Frustrated Lewis Pairs Boosting Electrochemical Production of Hydrogen Peroxide on Bi‐TiO2−x Nanocatalysts

Abstract Electrocatalytic two‐electron oxygen reduction (2e − ORR) offers an environmentally friendly route for H 2 O 2 production, yet faces challenges in O 2 activation and *OOH intermediate stabilization. Here, Bi‐TiO 2−x nanocatalysts are introduced featuring frustrated Lewis acid‐base pairs (FLPs) active sites, where the Bi single atoms with electron‐deficient characteristics serve as Lewis acidic (LA) sites and the O atoms surrounding the oxygen vacancy (O V ) act as Lewis basic (LB) sites. The Bi‐TiO 2−x catalyst exhibits high H 2 O 2 selectivity up to 96.5%. Furthermore, in a flowing electrolytic cell, the H 2 O 2 selectivity reaches 93.9% with a yield of 1.56 mol g catalyst −1 h −1 at −50 mA cm −2 and is able to maintain a stable reaction for 54 h. Theoretical calculations and in situ spectroscopic analyses indicate that the FLPs structure can effectively promote the dissociation of H 2 O and the activation of O 2 during the reaction, provide protons for the subsequent reaction, and facilitate the formation of *OOH intermediates. The coupling system of 2e − ORR with ethylene glycol oxidation significantly improves the selectivity of H 2 O 2 to 98.9% and the yield to 3.02 mol g catalyst −1 h −1 , meanwhile, the anode simultaneously produces formic acid as a co‐product, which improves the utilization of system resources.