interactions between Ni and the support seem to be a key parameter for the methanation reaction. The appropriate nickel–support interaction could suppress nickel sintering, resulting in high activity and good stability. Second, the promoters could affect the dispersion of the active phase, the acid–base properties of catalysts, and thus the catalytic activity and stability. Adding noble metals into Ni-based catalysts as promoters could improve the catalytic activity at low temperature. In addition, alkaline-earth oxides as promoters could improve the alkaline properties of the catalysts, which could promote the adsorption, activation, and reduction in CO2, thus enhancing the catalytic activity at low temperature. Third, CO2 methanation occurred via the formate pathway and CO pathway over Ni-based catalysts, and the addition of promoters and the nature of active metal affects the formation of intermediates, thus affecting the reaction mechanism. Fourth, appropriate basic sites on catalysts could promote the formation of monodentate formate species, thus enhancing CO2 methanation activity. Using different basic oxides as supports could adjust the basicity of the catalysts, enhancing the adsorption of CO2.
Although Ni-based catalysts have been widely used in CO2 methanation, many challenges and problems remain. To increase the activity of Ni-based catalysts at low temperature, the activation of CO2 and H2 at low temperature is important, and the properties of the nickel metal, support, and promoter would influence this. Some new technologies have been applied in CO2 methanation such as photo-catalysis, electro-catalysis, and plasma-catalysis. CO2 could be hydrogenated to produce CH4 by these methods at low temperature, but there are some challenges including the low CH4 selectivity and low efficiency. One recommended advancement to overcome these issues is to couple these new technologies with traditional thermo-catalysis such as thermal-photo catalysis, which could significantly improve the selectivity and yield of CH4. For example, solar-thermal CO2 reduction could achieve high-efficient conversion CO2 at mild conditions, which could overcome the low efficiency and very high operating temperature of photo-catalysis and thermo-catalysis, and achieve higher solar energy utilization efficiency. In addition, it is still a big challenge to experimentally determine CO2 methanation reaction pathways, and the effects of active sites, supports, and promoters on the reaction mechanism are still being debated. The precise elucidation of the activation of the C–O bond in CO2 and the relationship between CO2 activation and H2 activation are also challenging tasks.
Based on the above discussions, the following suggestions on CO2 methanation on Ni-based catalysts are proposed.
(1)
Design of CO2 methanation catalysts with high activity at low temperature simultaneously with high carbon deposition resistance and anti-sintering properties;
(2)
Try new materials and technologies such as MOF, alloy material, and plasma assisted technology for the design and preparation of CO2 methanation catalysts;
(3)
Combine photo-catalysis, electro-catalysis, and plasma-catalysis with traditional thermo-catalysis to integrate their advantages;
(4)
Investigate the mechanism of the activation and cleavage of C–O in CO2, and the relationship between CO2 activation and H2 activation as well as provide deep insights into the CO2 methanation reaction pathways and the key factors in the reaction mechanism; and
(5)
Combine the theoretical calculations with experiments to explore the role of the active metal, support, and the nickel–support surface in the CO2 methanation reaction process.

Author Contributions

M.S. and X.W. summarized the data; L.L. and W.Z. wrote the original draft and revision; C.H. and G.L. revised the manuscript; and C.H. was in charge of the funding acquisition. All authors have read and agreed to the published version of the manuscript.

Funding

This research was supported by the National Key R&D Program of China (2018YFB1501404), the 111 Program (B17030), and the Fundamental Research Funds for the Central Universities.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Catalysts 12 00244 g001 550
Figure 1. CO2 hydrogenation to produce CH4 via different catalysis methods.
Figure 1. CO2 hydrogenation to produce CH4 via different catalysis methods.
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Catalysts 12 00244 g002 550
Figure 2. The different supports of Ni-based catalysts.
Figure 2. The different supports of Ni-based catalysts.
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Catalysts 12 00244 g003 550
Figure 3. The promoters used for Ni-based catalysts in CO2 methanation.
Figure 3. The promoters used for Ni-based catalysts in CO2 methanation.
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Catalysts 12 00244 g004 550
Figure 4. Two different CO2 methanation reaction routes: formate route and CO route.
Figure 4. Two different CO2 methanation reaction routes: formate route and CO route.
Catalysts 12 00244 g004
Catalysts 12 00244 g005 550
Figure 5. CO2 methanation reaction route on (A) Ni/Ce0.5Zr0.5O2 and (B) Ni/γ-Al2O3.
Figure 5. CO2 methanation reaction route on (A) Ni/Ce0.5Zr0.5O2 and (B) Ni/γ-Al2O3.
Catalysts 12 00244 g005
Catalysts 12 00244 g006 550
Figure 6. CO2 methanation pathways on (A) Ni@SiXNS-H2O and (B)Ni@SiXNS-EtOH.
Figure 6. CO2 methanation pathways on (A) Ni@SiXNS-H2O and (B)Ni@SiXNS-EtOH.
Catalysts 12 00244 g006
Table
Table 1. The catalytic performance of different noble metal catalysts for CO2 methanation.
Table 1. The catalytic performance of different noble metal catalysts for CO2 methanation.
CatalystsMetal Loading (%)Synthesis MethodReaction ConditionsCO2 Con. (%)CH4 Yie.
(%)		CH4 Sel.
(%)		Ref.
Temp. (°C)H2: CO2GHSV/h−1
Ru-CeO2/Al2O32Impregnation3005:1100060nd99[86]
Ru/TiO22.5Impregnation3504:1600090nd~99[87]
Ru/TiO20.8“Dry” modification1804:1ndndnd100[88]
Ru/UiO-661Impregnation2504:1nd60nd100[89]
Ru/Al2O34Impregnation3755:110,00085ndnd[90]
RhY6Ion-exchange1503:160005.9nd99.8[91]
Rh/MSN5Impregnation3504:1500099nd100[42]
Rh/ACZ10Impregnation4024:1nd~5046.8nd[92]
Rh/CeO23Impregnation3504:1nd~46~41~100[93]
Pd/UiO-666Sol–gel3404:115,00056nd97.3[85]
Pd/Al2O35Impregnation2804:145,000ndnd40[94]
PdO@LaCoO33One-pot 3003:118,00062.3nd>99[95]
PdO/LaCoO33Impregnation3003:118,00031.8nd87.4[95]
Pd–Mg/SiO26.2Microemulsion4504:1732059.256.495.3[96]
nd: no data.
Table
Table 2. The catalytic activity of different Ni-based catalysts for CO2 methanation without balance gas.
Table 2. The catalytic activity of different Ni-based catalysts for CO2 methanation without balance gas.
CatalystsSynthesis MethodReaction ConditionsCO2 Con. (%)CH4 Yie.
(%)		CH4 Sel.
(%)		Ref.
Temp. (°C)H2: CO2GHSV/h−1
Ni/Pr2O3-CeO2Impregnation3504:125,00054.554.5100[107]
Ni-CeO2/γ-Al2O3Impregnation3004:136,00079nd100[26]
Ni/NaYImpregnation5004:1nd67nd94[108]
Ca-NiTiO3/γ-Al2O3Precipitation3504:1200084.7378.8499.95[109]
Ni/CaZrO2Impregnation3504:124,000~75nd99[110]
Ni-5Mg/SBA-15Ammonia evaporation (AE)4004:130,00075nd100[111]
Ni/γ-Al2O3Impregnation5004:1600077.2nd99.9[112]
Ni/F-SBA-15Impregnation4504:124,90099.798.2nd[113]
Ni/CeO2Sol–gel 2504:110,00080.5nd95.8[114]
Ni-Nb2O5Impregnation3504:120,60092nd99[115]
Ni/Al2O3-SiO2Sol–gel3503.5:112,00082.38nd98.19[116]
Ni/bentoniteSolution combustion3004:1360085nd100[117]
Ni-Mn/BnImpregnation2704:1360085.2nd99.8[118]
Ni/Al2O3-ZrO2Sol-gel3004:1600077nd~100[119]
Ru-Ni/Ce0.9Zr0.1O2One-pot hydrolysis3004:1240098.2nd100[120]
Ni-CeO2/MCM-41Deposition precipitation3804:1900085.6nd99.8[121]
Y2O3-Ni/MgO-MCM-41Direct synthesis4004:1900065.55nd84.44[122]
Ni-Ce/CNTUltrasonic-assisted co-impregnation3504:130,00083.8nd~100[123]
Ni/MSNImpregnation3504:150,00085.4nd99.9[42]
nd: no data.
Table
Table 3. The catalytic activity of different Ni-based catalysts for CO2 methanation with balance gas.
Table 3. The catalytic activity of different Ni-based catalysts for CO2 methanation with balance gas.
CatalystsSynthesis MethodReaction ConditionsCO2 Con. (%)CH4 Yie.
(%)		CH4 Sel.
(%)		Ref.
Temp. (°C)H2:CO2:Ar (N2, He)GHSV/h−1
Ni/Y2O3Impregnation3004:1:520,000778099.5[124]
CA-Ni/Y2O3Impregnation3504:1:5600092~90100[125]
Ca/Ni/Al2O3Impregnation2754:1:5160,00093nd99[126]
Ni/mpCeO2Precipitation35016:4:560,00081nd99[127]
Ni-RuAlGlycerol Assisted Impregnation (GAI)40016:4:530,00060nd99.5[128]
NiCeYPrecipitation45012:3:530,000nd8095[129]
NiLaAl-HTPrecipitation4504:1:1480,00088nd98[130]
Ni/zeolite XFusion method45012:3:512,00053nd>90[131]
Ni/La2O2CO3Impregnation45012:3:520,00091nd99.9[132]
Ni/CeO2Gas discharge plasma27516:4:556,00084.2nd99.5[133]
Ni/ZrO2Impregnation4004:1:543,50050nd100[76]
Ni-La/Mg-AlUrea hydrolysis20036:9:545,00061nd~100[134]
Ni/ZrO2Plasma decomposition35016:4:560,00079.176.5100[135]
Ni-La2O3/Na-BETAImpregnation3504:1:1.2510,00065nd99[136]
Ni-Pd/γ-Al2O3Impregnation3004:1:8.5570090.5nd98.7[137]
NiCo/Al2O3Evaporation-induced self-assembly40012:3:510,00078nd99[80]
Ni/CeO2-ZrO2Ammonia evaporation2758:2:1520,00055nd99.8[138]
Ni/USYImpregnation4504:1:15nd72.6nd95[139]
Ni/CaO–Al2O3nd40012:3:1015,0008180nd[140]
Ni/La2O3Impregnation3204:1:1325097.1nd100[141]
nd: no data.
Table
Table 4. The catalytic performance of some Ni-based catalysts with low nickel loading.
Table 4. The catalytic performance of some Ni-based catalysts with low nickel loading.
CatalystsNi Loading (%)Reaction Temp. (°C)CO2 Con. (%)CH4 Yie.
(%)		CH4 Sel.
(%)		Ref.
Ni/CeZrO4235063nd100[154]
Ni/CaZrO25350~75nd99[110]
Ni/NaY550067nd94[108]
Ni/Ce0.85Zr0.15O2550070nd~100[157]
Ni/MSN535085.4nd99.9[42]
Ni/F-SBA-15545099.798.2nd[113]
Ni/TiO26.1735073.2ndnd[158]
Ni/MgO- MgH27.930085.2nd99.5[44]
Ni/CeO21027584.2nd99.5[133]
Ni/SiO21031077.2nd~100[101]
Ni/Y2O310300778099.5[124]
12CA-Ni/Y2O31035092~90100[125]
Ni/CeO21030084nd100[159]
Ni/mpCeO21035081nd99[127]
Ni-10La2O3/Na-BETA1035065nd99[136]
Ni-Pd/γ-Al2O31030090.5nd98.7[137]
Ni3Co/Al2O31040078nd99[80]
Ni/CeO2-ZrO21027555nd99.8[138]
Ni/CeO21034091.1nd100[103]
Ni-5Mg/SBA-151040075nd100[111]
Ni/La2O31032097.1nd100[141]
nd: no data.
Table
Table 5. The catalytic performance of Ni-based catalysts by different preparation methods.
Table 5. The catalytic performance of Ni-based catalysts by different preparation methods.
CatalystsSynthesis MethodReaction Temp. (°C)CO2 Con. (%)CH4 Sel.
(%)		Ref.
Ni-La2O3/Na-BETAImpregnation3506599[136]
Ni/Pr2O3-CeO2Impregnation35054.5100[107]
Ni/Y2O3Impregnation3007799.5[124]
Ni/CeO2Impregnation30084100[159]
Ni/MSNImpregnation35085.499.9[42]
Ni-CeO2/Al2O3Impregnation35085nd[188]
Ni–La/SiCImpregnation25039.699.6[189]
NiO-CeO2/SBA-15Impregnation3007693[168]
Ni/ZrO2Impregnation40050100[76]
Ni/CeZrO4Impregnation35063100[154]
Ni-Mn/BnImpregnation27085.299.8[118]
Ni/TiO2Impregnation35073.2nd[158]
Ni-Pd/γ-Al2O3Impregnation30090.598.7[137]
NiCeUSYImpregnation40068.395.1[190]
Ni/La2O3Impregnation32097.1100[141]
Ni-CeO2/γ-Al2O3Impregnation30079100[26]
Ni/NaYImpregnation5006794[108]
Ni/CaZrO2Impregnation350~7599[110]
Ni/γ-Al2O3Impregnation50077.299.9[112]
Ni/F-SBA-15Impregnation45099.7nd[113]
Ni/Ce-ABCImpregnation36088.692.3[176]
Ni-La2O3/γ-Al2O3Impregnation30097>99[165]
Ni/USYImpregnation45072.695[139]
NiCe/CNTUltrasonic-assisted co-impregnation35083.8~100[123]
Ni-RuAlGlycerol Assisted Impregnation (GAI)4006099.5[128]
Ni/mpCeO2Precipitation3508199[127]
NiCeYPrecipitation450nd95[129]
NiLaAl-HTPrecipitation4508898[130]
Ca-NiTiO3/γ-Al2O3Precipitation35084.7399.95[109]
Ni-Ce-Al2O3Precipitation35073.299.1[163]
Ni/Ce0.85Zr0.15O2Precipitation50070~100[157]
Ni-CeO2/MCM-41Deposition precipitation38085.699.8[121]
Ni/CeO2Sol-gel25080.595.8[114]
Ni/Al2O3-SiO2Sol-gel35082.3898.19[116]
Ni/SiO2Sol-gel31077.2~100[101]
Ru-Ni/Ce0.9Zr0.1O2One-pot hydrolysis30098.2100[120]
Ni-La/Mg-AlUrea hydrolysis20061~100[134]
Ni/bentoniteSolution combustion30085100[117]
Ni-Mg/SBA-15Ammonia evaporation (AE)40075100[111]
Ni/CeO2-ZrO2Ammonia evaporation (AE)2755599.8[138]
Y2O3-Ni/MgO-MCM-41Direct synthesis40065.5584.44[122]
Ni/zeolite XFusion method45053>90[131]
RhNi/Al2O3Galvanic replacement (GR)25097>90[191]
Ni/CeO2Gas discharge plasma27584.299.5[133]
Ni/MgO- MgH2Mechanochemical ball-milling method30085.299.5[44]
Ni/ZrO2Plasma decomposition35079.1100[135]
NiCo/Al2O3Evaporation-induced self-assembly4007899[80]
NiRu/CaO-Al2O3Facile evaporation-induced self-assembly method38083.8100[192]
Ni/CeO2Hard template method34091.1100[103]
Ni/ZrO2Combustion method30060~97.5[193]
nd: no data.
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Li, L.; Zeng, W.; Song, M.; Wu, X.; Li, G.; Hu, C. Research Progress and Reaction Mechanism of CO2 Methanation over Ni-Based Catalysts at Low Temperature: A Review. Catalysts 2022, 12, 244. https://doi.org/10.3390/catal12020244

AMA Style

Li L, Zeng W, Song M, Wu X, Li G, Hu C. Research Progress and Reaction Mechanism of CO2 Methanation over Ni-Based Catalysts at Low Temperature: A Review. Catalysts. 2022; 12(2):244. https://doi.org/10.3390/catal12020244

Chicago/Turabian Style

Li, Li, Wenqing Zeng, Mouxiao Song, Xueshuang Wu, Guiying Li, and Changwei Hu. 2022. "Research Progress and Reaction Mechanism of CO2 Methanation over Ni-Based Catalysts at Low Temperature: A Review" Catalysts 12, no. 2: 244. https://doi.org/10.3390/catal12020244

APA Style

Li, L., Zeng, W., Song, M., Wu, X., Li, G., & Hu, C. (2022). Research Progress and Reaction Mechanism of CO2 Methanation over Ni-Based Catalysts at Low Temperature: A Review. Catalysts, 12(2), 244. https://doi.org/10.3390/catal12020244

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