Unlocking Synergistic Catalysis in NiP: Dual Role of Electronic Structure and Lewis Acidity for Enhanced Oxygen Evolution Reaction<span style="mso-fareast-font-family: DengXian; mso-fareast-theme-font: minor-fareast; mso-fareast-language: ZH-CN;">

Nickel phosphides (NixPy) are recognized as an important potential alternative to noble-metal catalysts for the oxygen evolution reaction (OER). Among nickel phosphides, NiP consisting of the equal stoichiometric ratio of Ni and P could help quantify the catalytic effect of P and Ni. In this work, density functional theory (DFT) is employed to investigate the OER mechanism of NiP surfaces. Electronic structure theory analysis reveals that P atoms tend to assist in stabilizing O* at the adsorption sites. The rich electron donation from the Ni atom can alter the local charge distribution and enhance the interaction between O* and P atom. Moreover, we find that both oxygen intermediate adsorption energy and OER overpotential exhibit linear correlations with adsorption site charge. Electron loss at the site induces the overall system exhibiting Lewis acid characteristics, making it favorable for the OER. Leveraging electronic structure theory and Lewis acid-base theory, we offer a new insight into the OER mechanism on NiP surface, demonstrating that the catalytic activity of bulk metallic surface materials like NiP can be optimized by tailoring the local chemical environment on the surface. This study may provide a reference for base metal catalyst design.