Novel Bioelectrocatalytic Strategies Based on Immobilized Redox Metalloenzymes on Tailored Electrodes

Abstract

[EN] The attachment of redox metalloenzymes to electroactive surfaces is of great importance for both fundamental and applied studies. Oriented covalent immobilization of a metalloenzyme on the electrode allows using electrochemical methods for studying its catalytic mechanism by direct electron transfer. Furthermore, redox metalloenzymes specifically catalyze many reactions of great interest in energy conversion process, such as H2 production/oxidation, O2 evolution/reaction and generation of biochemical power within living cells. Therefore, their optimized immobilization on electrodes has potential applications in biofuel cells development, electrochemical and photoelectrochemical cells for water splitting or CO2 valorization, and electroenzymatic systems for cofactor regeneration. In this chapter we review novel strategies that have been developed in the last years by our group and others for tailoring electrodes with the aim of specific, stable and oriented binding of redox metalloenzymes. We focus our review on the strategies designed for three different applications: i) development of efficient oxygen reduction biocathodes; ii) production of hybrid semiconductor/enzyme photoelectrocatalysts; iii) biomimetic reconstitution of membrane enzymes over electrodes.