Bioelectrocatalysis as the basis for the design of enzyme-based biofuel cells and semi-artificial biophotoelectrodes


Bioelectrocatalysis provides access to sustainable and highly efficient technological applications. However, several limitations related either to the intrinsic properties of the biocatalyst or to technical difficulties still hamper or even prevent the integration of such devices into technologically relevant large-scale processes. In this Review, we challenge the common viewpoint suggesting biology-based catalytic systems as a promising approach for the provision of sustainable stored energy and discuss the status of bioelectrocatalytic devices developed for energy conversion. In particular, we focus on two major research areas in the field, that is, H2-powered hydrogenase-based biofuel cells and biophotoelectrodes for solar energy harvesting. We identify the main limitations that have to be addressed to gain access to applied large-scale bio-based and bio-inspired advanced energy conversion systems. Moreover, we show recent examples and milestones that are paving the way towards potential realization of these technologies by overcoming existing limiting factors.

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Fig. 1: Redox proteins and redox active cofactors.

panel a reproduced from ref. 34, Wiley, under a Creative Commons license CC BY 4.0

Fig. 2: Photoactive protein complexes for integration in biophotoelectrodes.
Fig. 3: Protection and reactivation of hydrogenases.

panels a and b reproduced from ref. 50, Springer Nature Ltd; and panels c and d adapted from ref. 53, Springer Nature Ltd.

Fig. 4: Hydrogenase-based gas diffusion electrodes.

panel a reproduced from ref. 58, Wiley; panel b reproduced from ref. 62, Elsevier; and panels c and d reproduced from ref. 64, Springer Nature Ltd, under a Creative Commons license CC BY 4.0

Fig. 5: Synthesis of artificial enzymes.

panel a reproduced from ref. 76, Wiley; and panel b reproduced from ref. 71, RSC

Fig. 6: High surface area biophotoanodes for bias-free solar driven water splitting.

panels ac reproduced from ref. 88, RSC, under a Creative Commons license CC BY 3.0; and panel d reproduced from ref. 43, Springer Nature Ltd

Fig. 7: Reconstitution of a photoactive protein complex.

reproduced from ref. 94, Elsevier


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This work was supported by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) within the framework of the Cluster of Excellence RESOLV (EXC-2033; project number 390677874).

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Ruff, A., Conzuelo, F. & Schuhmann, W. Bioelectrocatalysis as the basis for the design of enzyme-based biofuel cells and semi-artificial biophotoelectrodes. Nat Catal 3, 214–224 (2020).

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