Sun Jun-Chao, Wang Yong
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China.
Chemphyschem. 2024 Dec 16;25(24):e202400785. doi: 10.1002/cphc.202400785. Epub 2024 Nov 3.
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=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.
在最近的研究中，钽基过渡金属催化剂对析氢反应（HER）表现出显著的催化活性。然而，磷化钽（TaP）在析氢反应中的应用尚未见报道。在此，通过密度泛函理论（DFT）对TaP催化剂进行了系统研究。预测了TaP(004)对析氢反应的性能。对吸附氢原子的Ta端和P端表面进行了热力学分析，并仔细研究了TaP(004)表面上的析氢反应机理。理论结果表明，TaP(004)表现出优异的析氢活性（ΔG = 0.0456 eV），在酸性条件下，Ta端和P端表面均遵循Volmer-Heyrovsky机理，其中Volmer步骤是速率决定步骤。还应用了混合表面策略来探索Ta端和P端表面的协同效应，这增强了析氢活性。此外，该研究筛选了掺杂剂以评估它们对析氢活性的影响，结果表明用S、Ni、Co、Fe和Cr掺杂可以改善析氢性能。
