Two-dimensional molybdenum carbide 2D-Mo<sub>2</sub>C as a superior catalyst for CO<sub>2</sub> hydrogenation.

Zhou, Hui; Chen, Zixuan; Kountoupi, Evgenia; Tsoukalou, Athanasia; Abdala, Paula M; Florian, Pierre; Fedorov, Alexey; Müller, Christoph R · Nat Commun · 2021

basic_science · Level V

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Abstract

Early transitional metal carbides are promising catalysts for hydrogenation of CO<sub>2</sub>. Here, a two-dimensional (2D) multilayered 2D-Mo<sub>2</sub>C material is prepared from Mo<sub>2</sub>CT<sub>x</sub> of the MXene family. Surface termination groups T<sub>x</sub> (O, OH, and F) are reductively de-functionalized in Mo<sub>2</sub>CT<sub>x</sub> (500 °C, pure H<sub>2</sub>) avoiding the formation of a 3D carbide structure. CO<sub>2</sub> hydrogenation studies show that the activity and product selectivity (CO, CH<sub>4</sub>, C<sub>2</sub>-C<sub>5</sub> alkanes, methanol, and dimethyl ether) of Mo<sub>2</sub>CT<sub>x</sub> and 2D-Mo<sub>2</sub>C are controlled by the surface coverage of T<sub>x</sub> groups that are tunable by the H<sub>2</sub> pretreatment conditions. 2D-Mo<sub>2</sub>C contains no T<sub>x</sub> groups and outperforms Mo<sub>2</sub>CT<sub>x</sub>, β-Mo<sub>2</sub>C, or the industrial Cu-ZnO-Al<sub>2</sub>O<sub>3</sub> catalyst in CO<sub>2</sub> 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 CO<sub>2</sub> hydrogenation.