Multiple Vacancies on (111) Facets of Single-Crystal NiFe₂ O₄ Spinel Boost Electrocatalytic Oxygen Evolution Reaction

Oxygen evolution reaction (OER) as the rate-determining reaction of water splitting has been attracting enormous attention. At present, only some noble-metal oxide materials (IrO₂ and RuO₂ ) have been reported as efficient OER electrocatalysts for OER. However, the high cost and scarcity of these noble-metal oxide materials greatly hamper their large-scale practical application. Herein, we synthesize 100% (111) faceted NiFe₂ O₄ single crystals with multiple vacancies (cation vacancies and O vacancies). The (111) facets can supply enough platform to break chemical bonds and enhance electrocatalytic activity, due to its high density of atomic steps and kink atoms. Compared to NiFe₂ O₄ (without vacancies), the as-synthesized NiFe₂ O₄ -Ar (with vacancies) exhibits a dramatically improved OER activity. The NiFe₂ O₄ -Ar-30 shows the lowest onset potential (1.45 V vs RHE) and the best electrocatalytic OER activity with the lowest overpotential of 234 mV at 50 mA cm^-2 . Furthermore, based on the theoretical calculations that the introduction of multiple vacancies can effectively modulate the electronic structure of active centers to accelerate charge transfer and reaction intermediates adsorption, which can reduce the reaction energy barrier and enhance the activity of electrochemical OER.