W.J.R. Song, Glenn Quek, Marion I. M. Short, Weiqi Li, Erwin Reisner, Bin Liu
Integrating semiconductors with microorganisms is attracting significant attention as a sustainable platform for solar-to-chemical conversion. This semibiological design combines the excellent light harvesting ability of semiconductor materials with intracellular biocatalytic pathways to enable efficient solar energy conversion into complex products with high selectivity. However, the effectiveness of this interdisciplinary biohybrid approach relies on a complex interfacial biotic-abiotic interaction, and it remains challenging to construct efficient and stable microbe-semiconductor systems for practical applications. In this review, we provide a systematic overview of the fundamental mechanisms behind microbe-semiconductor systems with an emphasis on interfacial electron transfer and highlight recent advancements in the assembly of biohybrids for solar-driven biosynthesis using nonphotosynthetic bacteria. First, we provide a comprehensive introduction of semibiological photosynthesis with an emphasis on extracellular electron transfer at the biotic-abiotic interfaces. Then, we discuss the engineering of biohybrid interfaces, the characterization of microbe-semiconductor interfacial electron transfer, and their deployment in solar-to-chemical conversion. We conclude by exploring the challenges in developing and optimizing biotic-abiotic interfaces as well as providing an outlook for potential future innovations. This review therefore presents the basic principles and provides guidance for the development of semibiological photosynthetic systems.