Chemo‐Biological Cascade Catalysis Assisted Semi‐Artificial Photosynthetic Systems for Improving the Synthesis of High‐Valued Chemicals

Abstract Semi‐artificial photosynthetic systems integrate the light‐capturing ability of photosensitizers with the selectivity of biocatalysis, enabling efficient conversion of solar energy into chemical energy. The photosensitizers can generate photogenerated charges (electrons and holes) under illumination. However, the holes not only damage microbial cells but also increase the charge carrier recombination rate, thereby reducing the conversion efficiency of semi‐artificial photosynthetic systems. Herein, a chemo‐biocatalytic cascade strategy is proposed to eliminate photogenerated holes. By cascading chemical reactions to produce nutrients within the hybrid system, the production of high‐valued chemicals exhibits a six‐fold increase compared to normal conditions. This improvement can be attributed to the chemical reactions introduced, which consume the photogenerated holes, promote the separation efficiencyof charge carriers, and facilitate an increased flow of photogenerated charges into the intracellular. In addition, the produced nutrients can serve as a new substrate source to support cellular metabolism. The versatility of this hybrid system is further explored by initiating a cascade reaction for the reform of microplastics. The strategy not only enhances the synthetic efficiency of semi‐artificial photosynthetic systems but also shows significant potential for converting waste plastics into high‐valued chemicals.