Two-dimensional molybdenum carbide 2D-Mo2C as a superior catalyst for CO2 hydrogenation

Early transitional metal carbides are promising catalysts for hydrogenation of CO₂. Here, a two-dimensional (2D) multilayered 2D-Mo₂C material is prepared from Mo₂CT_x of the MXene family. Surface termination groups T_x (O, OH, and F) are reductively de-functionalized in Mo₂CT_x (500 °C, pure H₂) avoiding the formation of a 3D carbide structure. CO₂ hydrogenation studies show that the activity and product selectivity (CO, CH₄, C₂-C₅ alkanes, methanol, and dimethyl ether) of Mo₂CT_x and 2D-Mo₂C are controlled by the surface coverage of T_x groups that are tunable by the H₂ pretreatment conditions. 2D-Mo₂C contains no T_x groups and outperforms Mo₂CT_x, β-Mo₂C, or the industrial Cu-ZnO-Al₂O₃ catalyst in CO₂ hydrogenation (evaluated by CO weight time yield at 430 °C and 1 bar). We show that the lack of surface termination groups drives the selectivity and activity of Mo-terminated carbidic surfaces in CO₂ hydrogenation.