Self-cleaning applications of TiO₂ by photo-induced hydrophilicity and photocatalysis

Self-cleaning materials have gained considerable attention for both their unique properties and practical applications in energy and environmental areas. Recent examples of many TiO₂-derived materials have been illustrated to understand the fundamental principles of self-cleaning hydrophilic and hydrophobic surfaces. Various models including those proposed by Wenzel, Cassie-Baxter and Miwa-Hashimoto are discussed to explain the mechanism of self-cleaning. Examples of semiconductor surfaces exhibiting the simultaneous occurrence of superhydrophilic and superhydrophobic domains on the same surface are illustrated, which can have various advanced applications in microfluidics, printing, photovoltaic, biomedical devices, anti-bacterial surfaces and water purification. Several strategies to improve the efficiency of photocatalytic self-cleaning property have been discussed including doping with metals and non-metals, formation of hetero-junctions between TiO₂ and other low bandgap semiconductors, and fabrication of graphene based semiconductor nano-composites. Different mechanisms such as band-gap narrowing, formation of localized energy levels within the bandgap and formation of intrinsic defects such as oxygen vacancies have been suggested to account for the improved activity of doped TiO₂ photocatalysts_. Various preparation routes for developing efficient superhydrophilic-superhydrophobic patterns have been reviewed. In addition, reversible photo-controlled surfaces with tuneable hydrophilic/hydrophobic properties and its technological applications are discussed. Examples of antireflective surfaces exhibiting self-cleaning properties for the applications in solar cells and flat panel displays have also been provided. Discussion is provided on TiO₂ based self-cleaning materials exhibiting hydrophilic and underwater superoleophobic properties and their utilities in water management, antifouling applications and separation of oil in water emulsions are discussed. In addition, ISO testing methods (ISO 27448: 2009, ISO 10678: 2010 and ISO 27447: 2009) for analysing self-cleaning activity and antibacterial action have also been discussed. Rapid photocatalytic self-cleaning testing methods using various photocatalytic activity indicator inks such as resazurin (Rz), basic blue 66 (BB66) and acid violet 7(AV7) for a broad range of materials such as commercial paints, tiles and glasses are also described. Various commercial products such as glass, tiles, fabrics, cement and paint materials developed based on the principle of photo-induced hydrophilic conversion of TiO₂ surfaces have also been provided. The wide ranges of practical applications of self-cleaning photocatalytic materials suggest further development to improve their efficiency and utilities. It was concluded that a rational fabrication of multifunctional photocatalytic materials by integrating biological inspired structures with tunable wettability would be favorable to address a number of existing environmental concerns.