Enhanced Interfacial Electron Transfer in Photocatalyst‐Natural Enzyme Coupled Artificial Photosynthesis System: Tuning Strategies and Molecular Simulations

Abstract Laccase is capable of catalyzing a vast array of reactions, but its low redox potential limits its potential applications. The use of photocatalytic materials offers a solution to this problem by converting absorbed visible light into electrons to facilitate enzyme catalysis. Herein, MIL‐53(Fe) and NH 2 ‐MIL‐53(Fe) serve as both light absorbers and enzyme immobilization carriers, and laccase is employed for solar‐driven chemical conversion. Electron spin resonance spectroscopy results confirm that visible light irradiation causes rapid transfer of photogenerated electrons from MOF excitation to T1 Cu(II) of laccase, significantly increasing the degradation rate constant of tetracycline (TC) from 0.0062 to 0.0127 min −1 . Conversely, there is only minimal or no electron transfer between MOF and laccase in the physical mixture state. Theoretical calculations demonstrate that the immobilization of laccase's active site and its covalent binding to the metal‐organic framework surface augment the coupled system's activity, reducing the active site accessible from 27.8 to 18.1 Å. The constructed photo‐enzyme coupled system successfully combines enzyme catalysis’ selectivity with photocatalysis's high reactivity, providing a promising solution for solar energy use.