Oxygen-oxygen bond cleavage enables efficient photocatalytic H2O2 production via an *O2 dissociation pathway

Abstract

Abstract Photocatalytic reduction of O 2 to H 2 O 2 is generally regarded to proceed through the *O 2 hydrogenation pathway (*O 2 → *OOH), which inevitably encounters a high energy barrier proton extraction process via cleavage of the H-O bond in H 2 O. Designing a K and Cs co-modified polymeric carbon nitride (CN-KCs) to create dual-end adsorption sites as frustrated Lewis pairs for O 2 , on which the O-O breaking energy is significantly reduced and a *O 2 dissociation pathway towards photocatalytic H 2 O 2 synthesis is realized (*O 2  → 2*O, then *O + *H 2 O → H 2 O 2 ). The CN-KCs presents a competitive photocatalytic H 2 O 2 yield of 1806.6 μmolh −1 , a high quantum efficiency of 72.3% at 420 nm, and a solar-to-H 2 O 2 conversion efficiency of 6.1% with presence of biomass derivative. Here, we show that regulating dual-end adsorption sites opens a door to new *O 2 dissociation avenue for efficient conversion of O 2 to H 2 O 2 .