Photoelectrochemical (PEC) water splitting is a promising strategy to improve the efficiency of oxygen evolution reactions (OERs). However, the efficient adsorption of visible light as well as long-term stability of light-harvesting electrocatalysis is the crucial issue in PEC cells. Metal–organic framework (MOF)-derived bimetallic electrocatalysis with its superior performance has wide application prospects in OER and PEC applications. Herein, we have fabricated a nickel and iron bimetallic organic framework (FeNi-MOF) deposited on top of anodized TiO₂ nanotube arrays (TNTA) for PEC and OER applications. The FeNi-MOF/TNTA was incorporated through the electrochemical deposition of Ni²⁺ and Fe³⁺ onto the surface of TNTA and then connected with organic ligands by the hydrothermal transformation. Therefore, FeNi-MOF/TNTA demonstrates abundant photoelectrocatalytic active sites that can enhance the photocurrent up to 1.91 mA/cm² under 100 mW/cm² and a negligible loss in activity after 180 min of photoreaction. The FeNi-MOF-doped photoanode shows predominant photoelectrochemical performance due to the boosted excellent light-harvesting ability, rapid photoresponse, and stimulated interfacial energy of charge separation under the UV-visible light irradiation conditions. The results of this study give deep insight into MOF-derived bimetallic nanomaterial synthesis for photoelectrochemical OER and provide guidance on future electrocatalysis design.

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.