Photosystem I‐based Biophotovoltaics on Nanostructured Hematite

The electronic coupling between a robust red algal photosystem I (PSI) associated with its light harvesting antenna (LHCI) and nanocrystalline n‐type semiconductors, TiO₂ and hematite (α‐Fe₂O₃) is utilized for fabrication of the biohybrid dye‐sensitized solar cells (DSSC). PSI‐LHCI is immobilized as a structured multilayer over both semiconductors organized as highly ordered nanocrystalline arrays, as evidenced by FE‐SEM and XRD spectroscopy. Of all the biohybrid DSSCs examined, α‐Fe₂O₃/PSI‐LHCI biophotoanode operates at a highest quantum efficiency and generates the largest open circuit photo­current compared to the tandem system based on TiO₂/PSI‐LHCI material. This is accomplished by immobilization of the PSI‐LHCI complex with its reducing side towards the hematite surface and nanostructuring of the PSI‐LHCI multilayer in which the subsequent layers of this complex are organized in the head‐to‐tail orientation. The biohybrid PSI‐LHCI‐DSSC is capable of sustained photoelectrochemical H₂ production upon illumination with visible light above 590 nm. Although the solar conversion efficiency of the PSI‐LHCI/hematite DSSC is currently below a practical use, the system provides a blueprint for a genuinely green solar cell that can be used for molecular hydrogen production at a rate of 744 μmoles H₂ mg Chl⁻¹ h⁻¹, placing it amongst the best performing biohybrid solar‐to‐fuel nanodevices.