Water Photo-Electrooxidation Using Mats of TiO₂ Nanorods, Surface Sensitized by a Metal–Organic Framework of Nickel and 1,2-Benzene Dicarboxylic Acid

Photoanodes comprising a transparent glass substrate coated with a thin conductive film of fluorine-doped tin oxide (FTO) and a thin layer of a photoactive phase have been fabricated and tested with regard to the photo-electro-oxidation of water into molecular oxygen. The photoactive layer was made of a mat of TiO₂ nanorods (TDNRs) of micrometric thickness. Individual nanorods were successfully photosensitized with nanoparticles of a metal–organic framework (MOF) of nickel and 1,2-benzene dicarboxylic acid (BDCA). Detailed microstructural information was obtained from SEM and TEM analysis. The chemical composition of the active layer was determined by XRD, XPS and FTIR analysis. Optical properties were determined by UV–Vis spectroscopy. The water photooxidation activity was evaluated by linear sweep voltammetry and the robustness was assessed by chrono-amperometry. The OER (oxygen evolution reaction) photo-activity of these photoelectrodes was found to be directly related to the amount of MOF deposited on the TiO₂ nanorods, and was therefore maximized by adjusting the MOF content. The microscopic reaction mechanism which controls the photoactivity of these photoelectrodes was analyzed by photo-electrochemical impedance spectroscopy. Microscopic rate parameters are reported. These results contribute to the development and characterization of MOF-sensitized OER photoanodes.