Self‐Optimized Reconstruction of Metal–Organic Frameworks Introduces Cation Vacancies for Selective Electrosynthesis of Hydrogen Peroxide

Abstract The electrocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) through the two‐electron oxygen reduction pathway represents a green production process that has gained increasing importance. Nevertheless, there is a dearth of efficacious catalysts to attain high activity under industrial current density. In this study, we present a strategy for cation vacancy generation through metal–organic frameworks self‐optimized reconfiguration for the efficient electrosynthesis of H 2 O 2 under industrial current densities in solid‐electrolyte cell. The ZIF‐ZC91@Co(OH) 2 ‐V Co electrocatalyst exhibits significant H 2 O 2 selectivity of 97.8%, and the H 2 O 2 productivity is up to 24.53 mol g catalyst −1 h −1 with a direct and continuous output of ∼3.36 wt% H 2 O 2 aqueous solutions under industrial current density (400 mA cm −2 ). Impressively, the ZIF‐ZC91@Co(OH) 2 ‐V Co possesses superb long‐term durability for over 220 h and can output H 2 O 2 aqueous solution with a concentration of ∼8.03 wt% in the pilot experiment. Theoretical calculations confirm that the introduction of modest cation vacancies optimizes the adsorption strength of *OOH intermediate and reduces both thermodynamic and kinetic barriers, thus balancing the selectivity of the two‐electron oxygen reduction. This work provides valuable insights into the rapid, eco‐friendly synthesis of H 2 O 2 and the rational design of highly active catalysts.