Modulating Local Proton Coverage and *OOH Generation via Coupled Multiple Sites for Enhanced Photocatalytic H<sub>2</sub>O<sub>2</sub> Production
Wengao Zeng, Yuchen Dong, Xiaoyuan Ye, Yi Zhao, Ziying Zhang, Tuo Zhang, Lei Zhang, Jie Chen, Xiangjiu Guan
Abstract
Rationally modulating the adsorption of reaction intermediates on the surface sites of carbon nitride-based catalysts could facilitate the photocatalytic reduction of O 2 to H 2 O 2 . Herein, theoretical calculations reveal that multiple sites of heteroatoms and defects can synergistically increase local proton coverage and lower the kinetic barrier for O 2 protonation, thereby promoting the production of *OOH and the subsequent generation of H 2 O 2 . As a proof of concept, carbon nitride (BPMC-Vs) with multiheteroatoms (B and P) and multidefects (N defects, ─C≡N) was successfully synthesized, achieving optimized solar-to-chemical conversion efficiency and selectivity of 0.33% and 95.2%, respectively. In situ spectroscopic characterization combined with theoretical calculations confirms that P atoms and ─C≡N groups increase proton coverage, while B atoms and N defects effectively promote the protonation of O 2 to *OOH, thereby significantly enhancing the generation of H 2 O 2 . This work provides insightful guidance for carbon nitride catalysis at the atomic scale for boosting photocatalytic H 2 O 2 production.