A Silicon-Based Heterojunction Integrated with a Molecular Excited State in a Water-Splitting Tandem Cell

Semiconductor-based photocathodes with high light-absorption capability are of interest in the production of solar fuels, but many of them are limited by low efficiencies due to rapid interfacial back electron transfer. We demonstrate here that a nanowire-structured p-type Si (p-Si) electrode, surface-modified with a perylene-diimide derivative (PDI'), can undergo photoreduction of a surface-bound, water reduction catalyst toward efficient H₂ evolution under a low applied bias. At the electrode interface, the PDI' layer converts green light into high-energy holes at its excited state for extraction of photogenerated electrons at the photoexcited p-Si. The photogenerated electrons at the reduced PDI' are subsequently transferred to the molecular H₂-evolution catalyst. Involvement of the photoexcited PDI' enables effective redox separation between the electrons at the reduced catalyst and the holes at the valence band of p-Si. The heterojunction photocathode was used in a tandem cell by coupling with a dye-sensitized photoanode for solar-driven water splitting into H₂ and O₂.