Dual d–p Orbital Hybridization in NiO x @RP@Co SA : A Synergistic Strategy for Enhanced Photocatalytic Benzyl Alcohol Oxidation and Hydrogen Evolution

ABSTRACT Although red phosphorus (RP) is a promising photocatalyst, its performance in simultaneous benzyl alcohol (BA) oxidation and H 2 evolution is constrained by undesirable carrier recombination and sluggish surface reaction kinetics. The d–p orbital hybridization, serving as a crucial mechanism for electronic structure regulation, offers an effective strategy to address the aforementioned challenges. Hence, RP is synergistically regulated by defect‐rich nickel oxide (NiO x ) and Co single atoms (Co SA ) to construct a dual d−p orbital hybridized photocatalyst (NiO x @RP@Co SA ). In the NiO x @RP@Co SA system, the Ni 3d–P 2p orbital hybridization optimizes the BA adsorption at Ni sites and reducing the C─H bond activation energy barrier. Meanwhile, the Co 3d–P 2p orbital hybridization is conducive to balancing the hydrogen reduction reaction. In situ characterization combined with density functional theory (DFT) calculations confirms that precise regulation of dual d–p orbital hybridization not only enhances charge separation efficiency but also promotes surface reaction kinetics. The 5NiO x @RP@0.2Co SA exhibited superior photocatalytic performance, which is approximately a 15.48‐fold enhancements compared to RP. This work not only elucidates the mechanism of dual d−p orbital hybridization but also establishes a novel paradigm for the design of efficient and multifunctional solar‐driven catalytic systems.