TiO 2 photocatalysis is widely used in a variety of applications and products in the environmental and energy fields, including self-cleaning surfaces, air and water purification systems, sterilization, hydrogen evolution, and photoelectrochemical conversion. The development of new materials, however, is strongly required to provide enhanced performances with respect to the photocatalytic properties and to find new uses for TiO 2 photocatalysis. In this review, recent developments in the area of TiO 2 photocatalysis research, in terms of new materials from a structural design perspective, have been summarized. The dimensionality associated with the structure of a TiO 2 material can affect its properties and functions, including its photocatalytic performance, and also more specifically its surface area, adsorption, reflectance, adhesion, and carrier transportation properties. We provide a brief introduction to the current situation in TiO 2 photocatalysis, and describe structurally controlled TiO 2 photocatalysts which can be classified into zero-, one-, two-, and three-dimensional structures. Furthermore, novel applications of TiO 2 surfaces for the fabrication of wettability patterns and for printing are discussed.

TiO2 photocatalysis: Design and applications

Design, and Applications Shutao Wang,†,‡ Kesong Liu, Xi Yao, and Lei Jiang*,†,‡,§ †Laboratory of Bio-inspired Smart Interface Science, Technical Institute of Physics and Chemistry, and ‡Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People’s Republic of China Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry and Environment, BeiHang University, Beijing 100191, People’s Republic of China Department of Biomedical Sciences, City University of Hong Kong, Hong Kong P6903, People’s Republic of China

Bioinspired Surfaces with Superwettability: New Insight on Theory, Design, and Applications

Mimicking natural superhydrophobic surfaces and grasping the wetting process: A review on recent progress in preparing superhydrophobic surfaces

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.

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Self-Cleaning Applications of TiO2 by Photo-Induced Hydrophilicity and Photocatalysis

The term superhydrophilicity is only 11–12 years old and was introduced just after the explosion of research on superhydrophobic surfaces, in response to the demand for surfaces and coatings with exceptionally strong affinity to water. The definition of superhydrophilic substrates has not been clarified yet, and unrestricted use of this term to hydrophilic surfaces has stirred controversy in the last few years in the surface chemistry community. In this review, we take a close look into major definitions of hydrophilic surfaces used in the past, before we review the physics behind the superhydrophilic phenomenon and make recommendation on defining superhydrophilic surfaces and coatings. We also review chemical and physical methods used in the fabrication of substrates on surfaces of which water spreads completely. Several applications of superhydrophilic surfaces, including examples from the authors' own research, conclude this review.

Hydrophilic and superhydrophilic surfaces and materials

A simple electrochemical and self-assembly method was adopted for the fabrication of superhydrophobic spongelike nanostructured TiO2 surfaces with markedly controllable adhesion. Water adhesion ranging from ultralow (5.0 μN) to very high (76.6 μN) can be tuned through adjusting the nitro cellulose dosage concentrations. The detailed experiments and analyses have indicated that the significant increase of adhesion by introducing nitrocellulose is ascribed to the combination of hydrogen bonding between the nitro groups and the hydroxyl groups at the solid/liquid interfaces and the disruption of the densely packed hydrophobic 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PTES) molecule. A mechanism has been proposed to explain the formation of superhydrophobic TiO2 films with distinct adhesion.

Jianying Huang

Papers

Markedly Controllable Adhesion of Superhydrophobic Spongelike Nanostructure TiO2 Films

Superhydrophilic-superhydrophobic micropattern on TiO2 nanotube films by photocatalytic lithography