Two-dimensional π-conjugated metal–organic nanosheets as single-atom catalysts for the hydrogen evolution reaction

Abstract

The design and synthesis of electrocatalysts with controllable active sites are highly desirable for producing hydrogen. Inspired by the experimental realization of two-dimensional metal–organic framework (2D-MOF) nanosheets, a computational screening was performed to find out the optimal single-atom catalysts for the hydrogen evolution reaction (HER) from 36 2D-MOFs composed of transition metal and benzene-like molecular ligands. Through first-principles calculations, six configurations were identified as potential catalysts for the HER with performance comparable to those of Pt-based catalysts due to the near-zero Gibbs free energy and favourable activation barriers originating from their appropriate d-orbital bonding mechanism with atomic hydrogen.