Dual d-p Orbital Hybridization in NiOx@RP@Co_SA: A Synergistic Strategy for Enhanced Photocatalytic Benzyl Alcohol...

Although red phosphorus (RP) is a promising photocatalyst, its performance in simultaneous benzyl alcohol (BA) oxidation and H₂ 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 (NiOx) and Co single atoms (Co_SA) to construct a dual d-p orbital hybridized photocatalyst (NiOx@RP@Co_SA). In the NiOx@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 5NiOx@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.