Facet-Dependent Surface Restructuring on Nickel (Oxy)hydroxides: A Self-Activation Process for Enhanced Oxygen...

Unraveling the catalyst surface structure and behavior during reactions is essential for both mechanistic understanding and performance optimization. Here we report a phenomenon of facet-dependent surface restructuring intrinsic to β-Ni(OH)₂ catalysts during oxygen evolution reaction (OER), discovered by the correlative ex situ and operando characterization. The ex situ study after OER reveals β-Ni(OH)₂ restructuring at the edge facets to form nanoporous Ni_1-O, which is Ni deficient containing Ni³⁺ species. Operando liquid transmission electron microscopy (TEM) and Raman spectroscopy further identify the active role of the intermediate β-NiOOH phase in both the OER catalysis and Ni₁O formation, pinpointing the complete surface restructuring pathway. Such surface restructuring is shown to effectively increase the exposed active sites, accelerate Ni oxidation kinetics, and optimize *OH intermediate bonding energy toward fast OER kinetics, which leads to an extraordinary activity enhancement of ∼16-fold. Facilitated by such a self-activation process, the specially prepared β-Ni(OH)₂ with larger edge facets exhibits a 470-fold current enhancement than that of the benchmark IrO₂, demonstrating a promising way to optimize metal-(oxy)hydroxide-based catalysts.