Zhonglong Yu, Jiehu Cui, Longkang Guo, Liang Xu, Shuxia Wang, Zhanjun Yu, Tao Zhang, Jialin Cai
Rational manipulation of electronic structure and surface reaction energetics is essential for the development of high-performance bifunctional electrocatalysts for overall water splitting. Herein, a transition-metal doping method is proposed to systematically evaluate the activity of Ni-FeOOH modified with V, Nb, Zr, Mn, and Zn. A new S,V, co-doped Ni-FeOOH heterostructure supported on Ni foam is constructed, which induces redistributed electron density, regulated lattice strain, and enriched oxygen vacancies. As a result, the S,V, co-doped Ni-FeOOH catalyst exhibits outstanding oxygen evolution reaction (OER) performance with a low overpotential of 264 mV at 50 mA cm-2, a small Tafel slope of 28.36 mV dec-1, ECSA of 25.67 mF cm-2, and the lowest charge-transfer resistance (Rct = 1.20 Ω). Meanwhile, the hydrogen evolution reaction (HER) activity is simultaneously enhanced, achieving an overpotential of 99 mV at 10 mA cm-2 with a Tafel slope of 141.2 mV dec-1, ECSA of 64.2 mF cm-2, and Rct = 1.25 Ω. Notably, the catalyst maintains stable OER/HER performance for 600 h at high current densities of 100, 200, and 400 mA cm-2, demonstrating exceptional durability under industrially relevant conditions. This work establishes a periodicity-guided dopant-synergy engineering strategy for simultaneously enhancing activity and durability in bifunctional electrocatalysts for alkaline water electrolysis.