Noble metal-modified copper surfaces for alkaline condition hydrogen evolution reaction

Cu-based materials would be attractive candidates for cost-effective alkaline hydrogen evolution reaction (HER) electrocatalysts due to high abundance, excellent conductivity, and excellent stability in alkaline environments, if not for the inherent inertness of Cu in HER. This inertness has led to a relative lack of research on Cu-based HER catalysts in both experimental and theoretical domains. Here, We report engineered Cu(111) surfaces that can significantly improve the poor activity of H ₂O dissociation on pure Cu(111) surface. We do this by introducing noble metal atoms (M = Ru, Rh, Pd, Ag, Os, Ir, Pt) through surface doping. These modified surfaces exhibit excellent thermodynamic and electrochemical stability, with the exception of Cu(111)-Ag. Notably, the H ₂O dissociation energy barrier on Cu(111)-Os ( E _b) is only 0.74 eV, which is much smaller than that (1.31 eV) of pure Cu(111), and is even lower than that of Pt ( E _b = 0.92 eV), which is commercially used for electrodes. The low E _b and resulting expected excellent performance of Cu(111)-Os for water splitting is related to the particular local electronic properties of doped Os atoms, specifically the electronic structure of the Os d-orbitals, which have a d-band center near Fermi level ( E _F) and a high density of states around E _F, including just above E _F. These results are expected to stimulate the investigation of surface alloyed Cu, leading to a new direction for the design of high-performance and low-cost electrocatalysts.