Interfacial Charge Transfer Complexes in TiO₂-Enediol Hybrids Synthesized by Sol-Gel

Metal oxide-organic hybrid semiconductors exhibit specific properties depending not only on their composition but also on the synthesis procedure, and particularly on the functionalization method, determining the interaction between the two components. Surface adsorption is the most common way to prepare organic-modified metal oxides. Here a simple sol-gel route is described as an alternative, finely controlled strategy to synthesize titanium oxide-based materials containing organic molecules coordinated to the metal. The effect of the molecular structure of the ligands on the surface properties of the hybrids is studied using three enediols able to form charge transfer complexes: catechol, dopamine, and ascorbic acid. For each system, the process conditions driving the transition from the sol to chemical, physical, or particulate gels are explored. The structural, optical, and photoelectrochemical characterization of the amorphous hybrid materials shows analogies and differences related to the organic component. In particular, electron paramagnetic resonance (EPR) spectroscopy at room temperature reveals the presence of organic radical species with different evolution and stability, and photocurrent measurements prove the effective photosensitization of TiO₂ in the visible range induced by interfacial ligand-to-metal charge transfer.