Enhanced H2O2 production by selective electrochemical reduction of O2 on fluorine-doped hierarchically porous carbon

Electrochemical synthesis of hydrogen peroxide (H 2 O 2 ) via two-electron pathway of oxygen reduction reaction is a promising alternative to the current anthraquinone process. The H 2 O 2 production from O 2 is a competing reaction with four-electron O 2 reduction to H 2 O, and the selectivity is related to the adsorption energy of the OOH intermediate on electrocatalysts surface. Generally, the properties for binding of OOH intermediate on catalysts can be controlled by changing its electronic structure. Herein, the electronic structure of porous carbon materials was tuned by doping different types and contents of fluorine species. The yield of H 2 O 2 generation depended on the F content and the best catalytic activity toward H 2 O 2 electrosynthesis was obtained with F content of 3.41 at.%. The resultant F-doped porous carbon (FPC) catalysts exhibited good H 2 O 2 selectivity of 97.5–83.0% and the H 2 O 2 production rate could reach 112.6–792.6 mmol h −1  g −1 over the potential range of 0.2 V to −0.3 vs. RHE (pH 1). The density functional theory (DFT) calculations and experiments revealed that the incorporation of CF 2, 3 into carbon plane promotes the activation of O 2 molecule and facilitates desorption of OOH intermediate, which was crucial to H 2 O 2 synthesis.