Single‐Crystalline Ultrathin Co3O4 Nanosheets with Massive Vacancy Defects for Enhanced Electrocatalysis

The role of vacancy defects is demonstrated to be positive in various energy‐related processes. However, introducing vacancy defects into single‐crystalline nanostructures with given facets and studying their defect effect on electrocatalytic properties remains a great challenge. Here this study deliberately introduces oxygen defects into single‐crystalline ultrathin Co₃O₄ nanosheets with O‐terminated {111} facets by mild solvothermal reduction using ethylene glycol under alkaline condition. As‐prepared defect‐rich Co₃O₄ nanosheets show a low overpotential of 220 mV with a small Tafel slope of 49.1 mV dec^?1 for the oxygen evolution reaction (OER), which is among the best Co‐based OER catalysts to date and even more active than the state‐of‐the‐art IrO₂ catalyst. Such vacancy defects are formed by balancing with reducing environments under solvothermal conditions, but are surprisingly stable even after 1000 cycles of scanning under OER working conditions. Density functional theory plus U calculation attributes the enhanced performance to the oxygen vacancies and consequently exposed second‐layered Co metal sites, which leads to the lowered OER activation energy of 2.26 eV and improved electrical conductivity. This mild solvothermal reduction concept opens a new door for the understanding and future designing of advanced defect‐based electrocatalysts.