Tailoring Electrocatalytic Hydrogen Evolution Activity in Topological Triangular Metal–Organic Frameworks

Abstract Metal–organic frameworks (MOFs) have attracted considerable attention in catalysis due to their exceptional structural and chemical tunability. However, high electrical conductivity is rare in MOFs, hindering their practical applications toward catalytic reactions. Recently, 2D topological MOFs stand out for the unique topologically nontrivial electronic structures. Particularly, their high electrical conductivity and chemical tunability make them promising candidates as high‐performance catalysts. In this study, theoretical investigations are conducted into the intrinsic electronic properties and chemical activity of a 2D topological Cu‐1,3,5‐tris(pyridyl)benzene (Cu‐TPyB) framework. It is found that the coordination environment of Cu with pyridyl groups plays a crucial role in modulating the electron density around the Fermi level, thereby enhancing the catalytic activity of Cu‐TPyB toward electrochemical hydrogen evolution reaction (HER). Furthermore, substituting the single embedded Cu atom with Cu 3 and Cu 4 Bi 3 clusters further increases the electron density around the Fermi level. Specifically, the Cu 4 Bi 3 ‐TPyB framework exhibits superior HER activity, which is attributed to its high electron density contributed by the p orbitals of Bi and the d orbitals of Cu. This work introduces a novel approach for optimizing the catalytic activity of 2D MOFs and developing high‐performance catalysts.