Recent advances in surface chemistry of electrodes to promote direct enzymatic bioelectrocatalysis

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Abstract Redox enzymes catalyze major reactions in microorganisms to supply energy for life. Their use in electrochemical biodevices requires their integration on electrodes, while maintaining their activity and optimizing their stability. In return, such applicative development puts forward the knowledge on involved catalytic mechanisms, providing a direct electrode connection of the enzyme is fulfilled. Enzymes being large molecules with active site embedded in an insulating moiety, direct bioelectrocatalysis supposes strategies for specific orientation of the enzyme to be developed. In this review, we summarize recent advances during the past 3 years in the chemical modification of electrodes favoring direct electrocatalysis. We present the different methodologies used according to the electrode materials, including metals, carbon-based electrodes, or porous structures and discuss the gained insights into bioelectrocatalysis. We especially focus on enzyme engineering, which appears as an emerging strategy for enzyme anchoring. Remaining challenges will be discussed with regard to these later findings.