De Novo Approach to Encapsulating Biocatalysts into Synthetic Matrixes: From Enzymes to Microbial Electrocatalysts

Biocatalysts hold great promise in chemical and electrochemical reactions. However, biocatalysts are prone to inhospitable physiochemical conditions. Encapsulating biocatalysts into a synthetic host matrix can improve their stability and activity, and broaden their operational conditions. In this Review, we summarize the emerging de novo approaches to encapsulating biocatalysts into synthetic matrixes. Here, de novo means that embedding of biocatalysts and construction of matrixes take place simultaneously. We discuss the advantages and limitations of the de novo approach. On the basis of the nature of the biocatalysts and the synthetic frameworks, we specifically focus on two aspects: (1) encapsulation of enzymes (in vitro) in metal–organic frameworks and (2) encapsulation of microbial electrocatalysts (in vivo) on the electrode. For both cases, we discuss how the encapsulation improves biocatalysts' performance (stability, viability, activity, and etc.). We also highlight the benefit of encapsulation in facilitating the transport of charge carriers in microbial electrocatalysis.