Beyond Natural Evolution Enables Yeast With an Acquired Solar‐to‐Hydrogen Feature by Biomineralization Triggering Biotic‐Abiotic Synergies

The “cell factory” strategy, which integrates microbial biocatalysis with semiconductor photoelectrochemical properties, offers a viable route for solar‐to‐hydrogen conversion. However, engineering hydrogenase‐independent microorganisms for direct solar fuel production through the mutual regulation between biomolecules and mineralized materials, while avoiding metabolic disorder, remains highly challenging. Here, yeast is conferred with an acquired capability for sustainable solar‐to‐hydrogen conversion by employing a biomineralization strategy to trigger synergistic catalysis between the cells and a ZnCdS nanoassembly grown on the cell surfaces (Yeast@Zn x Cd 1‐x S). The solid solution nanoassembly, aggregated by about 5 nm nanocrystals, possesses abundant sulfur vacancies (S v ) than chemically synthesized Zn x Cd 1‐x S (Chem‐Zn x Cd 1‐x S), realizing stronger reducing ability and efficient photocarriers separation. The photoelectrons from Zn x Cd 1‐x S are transferred into cells through transmembrane proteins (TMPs), where they participate in glycolysis and enable the regeneration of the essential reducing equivalent NADH (reduced nicotinamide adenine dinucleotide), thereby supplying intracellular protons for hydrogen evolution. The Yeast@Zn 0.55 Cd 0.45 S achieves exceptional photocatalytic hydrogen evolution rate of 5095.41 µmol g −1 Zn 0.55 Cd 0.45 S h −1 , nearly double that of Chem‐Zn 0.55 Cd 0.45 S (2909.75 µmol g −1 Zn 0.55 Cd 0.45 S h −1 ). This work offers an avenue for “cell function reorganization” by biomineralization triggering biotic‐abiotic synergies bypasses the natural enzymatic pathways, enabling solar‐to‐chemicals in non‐photosynthetic microorganisms.