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The utilization of fossil fuel has increased atmospheric carbon dioxide (CO2) concentrations drastically over the last few decades. This leads to global warming and climate change, increasing the occurrence of more severe weather around the world. One promising solution to reduce anthropogenic CO2 emissions is methanation. Many researchers and industries are interested in CO2 methanation as a power-to-gas technology and carbon capture and storage (CCS) system. Producing an energy carrier, methane (CH4), via CO2 methanation and water electrolysis is an exceptionally effective method of capturing energy generated by renewables. To enhance methanation efficiency, numerous researches have been conducted to develop catalysts with high activity, CH4 selectivity, and stability against the reaction heat. Therefore, in this mini-review, the characteristics and recent advances of metal-based catalysts in methanation of CO2 is discussed. [ABSTRACT FROM AUTHOR]

A large amount of greenhouse gases, such as carbon dioxide and methane, are released during the production process of bioethanol and biogas. Converting CO2 into methane is a promising way of capturing CO2 and generating high-value gas. At present, CO2 methanation technology is still in the early stage. It requires high temperature (300–400 ℃) and pressure (> 1 MPa), leading to high cost and energy consumption. In this study, a new catalyst, Ni–Fe/Al–Ti, was developed. Compared with the activity of the common Ni/Al2O3 catalyst, that of the new catalyst was increased by 1/3, and its activation temperature was reduced by 100℃. The selectivity of methane was increased to 99%. In the experiment using simulated fermentation gas, the catalyst showed good catalytic activity and durability at a low temperature and atmospheric pressure. Based on the characterization of catalysts and the study of reaction mechanisms, this article innovatively proposed a Ni–Fe/Al–Ti quaternary catalytic system. Catalytic process was realized through the synergism of Al–Ti composite support and Ni–Fe promotion. The oxygen vacancies on the surface of the composite carrier and the higher activity metals and alloys promoted by Fe accelerate the capture and reduction of CO2. Compared with the existing catalysts, the new Ni–Fe/Al–Ti catalyst can significantly improve the methanation efficiency and has great practical application potential. [ABSTRACT FROM AUTHOR]

In recent years, major economies have implemented carbon reduction and carbon neutrality policies. Furthermore, with advancements in science and technology, carbon dioxide (CO2) is now considered a valuable raw material for producing carbon-based fuels through hydrogenation. Various concentrations of yttrium (referred to as Y hereafter) were introduced to assess their influence on the catalytic performance of CO2 methanation. At a temperature of 300 °C, the catalyst exhibited an impressive CO2 conversion rate of 78.4% and maintained remarkable stability throughout a rigorous 100 h stability assessment. The findings suggest that the inclusion of yttrium (Y) promotes the formation of oxygen vacancies and alkaline sites on the catalyst. This, in turn, enhances the reducibility of nickel species, improves the dispersion of nickel particles, and plays a pivotal role in enhancing thermal stability. Furthermore, it offers an innovative design approach for creating highly efficient composite CO2 methanation catalysts by controlling particle size and harnessing synergistic catalytic effects at the metal/support interface. [ABSTRACT FROM AUTHOR]

Catalytic gas-phase hydrogenation of CO2 into CH4 was tested under three different nickel/aluminate catalysts obtained from precursors of hexaaluminate composition (MAl16O19, M = Mg, Ca, Ba). These catalysts were prepared using a carbon template method, where carbon is self-generated from a sol-gel that contains an excess of citric acid and the Al and M salts (Ba2+, Ca2+, Mg2+) by two-step calcination in an inert/oxidizing atmosphere. This procedure yielded Ni particles decorating the surface of a porous high surface area matrix, which presents a typical XRD pattern of aluminate structure. Ni particles are obtained with a homogeneous distribution over the surface and an average diameter of ca 25–30 nm. Obtained materials exhibit a high conversion of CO2 below 500 °C, yielding CH4 as a final product with selectivity >95%. The observed trend with the alkaline earth cation follows the order NiBaAlO-PRx > NiCaAlO-PRx > NiMgAlO-PRx. We propose that the high performance of the NiBaAlO sample is derived from both an appropriate distribution of Ni particle size and the presence of BaCO3, acting as a CO2 buffer in the process. [ABSTRACT FROM AUTHOR]

Catalytic carbon dioxide (CO2) hydrogenation to carbon monoxide (CO) via reverse water-gas shift (RWGS) reaction is of particular interest due to its direct use in various industrial processes as feedstock. However, the competitive CO2 methanation process severely limits the RWGS reaction in a lower temperature range. In this context, we propose a novel nanocatalyst (NC) comprising oxygen vacancy-enriched subnanometer-scale CoPd hybrid cluster (CoOxVPd)-anchored Pd nanoparticles (NPs) on cobalt oxide support underneath (denoted as CP-CoOxVPd) by using a galvanic replacement reaction-assisted wet chemical reduction method. As-developed CP-CoOxVPd NC initiated the RWGS reaction at 423 K temperature while showing an optimum CO production yield of ∼3414 μmol g−1catalyst and a CO selectivity as high as ∼99% at 523 K in the reaction gas of CO2:H2 = 1:3. The results of physical characterizations along with electrochemical and gas chromatography (GC) suggest that abundant oxygen vacancies in the surface-anchored CoOxVPd clusters are vital for CO2 adsorption and subsequent activation, while neighboring Pd domains facilitate the H2 dissociation. The obtained results are expected to provide a feasible design of Co-based NCs for the RWGS reaction. [ABSTRACT FROM AUTHOR]

An Ni-CeO2 catalyst with high Ni loading (50 wt.%) prepared by a salt-assisted solution combustion method was characterized by different methods and used for CO2 methanation. The specific surface area of the Ni-CeO2 catalyst prepared by salt-assisted solution combustion is 7 times that of the catalyst prepared by conventional solution combustion. The Ni-CeO2 catalyst prepared by salt-assisted solution combustion has smaller particle sizes of Ni and exhibits excellent activity at low temperatures. The high Ni loading and small Ni particle size can provide more metal Ni site and Ni-CeO2 interface, which help to improve the CO2 methanation performance. [ABSTRACT FROM AUTHOR]

A series of Ni-xSi/ZrO2 (x = 0, 0.1, 0.5, 1 wt%, the controlled contents of Si) catalysts with a controlled nickel content of 10 wt% were prepared by the co-impregnation method with ZrO2 as support and Si as a promoter. The effect of different amounts of Si on the catalytic performance was investigated for CO2 methanation with the stoichiometric H2/CO2 molar ratio (4/1). The catalysts were characterized by BET, XRF, H2-TPR, H2-TPD, H2-chemisorption, CO2-TPD, XRD, TEM, XPS, and TG-DSC. It was found that adding the appropriate amount of Si could improve the catalytic performance of Ni/ZrO2 catalyst at a low reaction temperature (250 °C). Among all the catalysts studied, the Ni-0.1Si/ZrO2 catalyst showed the highest catalytic activity, with H2 and CO2 conversion of 73.4% and 72.5%, respectively and the yield of CH4 was 72.2%. Meanwhile, the catalyst showed high stability and no deactivation within a 10 h test. Adding the appropriate amount of Si could enhance the interaction between Ni and ZrO2, and increase the Ni dispersion, the amounts of active sites including surface Ni0, oxygen vacancies, and strong basic sites on the catalyst surface. These might be the reasons for the high activity and selectivity of the Ni-0.1Si/ZrO2 catalyst. [ABSTRACT FROM AUTHOR]

The increasing utilization of renewable sources for electricity production turns CO2 methanation into a key process in the future energy context, as this reaction allows storing the temporary renewable electricity surplus in the natural gas network (Power-to-Gas). This kind of chemical reaction requires the use of a catalyst and thus it has gained the attention of many researchers thriving to achieve active, selective and stable materials in a remarkable number of studies. The existing papers published in literature in the past few years about CO2 methanation tackled the catalysts composition and their related performances and mechanisms, which served as a basis for researchers to further extend their in-depth investigations in the reported systems. In summary, the focus was mainly in the enhancement of the synthesized materials that involved the active metal phase (i.e., boosting its dispersion), the different types of solid supports, and the frequent addition of a second metal oxide (usually behaving as a promoter). The current manuscript aims in recapping a huge number of trials and is divided based on the support nature: SiO2, Al2O3, CeO2, ZrO2, MgO, hydrotalcites, carbons and zeolites, and proposes the main properties to be kept for obtaining highly efficient carbon dioxide methanation catalysts. [ABSTRACT FROM AUTHOR]

CO2 hydrogenation toward methane, a reaction of high environmental and sustainable energy importance, was investigated at 200–600 °C and H2/CO2 = 4/1, over Rh nanoparticles dispersed on supports with different oxygen storage capacity characteristics (γ-Al2O3, alumina-ceria-zirconia, and ceria-zirconia). The effects of the support OSC and Rh particle size on reaction behavior under both integral and differential conditions were investigated, to elucidate the combined role of these crucial catalyst design parameters on methanation efficiency. A volcano-type variation of methanation turnover frequency was found in respect to support OSC; Rh/ACZ, with intermediate OSC, was the optimal catalyst. The structure sensitivity of the reaction was found to be a combined function of support OSC and Rh particle size: For Rh/γ-Al2O3 (lack of OSC) methanation was strongly favored on small particles—the opposite for Rh/CZ (high OSC). The findings are promising for rational design and optimization of CO2 methanation catalysts by tailoring the aforementioned characteristics. [ABSTRACT FROM AUTHOR]

High surface area cobalt-lanthanide bimetallic aerogels were successfully synthesized by the epoxide addition method. The bimetallic aerogels were calcined at two different temperatures and either bimetallic oxides containing oxychlorides, Co3O4.3LnOCl (Ln = La, Sm, Gd, Dy and Yb) or perovskites, LnCoO3 (Ln = La, Sm, Gd and Dy) were obtained at 500 or 900 °C, respectively. The exceptions are the aerogels of cerium and ytterbium, which after oxidation at 500 and 900 °C, stabilize as sesquioxides: Co3O4.3CeO2 and 2Co3O4.3Yb2O3, the first at both temperatures and the second only at the highest temperature. The bimetallic cobalt-lanthanide oxychlorides or perovskites were tested as catalysts for the methanation of CO2. The cobalt catalytic activity is determined by the type and acid-base properties of the lanthanide oxide phase and by its pre-reduction under hydrogen. The best results were those obtained over the calcined aerogels pre-reduced under hydrogen. In particular, the highest values were those obtained over the Co-Ce aerogel calcined at 900 °C that in the same conditions present an activity comparable to that measured over a 5 wt.% Rh catalyst supported on alumina, one of the literature references. The activity and the selectivity increase with the catalysts' basicity, showing an inverse dependence of the reduction temperature that decreases along the lanthanide series either for the aerogels calcined at 500 or 900 °C. In general, the basicity of the aerogels calcined at 900 °C (perovskites) is higher and they are more active but less selective than those calcined at 500 °C (oxychlorides), which to our knowledge is for the first time reported for the methanation of CO2. [ABSTRACT FROM AUTHOR]

Mesoporous Ni-based catalysts with Ni confined in nanochannels are widely used in CO2 methanation. However, when Ni loadings are high, the nanochannels are easily blocked by nickel particles, which reduces the catalytic performance. In this work, three-dimensional mesoporous Ni-CeO2-CSC catalysts with high Ni loadings (20−80 wt %) were prepared using a colloidal solution combustion method, and characterized by nitrogen adsorption–desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and H2 temperature programmed reduction (H2-TPR). Among the catalysts with different Ni loadings, the 50% Ni-CeO2-CSC with 50 wt % Ni loading exhibited the best catalytic performance in CO2 methanation. Furthermore, the 50% Ni-CeO2-CSC catalyst was stable for 50 h at 300° and 350 °C in CO2 methanation. The characterization results illustrate that the 50% Ni-CeO2-CSC catalyst has Ni particles smaller than 5 nm embedded in the pore walls, and the Ni particles interact with CeO2. On the contrary, the 50% Ni-CeO2-CP catalyst, prepared using the traditional coprecipitation method, is less active and selective for CO2 methanation due to the larger size of the Ni and CeO2 particles. The special three-dimensional mesoporous embedded structure in the 50% Ni-CeO2-CSC can provide more metal–oxide interface and stabilize small Ni particles in pore walls, which makes the catalyst more active and stable in CO2 methanation. [ABSTRACT FROM AUTHOR]

Ni-Ce-Zr-Oδ catalysts were prepared via one-pot hydrothermal synthesis. It was found that Ni can be partially incorporated into the Ce-Zr lattice, increasing surface oxygen species. The catalysts possess high surface areas even at high Ni loadings. The catalyst with Ni content of 71.5 wt.% is able to activate CO2 methanation even at a low temperature (200 °C). Its CO2 conversion and methane selectivity were reported at 80% and 100%, respectively. The catalyst was stable for 48 h during the course of CO2 methanation at 300 °C. Catalysts with the addition of medium basic sites were found to have better catalytic activity for CO2 methanation. [ABSTRACT FROM AUTHOR]

The resistance to sintering of Ni/Al2O3 catalysts with different additives for methanation reaction was modeled and predicted by data mining. In the screening, the resistance to sintering of Na, Ca, Ce, Mg, La, Cu, Zn, Zr, In, Mo, and Ti promoted Ni/Al2O3 catalyst were measured in terms of the increased rate of the size of the metallic nickel particles. The resistance to sintering of catalysts, described by the increased rate of Ni particle size as well as basic physicochemical properties of the 11 selected elements, was adopted for optimization model construction by data mining. Through regression model prediction and experimental verification, Cs was found to be an additive, and promotes the resistance to sintering mostly for Ni/Al2O3 catalysts. This result provides further evidence that data mining techniques can be employed as a highly efficient tool for the discovery of new catalysts in comparison with the traditional experimental method. [ABSTRACT FROM AUTHOR]

In this work, we present an investigation concerning the evaluation of the catalytic properties of Ni nanoparticles supported on ZrO2, SiO2, and MgAl2O4 for CO2 hydrogenation to methane. The supports were prepared by coprecipitation and sol-gel, while Ni was incorporated by impregnation (10–20 wt %). X-ray diffraction, nitrogen physisorption, temperature-programmed reduction, H2 pulse chemisorption, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy were the main characterization techniques employed. A laboratory fixed-bed reactor operated at atmospheric pressure, a temperature range of 350–500 °C, and a stoichiometric H2/CO2 molar ratio was used for catalyst evaluation. The most outstanding results were obtained with nickel catalysts supported on ZrO2 with CO2 conversions of close to 60%, and selectivity to methane formation was 100% on a dry basis, with high stability after 250 h of reaction time. The majority presence of tetragonal zirconia, as well as the strong Ni–ZrO2 interaction, were responsible for the high catalytic performance of the Ni/ZrO2 catalysts. [ABSTRACT FROM AUTHOR]