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

The electrocatalytic synthesis of hydrogen peroxide (H2O2) 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 H2O2 under industrial current densities in solid‐electrolyte cell. The ZIF‐ZC91@Co(OH)2‐VCo electrocatalyst exhibits significant H2O2 selectivity of 97.8%, and the H2O2 productivity is up to 24.53 mol gcatalyst−1 h−1 with a direct and continuous output of ~3.36 wt% H2O2 aqueous solutions under industrial current density (400 mA cm−2). Impressively, the ZIF‐ZC91@Co(OH)2‐VCo possesses superb long‐term durability for over 220 h and can output H2O2 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 H2O2 and the rational design of highly active catalysts.