This review presents a comprehensive summary of the material-microorganism interface in microbial hybrid electrocatalysis systems. Microbial hybrid electrocatalysis has been developed to combine the advantages of inorganic electrocatalysis and microbial catalysis. However, electron transfer at the interfaces between microorganisms and materials is a very critical issue that affects the efficiency of the system. Therefore, this review focuses on the electron transfer at the material-microorganism interface and the strategies for building efficient microorganism and material interfaces. We begin with a brief introduction of the electron transfer mechanism in both the bioanode and biocathode of bioelectrochemical systems to understand the material-microorganism interface. Next, we summarise the strategies for constructing efficient material-microorganism interfaces including material design and modification and bacterial engineering. We also discuss emerging studies on the bio-inorganic hybrid electrocatalysis system. Understanding the interface between electrode/active materials and the microorganisms, especially the electron transfer processes, could help to drive the evolution of material-microorganism hybrid electrocatalysis systems towards maturity.
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