Hydrogen-bonded organic framework@conductive metal-organic framework heterostructures for ampere-level hydrogen peroxide production

Abstract Electrochemical two-electron oxygen reduction reaction (2e – ORR) in neutral environments holds remarkable promise for sustainable hydrogen peroxide (H 2 O 2 ) production. However, its practical application is largely hindered due to the scarcity of electrocatalysts with high selectivity and durability under ampere-level current densities. Herein, a hydrogen-bonded organic framework@conductive metal-organic framework (HOF@ c MOF) heterostructure is designed for industrial-level H 2 O 2 electrosynthesis. Through integrating DAT-HOF (DAT=diaminotriazole) and Co- c MOF, Co-N bonds formed at the heterointerface modulates the electronic structure of Co sites, optimizing the adsorption strength of oxygen intermediates with improved activity and selectivity. Besides, the formation of built-in electric field drives the proton migration from DAT-HOF to Co- c MOF, facilitating the O 2 protonation to H 2 O 2 at Co sites. In further combination with the high proton donation capability of DAT-HOF and high conductivity of Co- c MOF, efficient H 2 O 2 production is achieved with a H 2 O 2 Faradic efficiency of 97.1 ± 0.4%, a H 2 O 2 yield of 738.9 mg h⁻ 1 cm⁻ 2 and a long-term durability over 100 h at 1200 mA cm⁻ 2 . This work offers a high-performance electrocatalyst for promoting the industrial implementation of H 2 O 2 electrosynthesis.