Molybdenum (VI)‐oxo Clusters Incorporation Activates g‐C₃N₄ with Simultaneously Regulating Charge Transfer and Reaction Centers for Boosting Photocatalytic Performance

Abstract Establishing local built‐in electric field of 2D semiconductors is one of the promising strategies to regulate the oriented charge delivery to active centers for enhancing photocatalytic performance. Herein, a novel heptamolybdate polyanions‐intercalated porous g‐C₃N₄ ([Mo₇O₂₄]⁶⁻‐pCN) catalyst with integrating highly desirable visible‐light photocatalytic features is reported. After intercalation, the apparent reaction rate constants (k_app) of [Mo₇O₂₄]⁶⁻‐pCN for bisphenol A (BPA) and 4‐chlorophenol (4‐CP) photodegradation are remarkably enhanced, which are 9.0 and 6.4 times faster than those of pCN, respectively. Analogously, the k_app values of [Mo₇O₂₄]^6–‐CN for BPA and 4‐CP removal are also improved by contrast with CN. The experimental results and density functional theory calculations indicate that a local built‐in electric field is formed in [Mo₇O₂₄]⁶⁻‐pCN with a polarization direction from aromatic rings of g‐C₃N₄ to the inserted [Mo₇O₂₄]⁶⁻ clusters. Driven by the electric field, photogenerated carriers can be efficiently separated for better reactive oxidative species (ROSs) production. These O atoms are also proved as adsorption sites for phenols, greatly reducing the migration distance of ROSs and thus improving photocatalytic performances. This work offers a reliable strategy to construct local built‐in electric field via polyoxometalates intercalation for effective solar energy conversion and phenolic wastewater remediation.