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.
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