Z‑Schematic Artificial Leaf Structure for Biosolar Oxyfunctionalization of Hydrocarbons

The natural Z-schematic photosynthesis is a promising catalytic model for solar-to-chemical conversion. Here, we construct a Z-schematic, wireless photoelectrocatalytic (PEC) system (i.e., artificial leaf) for biocatalytic oxyfunctionalization of hydrocarbons. The monolithic leaf structure consists of a tandem photoanode|photocathode configuration that uses sunlight as the sole energy source to drive redox reactions. Under solar light, the ferric oxyhydroxide-coated, molybdenum-doped bismuth vanadate (FeOOH|Mo:BVO) photoanode extracts electrons from H₂O electron feedstock and transfers the electrons to the conjugated polyterthiophene (pTTh) photocathode. Meanwhile, the pTTh photocathode absorbs FeOOH|Mo:BVO-filtered light for O₂ reduction to H₂O₂. The in situ generated H₂O₂ activates unspecific peroxygenases (UPOs) to drive enantioselective C–H oxyfunctionalization (e.g., hydroxylation and epoxidation). Furthermore, we solve HO^•-mediated inactivation of UPOs using a cellulose membrane, which increases enzymatic productivity with a benchmark total turnover number of 193 000 among PEC and photocatalytic platforms that trigger UPO-mediated synthesis.