Abstract The surface composition segregation can have important effects on the catalytic and electrochemical properties of an alloy catalyst. We have performed density-functional theory (DFT) calculations to investigate the effects of a third transition metal (M) addition into the Ni3Mo alloy on the surface segregation and the stability of bulk-terminated and Ni-segregated Ni3Mo/M(111) surfaces. The third transition metals (M Tc, Ru, W, Re, or Os) are found to enhance the Ni surface segregation, while M Ti, V, Cr, Mn, Fe, Co, Cu, Nb, Rh, Hf, Ta, or Ir retain the Ni-segregated surface but weaken the Ni surface segregation tendency. The remaining transition metals (M Sc, Zn, Y, Zr, Pd, Ag, Cd, Pt, or Au) show a complete suppression of the Ni surface segregation. We find the transition metals (Ti, V, Cr, Mn, Fe, Co, Cu, Hf, and W) can stabilize a special atomic configuration that is predicted to have an outstanding catalytic performance for water electrolysis. Furthermore, we analyze the factors that control the Ni surface segregation behavior in the Ni3Mo/M(111) surface. The present study provides useful theoretical guide for developing highly active Ni-Mo-M hydrogen evolution electrodes.

中文翻译：

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通过向 Ni 3 Mo 中添加第三种过渡金属来设计高效镍基水电解催化剂

摘要 表面成分偏析对合金催化剂的催化和电化学性能有重要影响。我们已经进行了密度泛函理论 (DFT) 计算，以研究在 Ni3Mo 合金中添加第三种过渡金属 (M) 对表面偏析和体端接和 Ni 偏析 Ni3Mo/M(111) 表面稳定性的影响. 发现第三种过渡金属（M Tc、Ru、W、Re 或 Os）可增强 Ni 表面偏析，而 M Ti、V、Cr、Mn、Fe、Co、Cu、Nb、Rh、Hf、Ta、或 Ir 保留 Ni 偏析表面但削弱 Ni 表面偏析趋势。剩余的过渡金属（M Sc、Zn、Y、Zr、Pd、Ag、Cd、Pt 或 Au）完全抑制了 Ni 表面偏析。我们找到过渡金属（Ti、V、Cr、Mn、Fe、Co、Cu、Hf、和 W) 可以稳定一种特殊的原子构型，预计该构型对水电解具有出色的催化性能。此外，我们分析了控制 Ni3Mo/M(111) 表面中 Ni 表面偏析行为的因素。本研究为开发高活性 Ni-Mo-M 析氢电极提供了有用的理论指导。