Reversing Electron Transfer Chain for Light-Driven Hydrogen Production in Biotic–Abiotic Hybrid Systems

The biotic–abiotic photosynthetic system integrating inorganic light absorbers with whole-cell biocatalysts innovates the way for sustainable solar-driven chemical transformation. Fundamentally, the electron transfer at the biotic–abiotic interface, which may induce biological response to photoexcited electron stimuli, plays an essential role in solar energy conversion. Herein, we selected an electro-active bacterium Shewanella oneidensis MR-1 as a model, which constitutes a hybrid photosynthetic system with a self-assembled CdS semiconductor, to demonstrate unique biotic–abiotic interfacial behavior. The photoexcited electrons from CdS nanoparticles can reverse the extracellular electron transfer (EET) chain within S. oneidensis MR-1, realizing the activation of a bacterial catalytic network with light illumination. As compared with bare S. oneidensis MR-1, a significant upregulation of hydrogen yield (711-fold), ATP, and reducing equivalent (NADH/NAD+) was achieved in the S. oneidensis MR-1-CdS under visible light. This work sheds light on the fundamental mechanism and provides design guidelines for biotic–abiotic photosynthetic systems.