Potential in “Imperfection”: From Precise Construction to Electrocatalytic Enhancement of Vacancy Engineering

Abstract Driven by the “dual carbon” strategic goals, electrocatalytic reactions have increasingly become a research frontier in the fields of energy and materials science due to their crucial role in the conversion of clean energy and environmental governance. Vacancy engineering has great potential in enhancing catalytic activity and selectivity. Systematically and deeply revealing the mechanism of vacancies in the electrocatalytic process has important value for achieving precise structural regulation and performance optimization of electrocatalysts. This work systematically reviews the research progress of vacancy modification electrocatalysts in recent years. The detection technology of vacancies is introduced, the synthetic strategies for vacancy construction are summarized, the catalytic functions of vacancies in various typical electrocatalytic reactions and their internal regulatory mechanisms are mainly discussed, and the regulatory effect of vacancies on the adsorption behavior of intermediates is analyzed. The structure–function relationship laws of factors such as vacancy type, concentration, and spatial distribution on catalytic performance are further summarized, providing theoretical support for the rational design of vacancy engineering. Finally, the future development direction of vacancy engineering is prospected, with the expectation of providing a theoretical basis and research ideas for constructing new electrocatalytic materials that are efficient, stable, and applicable on a large scale.