Developing excellent activity and stability bifunctional electrocatalysts for alkaline water splitting remains challenging. This work constructs ultrathin MOx/Rh metallene heterostructures (M = Fe, Co, Ni) via atmosphere-controlled solvothermal synthesis, achieving uniform MOx nanoclusters on Rh metallene with optimized interfaces. The FeOx/Rh catalyst demonstrates exceptional bifunctional activity, requiring only 1.53 V for overall water splitting at 10 mA cm-2 with robust durability. Leveraging the unique oxygen-affinity of FeOx and its strong electronic coupling with Rh, this study reveals the critical role of the high-energy interface in accelerating the kinetics of the rate-limiting four-electron oxygen evolution reaction. Mechanistic insights reveal that FeOx promotes water dissociation via optimized orbital hybridization, while electronically modulated Rh optimizes hydrogen adsorption (ΔGH* = -0.057 eV) via d-band downshifting. This interfacial engineering strategy enables efficient solar-driven hydrogen production, offering a sophisticated paradigm for designing high-performance bifunctional metallene catalysts.
Wei et al. (Mon,) studied this question.