Theoretical Investigation of Single-Atom Catalysts for Hydrogen Evolution Reaction Based on Two-Dimensional Tetragonal V2C2 and V3C3

Developing stable and effective catalysts for the hydrogen evolution reaction (HER) has been a long-standing pursuit. In this work, we propose a series of single-atom catalysts (SACs) by importing transition-metal atoms into the carbon and vanadium vacancies of tetragonal V₂C₂ and V₃C₃ slabs, where the transition-metal atoms refer to Ti, V, Cr, Mn, Fe, Co, Ni, and Cu. By means of first-principles computations, the possibility of applying these SACs in HER catalysis was investigated. All the SACs are conductive, which is favorable to charge transfer during HER. The Gibbs free energy change (Δ<i>G</i>_H*) during hydrogen adsorption was adopted to assess their catalytic ability. For the V₂C₂-based SACs with V, Cr, Mn, Fe, Ni, and Cu located at the carbon vacancy, excellent HER catalytic performance was achieved, with a |Δ<i>G</i>_H*| smaller than 0.2 eV. Among the V₃C₃-based SACs, apart from the SAC with Mn located at the carbon vacancy, all the SACs can act as outstanding HER catalysts. According to the Δ<i>G</i>_H*, these excellent V₂C₂- and V₃C₃-based SACs are comparable to the best-known Pt-based HER catalysts. However, it should be noted that the V₂C₂ and V₃C₃ slabs have not been successfully synthesized in the laboratory, leading to a pure investigation without practical application in this work.