Integration of a Hydrogenase in a Lead Halide Perovskite Photoelectrode for Tandem Solar Water Splitting

Lead halide perovskite solar cells are notoriously moisture-sensitive, but recent encapsulation strategies have demonstrated their potential application as photoelectrodes in aqueous solution. However, perovskite photoelectrodes rely on precious metal co-catalysts, and their combination with biological materials remains elusive in integrated devices. Here, we interface [NiFeSe] hydrogenase from Desulfovibrio vulgaris Hildenborough, a highly active enzyme for H₂ generation, with a triple cation mixed halide perovskite. The perovskite-hydrogenase photoelectrode produces a photocurrent of -5 mA cm^-2 at 0 V vs RHE during AM1.5G irradiation, is stable for 12 h and the hydrogenase exhibits a turnover number of 1.9 × 10⁶. The positive onset potential of +0.8 V vs RHE allows its combination with a BiVO₄ water oxidation photoanode to give a self-sustaining, bias-free photoelectrochemical tandem system for overall water splitting (solar-to-hydrogen efficiency of 1.1%). This work demonstrates the compatibility of immersed perovskite elements with biological catalysts to produce hybrid photoelectrodes with benchmark performance, which establishes their utility in semiartificial photosynthesis.