Plasma-Induced Defect Engineering and Cation Refilling of NiMoO₄ Parallel Arrays for Overall Water Splitting

Developing highly active water splitting electrocatalysts with ordered micro/nanostructures and uniformly distributed active sites can meet the increasing requirement for sustainable energy storage/utilization technologies. However, the stability of complicated structures and active sites during a long-term process is also a challenge. Herein, we fabricate a novel approach to create sufficient atomic defects via N₂ plasma treatment onto parallel aligned NiMoO₄ nanosheets, followed by refilling of these defects via heterocation dopants and stabilizing them by annealing. The parallel aligned nanosheet arrays with an open structure and quasi-two-dimensional long-range diffusion channels can accelerate the mass transfer at the electrolyte/gas interface, while the incorporation of Fe/Pt atoms into defect sites can modulate the local electronic environment and facilitate the adsorption/reaction kinetics. The optimized Pt-NP-NMC/CC-5 and Fe-NP-NMC/CC-10 electrodes exhibit low overpotentials of 71 and 241 mV at 10 mA cm^-2 for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), respectively, and the assembled device reveals a low voltage of 1.55 V for overall water splitting. This plasma-induced high-efficiency defect engineering and coupled active site stabilization strategy can be extended to large-scale fabrication of high-end electrocatalysts.