Covalent Immobilization of Oriented Photosystem II on a Nanostructured Electrode for Solar Water Oxidation

[Image: see text] Photosystem II (PSII) offers a biological and sustainable route of photochemical water oxidation to O(2) and can provide protons and electrons for the generation of solar fuels, such as H(2). We present a rational strategy to electrostatically improve the orientation of PSII from a thermophilic cyanobacterium, Thermosynechococcus elongatus, on a nanostructured indium tin oxide (ITO) electrode and to covalently immobilize PSII on the electrode. The ITO electrode was modified with a self-assembled monolayer (SAM) of phosphonic acid ITO linkers with a dangling carboxylate moiety. The negatively charged carboxylate attracts the positive dipole on the electron acceptor side of PSII via Coulomb interactions. Covalent attachment of PSII in its electrostatically improved orientation to the SAM-modified ITO electrode was accomplished via an amide bond to further enhance red-light-driven, direct electron transfer and stability of the PSII hybrid photoelectrode.