A Decaheme Cytochrome as a Molecular Electron Conduit in Dye‐Sensitized Photoanodes

In nature, charge recombination in light‐harvesting reaction centers is minimized by efficient charge separation. Here, it is aimed to mimic this by coupling dye‐sensitized TiO₂ nanocrystals to a decaheme protein, MtrC from Shewanella oneidensis MR‐1, where the 10 hemes of MtrC form a ≈7‐nm‐long molecular wire between the TiO₂ and the underlying electrode. The system is assembled by forming a densely packed MtrC film on an ultra‐flat gold electrode, followed by the adsorption of approximately 7 nm TiO₂ nanocrystals that are modified with a phosphonated bipyridine Ru(II) dye (RuP). The step‐by‐step construction of the MtrC/TiO₂ system is monitored with (photo)electrochemistry, quartz‐crystal microbalance with dissipation (QCM‐D), and atomic force microscopy (AFM). Photocurrents are dependent on the redox state of the MtrC, confirming that electrons are transferred from the TiO₂ nanocrystals to the surface via the MtrC conduit. In other words, in these TiO₂/MtrC hybrid photodiodes, MtrC traps the conduction‐band electrons from TiO₂ before transferring them to the electrode, creating a photobioelectrochemical system in which a redox protein is used to mimic the efficient charge separation found in biological photosystems.