QM/MM Molecular Modeling and Marcus Theory in the Molecular Design of Electrodes for Enzymatic Fuel Cells

New and environmentally friendly technologies are needed for the fabrication of small devices able to produce electricity for biomedical and electronic applications. Enzymatic fuel cells are promising devices for micropower sources operating under mild conditions. The electron transfer (ET) between the redox‐active site of the protein and the electrode surface is a key issue that should be considered in the design of enzymatic fuel cells. The rational molecular design and the optimization of direct ET is still a challenging goal in the bioelectrochemical field. This review discusses the use of Marcus theory and hybrid quantum mechanics/molecular mechanics (QM/MM) modeling techniques to describe and predict the intramolecular ET between enzymes and electrode surfaces for the design of more efficient enzymatic electrodes and enzymatic fuel cells.