Tailoring <i>D‐p</i> Orbital Hybridization for Enhanced Photocatalytic H ₂ O ₂ Production Coupled with Glycerol Green Oxidation

Abstract The process of photocatalytic hydrogen peroxide (H 2 O 2 ) synthesis is mostly controlled by O 2 adsorption and activation. Accurately adjusting O 2 adsorption and O 2 activation is still quite difficult. Tailoring d‐p orbital hybridization technique to accurately modify O 2 adsorption and O 2 activation in O V ‐Bi 2 O 2 S/CuInS 2 (O V ‐BOS/CIS) photocatalyst is proposed. According to theoretical calculations, the addition of O V ‐Bi 2 O 2 S (O V ‐BOS) to the O V ‐BOS/CIS catalyst progressively enhanced the d‐p orbital hybridization between Cu 3 d and O 2 p , leading to a d ‐orbital electron band ( d ‐band) widening and controlled d ‐band centre on Cu sites. The optimized d ‐band enabled for fine manipulation of O 2 adsorption and O 2 activation in the O V ‐BOS/CIS, resulting in a remarkable H 2 O 2 production activity of 42.39 mmol g −1 h −1 , coupled with glycerol (GLY) oxidation. Moreover, as a unique proton donor, GLY successfully captured holes to boost H 2 O 2 production while also producing valuable oxidation product glycolic acid (GA). The work sheds light on the optimal design for potential H 2 O 2 production and GLY oxidation catalysts.