Near‐Theoretical Solar‐Powered Hydrogen Production From a Photosensitive MOF Nanozyme‐Microbe Hybrid

ABSTRACT Photo‐biological hybrid hydrogen production systems integrate the advantages of microbial whole‐cell catalysis and functional catalytic materials, but reactive oxygen species (ROS) generated by photoactive materials often impair metabolic activity and electron transfer efficiency. Here, we reported a photosensitive MOF nanozyme‐microbe hybrid engineered to achieve ROS‐mitigated interfacial electron transfer and highly efficient light‐driven hydrogen production. By anchoring Rose Bengal sodium (RB) onto MIL‐101, we constructed a bifunctional photosensitizing nanozyme MIL‐101‐nRB with a tunable bandgap, RB‐dependent peroxidase‐like activity, and excellent biocompatibility. Under illumination, triethanolamine (TEOA) mediates directional electron transfer from MIL‐101‐nRB to the microbe surface, reshaping intracellular redox fluxes and promoting photo‐fermentation hydrogen metabolism. This metabolic reprogramming is evidenced by the near‐complete depletion of volatile fatty acids (VFAs) at the end of hydrogen production. Under sufficient light intensity, the hybrid achieved a record‐high cumulative hydrogen yield of 11.88 mol/mol‐glucose, unambiguously demonstrating a genuinely light‐driven process. Our hybrid system exhibits an exceptional apparent quantum yield of 23.56% at 470 nm, exceeding those of most reported hybrid systems. This work establishes a generalizable strategy to resolve ROS‐induced toxicity while enhancing interfacial electron transfer in MOF‐based biological hybrid systems, advancing the development of high‐efficiency, solar‐powered green hydrogen technologies.