Photosynthetic Biohybrid System for Enhanced Abiotic N₂-to-NH₃ Conversion under Ambient Conditions

Photosynthetic biohybrid systems (PBSs) offer an eco-friendly approach to transforming solar energy into value-added products by integrating biological entities with inorganic semiconductors. However, the chemical conversion capacity of most PBSs has inherent limitations, as whole-cell bacteria and isolated enzymes require fine-tuning of environmental conditions. Here, we report a new PBS developed by introducing free-standing ceria nanoparticles into the purple membrane (PM) of Halobacterium salinarum archaea, which can unidirectionally transfer charge carriers in response to incident photons, even after separation from living archaea at various conditions. Our microscopy, spectroscopy, and synchrotron X-ray scattering analyses confirm that the electrostatic assembly between ceria and PM creates seamless interfacial contact, thereby enhancing the photocatalytic capacity of ceria. Although the conversion of dinitrogen (N₂) to ammonia (NH₃) is thermodynamically challenging due to the triple bond in N₂ and a series of charge-transfer reactions, our PM-ceria (PMC) hybrid nanoparticle efficiently produces NH₃ by reducing N₂ using solar energy even under atmospheric pressure and room temperature while simultaneously converting glycerol into value-added derivatives. Additionally, our PMC nanoparticle involves neither toxic/precious metals nor bioengineering processes to achieve enhanced photocatalytic N₂-to-NH₃ conversion. This study sheds light on the new aspect of PBSs by employing PM to potentially resolve the global energy and environmental challenges posed by the conventional Haber-Bosch process.