Co₃O₄ Nanocrystals with an Oxygen Vacancy-Rich and Highly Reactive (222) Facet on Carbon Nitride Scaffolds for Efficient Photocatalytic Oxygen Evolution

Oxygen evolution reaction (OER) with sluggish kinetics is the rate-determining step of water splitting, which dominates the solar-to-hydrogen fuel conversion efficiency. Herein, we constructed an oxygen vacancy-rich and highly reactive (222) facet in Co3O4 nanocrystals anchored on carbon nitride nanofiber (CNF) by a solvothermal reduction method. The resulting Co3O4 nanocrystals/CNF (COCNF) demonstrated a dramatically enhanced OER with a rate of 24.9 μmol/h under visible light, which is 124 times higher than that of CNF. This excellent catalytic activity of COCNF is based on a synergistic effect between its binary components for charge separation, oxygen vacancies for enhanced conductivity, and facet (222) exposure of Co3O4 nanocrystals for improved heterogeneous kinetics. Density functional theory (DFT) calculations revealed the water oxidation mechanism at different facets and found that the formed oxygen vacancies lead to a reduction of the materials’ bandgap. The correlation between Co3O4 crystal facets and the inherent OER catalytic activities under acidic solution was in the order of (222) > (220) > (311).