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

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 NH2‐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. A photo‐enzyme catalytic system using laccase as a biocatalyst and MIL‐53(Fe) and NH2‐MIL‐53(Fe) as photocatalysts shows stimulated photoelectron transfer under visible light. Electrons trapped by laccase's T1Cu enable effective catalysis. The immobilization method and interfacial distance between laccase and metal‐organic frameworks are critical for reaction activity.