Metal clusters supported on transition metal carbides for efficient CH4 and CO2 conversion

Small particles of transition metals (TM) supported on transition metal carbides (TMC) -TMn@TMC- provide a plethora of design opportunities for catalytic applications due to their highly exposed active centres, efficient atom utilisation and the physicochemical properties of the TMC support, which polarises the electron density of the supported particle enhancing its catalytic properties. To date, however, only a very small subset of TMn@TMC catalysts have been tested experimentally and it is unclear which combinations may best catalyse which chemical reactions. Herein, we address this question by performing a high-throughput screening study using periodic Density Functional Theory calculations to elucidate the stability and catalytic performance of all possible combinations between 7 metals (Rh, Pd, Pt, Au, Co, Ni and Cu) supported on 11 stable surfaces of TMCs with 1:1 stoichiometry (TiC, ZrC, HfC, VC, NbC, TaC, MoC and WC) towards CH4 and CO2 conversion technologies. We analyse the generated database to unravel trends or simple descriptors in their resistance towards metal aggregate formation and sintering, oxidation, stability in the presence of adsorbate species, and study their adsorptive and catalytic properties, to facilitate the discovery of novel materials in the future. In addition, we identify Pdn@ZrC, Ptn@ZrC, Pdn@HfC, Ptn@HfC, Nin@VC, Pdn@VC, Nin@NbC and Pdn@NbC as promising catalysts, all of them being new for experimental validation, thus expanding the chemical space for efficient conversion of CH4 and CO2.