The surface functionalization of TiO₂-based materials with alkylsilanes is attractive in several cutting-edge applications, such as photovoltaics, sensors, and nanocarriers for the controlled release of bioactive molecules. (3-Aminopropyl)triethoxysilane (APTES) is able to self-assemble to form monolayers on TiO₂ surfaces, but its adsorption geometry and solar-induced photodegradation pathways are not well understood. We here employ advanced experimental (XPS, NEXAFS, AFM, HR-TEM, and FT-IR) and theoretical (plane-wave DFT) tools to investigate the preferential interaction mode of APTES on anatase TiO₂. We demonstrate that monomeric APTES chemisorption should proceed through covalent Si–O–Ti bonds. Although dimerization of the silane through Si–O–Si bonds is possible, further polymerization on the surface is scarcely probable. Terminal amino groups are expected to be partially involved in strong charge-assisted hydrogen bonds with surface hydroxyl groups of TiO₂, resulting in a reduced propensity to react with other species. Solar-induced mineralization proceeds through preferential cleavage of the alkyl groups, leading to the rapid loss of the terminal NH₂ moieties, whereas the Si-bearing head of APTES undergoes slower oxidation and remains bound to the surface. The suitability of employing the silane as a linker with other chemical species is discussed in the context of controlled degradation of APTES monolayers for drug release and surface patterning.

Recently, we have witnessed a booming development of composites and multi-dopant metal oxides to be employed as novel photocatalysts. Yet the practical application of photocatalysis for environmental purposes is still elusive. Concerns about the unknown fate and toxicity of nanoparticles, unsatisfactory performance in real conditions, mass transfer limitations and durability issues have so far discouraged investments in full-scale applications of photocatalysis. Herein, we provide a critical overview of the main challenges that are limiting large-scale application of photocatalysis in air and water/wastewater purification. We then discuss the main approaches reported in the literature to tackle these shortcomings, such as the design of photocatalytic reactors that retain the photocatalyst, the study of degradation of micropollutants in different water matrices, and the development of gas-phase reactors with optimized contact time and irradiation. Furthermore, we provide a critical analysis of research–practice gaps such as treatment of real water and air samples, degradation of pollutants with actual environmental concentrations, photocatalyst deactivation, and cost and environmental life-cycle assessment.