Theoretical Prediction of Enhanced Hydrogen Evolution Reaction Electrocatalysts Based on Tantalum Phosphide

Abstract Ta‐based transition metal catalysts have shown significant catalytic activity for the hydrogen evolution reaction (HER) in recent studies. However, the application of tantalum phosphide (TaP) in the HER has not been documented. Herein, a systematic study of TaP catalysts was performed through density functional theory (DFT). The performance of TaP (004) for the HER was predicted. Thermodynamic analyses of Ta‐terminated and P‐terminated surfaces with adsorbed hydrogen atoms were conducted, and the HER mechanism on TaP (004) surfaces was carefully investigated. Theoretical results revealed that TaP (004) exhibits excellent HER activity (ΔG H* =0.0456 eV), and both the Ta‐terminated and P‐terminated surfaces follow the Volmer‐Heyrovsky mechanism under acidic conditions, with the Volmer step being the rate‐determining step. A mixed surface strategy was also applied to explore the synergistic effects of Ta‐terminated and P‐terminated surfaces, which enhanced the HER activity. Additionally, the study screened dopants to assess their impact on the HER activity, revealing that doping with S, Ni, Co, Fe, and Cr could improve the HER performance.