Abstract
Focusing on five key concepts, we review the roles of cation and oxygen vacancies in determining the surface reconstruction pathway, reaction mechanism, and ultimate activity of cobalt-based oxygen evolution reaction (OER) electrocatalysts. Cation and oxygen vacancies can initiate reactant adsorption, facilitating active surface reconstruction, and can switch the dominant mechanism from the adsorbate evolution mechanism (AEM) to the lattice oxygen evolution mechanism (LOEM). However, these effects are facet-dependent. Rigorous oxygen vacancy quantification promises to identify the OER mechanism steering thresholds and unlock the full potential of vacancy engineering. Finally, oxygen vacancy quantification strategies are critically examined to facilitate this goal.