Oxygen Vacancy and Core–Shell Heterojunction Engineering of Anemone‐Like CoP@CoOOH Bifunctional Electrocatalyst for Efficient Overall Water Splitting

Constructing cost-efficient and robust bifunctional electrocatalysts for both neutral and alkaline water splitting is highly desired, but still affords a great challenge, due to sluggish hydrogen/oxygen evolution reaction (HER/OER) kinetics. Herein, an in situ integration engineering strategy of oxygen-vacancy and core-shell heterojunction to fabricate an anemone-like CoP@CoOOH core-shell heterojunction with rich oxygen-vacancies supported on carbon paper (CoP@CoOOH/CP), is described. Benefiting from the synergy of CoP core and oxygen-vacancy-rich CoOOH shell, the as-obtained CoP@CoOOH/CP catalyst displays low overpotentials at 10 mA cm-2 for HER (89.6 mV/81.7 mV) and OER (318 mV/200 mV) in neutral and alkaline media, respectively. Notably, a two-electrode electrolyzer, using CoP@CoOOH/CP as bifunctional catalyst to achieve 10 mA cm-2 , only needs low-cell voltages in neutral (1.65 V) and alkaline (1.52 V) electrolyte. Besides, systematically experimental and theoretical results reveal that the core-shell heterojunction efficiently accelerates the catalytic kinetics and strengthens the structural stability, while rich oxygen-vacancies efficiently decrease the kinetic barrier and activation energy, and reduce the energy barrier of the rate-determining-step for OER intermediates, thus intrinsically boosting OER performance. This work clearly demonstrates that oxygen-vacancy and core-shell heterojunction engineering provide an effective strategy to design highly-efficient non-precious, bi-functional electrocatalysts for pH-universal water splitting.