Stability and Reactivity of Metal Nanoclusters Supported on Transition Metal Carbides.

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. 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 develop a high-throughput screening approach to catalyst design for supported nanoclusters based on density functional theory, and apply it to elucidate the stability and catalytic performance of all possible combinations between 7 monometallic nanoclusters (Rh, Pd, Pt, Au, Co, Ni and Cu) and 11 stable support 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. We identify 8 TMn@TMC combinations as promising catalysts, all of them being new for experimental validation, thus expanding the chemical space for efficient conversion of CH4 and CO2.