Sporomusa ovata, a typical electroautotrophic microorganism, has been utilized in bioelectrosynthesis for carbon dioxide fixation to multicarbon organic chemicals. However, additional photovoltaic devices are normally needed to convert photo energy to electric energy to power the carbon dioxide fixation, which restricts the overall energy conversion efficiency. Herein, we report Sporomusa ovata−CdS biohybrids for artificial photosynthesis driven by light without any other power source. The quantum yield can reach 16.8 ± 9%, and the active duration time of the system can last for 5 days. During the artificial photosynthesis, carbon dioxide is first reduced to formate and finally converted to acetate via the Wood−Ljungdahl pathway. The carbon dioxide fixation, electron transfer, energy metabolism, and reactive oxygen species damage repair processes in the biohybrid system were characterized by proteomic analysis. Key enzymes, e.g., flavoprotein, ferredoxin, formate-tetrahydrofolate ligase, 5-methyltetrahydrofolate:corrinoid iron−sulfur protein methyltransferase, thioredoxin, and rubrerythrin, were found up-regulated in the biohybrid system. The findings are helpful in understanding the mechanism of the artificial photosynthesis and useful for the development of new biohybrid systems using genetically engineered microbes in the future. The study is expected to boost the development of bioabiotic hybrid system in solar energy harvest.

By simulating natural photosynthesis, the desirable high-value chemical products and clean fuels can be sustainably generated with solar energy. Whole-cell-based photosensitized biohybrid system, which innovatively couples the excellent light-harvesting capacity of semiconductor materials with the efficient catalytic ability of intracellular biocatalysts, is an appealing interdisciplinary creature to realize photodriven chemical synthesis. In this review, we summarize the constructed whole-cell-based biohybrid systems in different application fields, including carbon dioxide fixation, nitrogen fixation, hydrogen production, and other chemical synthesis. Moreover, we elaborate the charge transfer mechanism studies of representative biohybrids, which can help to deepen the current understanding of the synergistic process between photosensitizers and microorganisms, and provide schemes for building novel biohybrids with less electron transfer resistance, advanced productive efficiency, and functional diversity. Further exploration in this field has the prospect of making a breakthrough on the biotic–abiotic interface that will provide opportunities for multidisciplinary research.