A Self‐Assembled MOF‐Escherichia Coli Hybrid System for Light‐Driven Fuels and Valuable Chemicals Synthesis

The development of semi‐artificial photosynthetic systems, which integrate metal–organic frameworks (MOFs) with industrial microbial cell factories for light‐driven synthesis of fuels and valuable chemicals, represents a highly promising avenue for both research advancements and practical applications. In this study, an MOF (PCN‐222) utilizing racemic‐(4‐carboxyphenyl) porphyrin and zirconium chloride (ZrCl4) as primary constituents is synthesized. Employing a self‐assembly process, a hybrid system is constructed, integrating engineered Escherichia coli (E. coli) to investigate light‐driven hydrogen and lysine production. These results demonstrate that the light‐irradiated biohybrid system efficiently produce H2 with a quantum efficiency of 0.75% under full spectrum illumination, the elevated intracellular reducing power NADPH is also observed. By optimizing the conditions, the biohybrid system achieves a maximum lysine production of 18.25 mg L−1, surpassing that of pure bacteria by 332%. Further investigations into interfacial electron transfer mechanisms reveals that PCN‐222 efficiently captures light and facilitates the transfer of photo‐generated electrons into E. coli cells. It is proposed that the interfacial energy transfer process is mediated by riboflavin, with facilitation by secreted small organic acids acting as hole scavengers for PCN‐222. This study establishes a crucial foundation for future research into the light‐driven biomanufacturing using E. coli‐based hybrid systems. A self‐assembly biohybrid is constructed by combining Escherichia coli with a metal‐organic framework via multiple interactions. Under illumination, the system demonstrates a remarkable improvement in H2 production and NADPH level, leading to an increased production of NADPH‐dependent lysine. Mechanistic investigations indicate riboflavin plays a role in electron transfer, while secreted small organic acids act as hole scavengers and carbon source.