Screening and design of 2D metal–organic frameworks for hydrogen evolution reaction through controlling transition metals and heteroligands

Two-dimensional (2D) metal–organic frameworks (MOFs) are potential electrocatalysts for hydrogen evolution reaction (HER). However, the origin of HER catalytic activities of 2D MOFs remains unclear. We herein design a series of 2D triphenylene-based MOFs as HER electrocatalysts candidates by tuning the composition of transition metals and homoligands/heteroligands. Among the 230 candidates, CuOS and AgOS were identified as ideal candidates as HER electrocatalysts, through a four-step screening strategy evaluating their stability, Gibbs free energies of H adsorption, different H coverages, and the kinetic barriers. In particular, we pointed that the p-band and p+d-band centers as intrinsic descriptors can directly evaluate the HER performance of 2D MOFs, due to the interaction between metals and ligands that can tune the electronic structure of the active center. Our work not only elucidates the structure–performance correlations of 2D MOFs but also provides the theoretical platform to design new 2D MOFs as efficient HER electrocatalysts.