Abstract
The integration of microbial nitrogen (N(2)) fixation with photochemical processes using inorganic light-absorbing nanomaterials is a burgeoning field in sustainable energy production. Here, we explore the synergistic combination of inorganic semiconductor nanowires (NWs) with whole-cell microorganisms to create an inorganic-bacterial biohybrid system. Specifically, we employ Cu(2)O@TiO(2) NWs with a core/shell structure to harness sunlight and generate photoexcited electrons. Azotobacter vinelandii, serving as a biocatalyst, adsorbs onto these NWs and facilitates the reception of photoexcited electrons, thereby enhancing the efficiency of the photoelectrochemical N(2) fixation reaction (PEC-NRR). The biohybrid system achieves an impressive ammonia (NH(3)) yield of (1.49 ± 0.05) × 10(-9 ) mol s(-1) cm(-2) (5.36 ± 0.18 μmol h(-1) cm(-2)). The enhancement in NH(3) synthesis within the Cu(2)O@TiO(2) NWs/A. vinelandii biohybrid is attributed to the increased concentrations of nicotinamide adenine dinucleotide-hydrogen (NADH) and adenosine 5'-triphosphate (ATP), as well as the overexpression of N(2)-fixing genes like nifH and nifD within the nitrogenase enzyme complex. This study underscores the potential of inorganic-bacterial biohybrid systems in solar-chemical conversion, paving the way for more diverse and functional approaches to harnessing solar energy for sustainable chemical production.