CH4 is the main component of natural gas; there is a need for heterogeneous catalysts that can directly convert it into useful substances. On active metal surfaces, e.g., Pt surfaces, CH4 is sequentially dehydrogenated to CH or C. It is very difficult to obtain useful C2 products from them. We here present a catalytic informatics strategy with DFT calculations and databases to discover bimetallic alloy catalysts for selective methane coupling, which cannot be achieved with monometal catalysts. Considering two properties required for a methane conversion catalyst, i.e., reactivity and selectivity, alloy surfaces that allow the initial C–H bond cleavage reaction of methane to proceed and that stabilize CH2 and CH3 species more than CH and C species will be suitable catalysts for direct methane conversion. An exhaustive screening of alloys satisfying such conditions is carried out using density functional theory calculations. As a result, MgPt is predicted to be one of the most useful catalysts; on its surface, the activity of Pt is moderately suppressed due to Mg, and CH3 and CH2 species get more stable than CH and C species. The calculations predict that the C–C coupling reaction with the lowest activation barrier on the MgPt surface occurs for the pair of CH3 and CH2, producing the C2H5 adsorbed species; it becomes ethane if hydrogenated and ethylene if dehydrogenated. In addition, the optimal Mg/Pt ratio for the reaction is computationally explored, and it is found that the Mg/Pt ratio of 1:1 is the best. Eventually, experimental verification is carried out by actually synthesizing an alloy satisfying this ratio; the nonoxidative coupling reaction of methane molecules is tested in the presence of the MgPt catalyst, and the formation of C2 hydrocarbons as primary products is confirmed.

two major greenhouse gases, carbon dioxide (CO 2 ) and methane (CH 4 ), into industrially valuable chemical products. [1,2] Dry reforming of methane (DRM: CH 4 + CO 2 → 2H 2 + 2CO) is of the highest potential to utilize both the CH 4 and CO 2 . [3,4] Moreover, DRM products, hydrogen (H 2 ) or synthesis gas (CO/H 2 ), can be widely used in ammonia synthesis, methanol synthesis, Fischer-Tropsch synthesis, etc. However, the current DRM is usually conducted via heterogeneous catalysis at high temperatures over 800 °C to promote the strongly endothermic reaction (ΔH 298 K = +247 kJ mol −1 ). [5] Such high-temperature process results in huge consumption of fuels and short lifetime of DRM catalysts. [5][6][7] It is highly desirable to develop high-performance catalysts that drive DRM in a low-temperature range from 400 °C through 600 °C (low-temperature DRM or LT-DRM). But at such low temperatures the side reactions, including methane decomposition (CH 4 → 2H 2 + C(s); ΔH 298 K = +75 kJ mol −1 ), the Boudouard reaction (2CO → CO 2 + C(s): ΔH 298 K = −171 kJ mol −1 ), and reverse water gas shift (CO 2 + H 2 → CO + H 2 O; ΔH 298 K = +41.2 kJ mol −1 ), can compete with the DRM pathway, leading to severe catalyst degradation. [5,8,9] It is acknowledged that precious metals (PM: Pd, Pt, etc.), as catalytic centers, are highly active in DRM. Extensive studies have reported that they possessed higher activity and more resistant to carbon deposition than nickel (Ni)-based catalysts. [5,[10][11][12][13] However, high materials cost precluded widespread use of these PM-based catalysts in DRM. In contrast, low-cost Ni-based catalysts would be more promising in large-scale industrial DRM applications. In addition, there have been a number of attempts to develop magnesium oxide (MgO) as catalyst support or promoter in DRM because its basic nature can enhance chemisorption of CO 2 and inhibit carbon deposition. [14][15][16] Although considerable efforts have been spent on these designs, few studies have succeeded in fabrication of MgO catalysts with long-term stability in DRM. [17,18] Therefore, to realize high performance and long-term stability over the basic MgO support and low-cost Ni metal, it is very necessary to explore an efficient spatial structure for these two components.Here we present a nanoporous composite catalyst with an intertwined network structure consisting of fibrous Ni-and MgO phases (average thickness = 10 nm), i.e., n-Ni#MgO. The intertwined, porous network of n-Ni#MgO is fabricated from A nanoporous catalyst consisting of intertwined, fibrous networks of nickel and magnesium oxide, i.e., n-Ni#MgO, is fabricated from a Ni-Mg alloy via atmospheric treatments followed by acid leaching. The n-Ni#MgO efficiently catalyzes reforming of the two major greenhouse gases, methane (CH 4 ) and carbon dioxide (CO 2 ), in a low-temperature range (<600 °C). Moreover, it exhibits higher coking tolerance than conventional nickel-based catalysts and can rival commercial precious metal catalysts in terms of both the reaction act...

In article number 2000041, Xiaobo Peng, Hideki Abe and co‐workers report the development of a novel catalyst n‐Ni#MgO, which efficiently converts two major greenhouse gases, methane and carbon dioxide, into value‐added synthesis gas (a mixture of hydrogen and carbon monoxide) at a high reaction selectivity. The nanostructure of n‐Ni#MgO consists of intertwined, fibrous metal nickel and magnesium oxide, and acts as a high‐performance catalysis center.