Two-dimensional π-conjugated metal bis(dithiolene) nanosheets as promising electrocatalysts for carbon dioxide reduction: a computational study

A highly efficient and low-cost catalyst for the carbon dioxide reduction reaction (CO2RR) is of critical importance to convert CO2 into valuable fuels and chemicals. Herein, the potential of several pi-conjugated metal bis(dithiolene) complex nanosheets (M3C12S12, where M denotes Fe, Co, Ni, Ru, Rh, and Pd) as CO2RR electrocatalysts was systemically investigated by means of comprehensive density functional theory (DFT) computations. The results reveal that among the studied candidates, Rh3C12S12 nanosheets exhibit the highest CO2RR catalytic activity due to their low limiting potential (-0.43 V) and activation barrier (1.60 eV). In particular, CH4 is identified as the product, and CHO* formation is the potential/rate-determining step. Thus, by carefully controlling the type of metal atoms, M3C12S12 can be utilized as a promising electrocatalyst for the CO2RR, which may provide a new avenue to design novel metal organic framework (MOF)-based electrocatalysts.