2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Semiconductor-based Photocatalytic Hydrogen Generation

Fujishima and Honda (1972) demonstrated the potential of titanium dioxide (TiO2) semiconductor materials to split water into hydrogen and oxygen in a photo-electrochemical cell. Their work triggered the development of semiconductor photocatalysis for a wide range of environmental and energy applications. One of the most significant scientific and commercial advances to date has been the development of visible light active (VLA) TiO2 photocatalytic materials. In this review, a background on TiO2 structure, properties and electronic properties in photocatalysis is presented. The development of different strategies to modify TiO2 for the utilization of visible light, including non metal and/or metal doping, dye sensitization and coupling semiconductors are discussed. Emphasis is given to the origin of visible light absorption and the reactive oxygen species generated, deduced by physicochemical and photoelectrochemical methods. Various applications of VLA TiO2, in terms of environmental remediation and in particular water treatment, disinfection and air purification, are illustrated. Comprehensive studies on the photocatalytic degradation of contaminants of emerging concern, including endocrine disrupting compounds, pharmaceuticals, pesticides, cyanotoxins and volatile organic compounds, with VLA TiO2 are discussed and compared to conventional UV-activated TiO2 nanomaterials. Recent advances in bacterial disinfection using VLA TiO2 are also reviewed. Issues concerning test protocols for real visible light activity and photocatalytic efficiencies with different light sources have been highlighted.

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A review on the visible light active titanium dioxide photocatalysts for environmental applications

Titanium dioxide (TiO2), as an important semiconductor metal oxide, has been widely investigated in the field of photocatalysis. The properties of TiO2, including its light absorption, charge transport and surface adsorption, are closely related to its defect disorder, which in turn plays a significant role in the photocatalytic performance of TiO2. Among all the defects identified in TiO2, oxygen vacancy is one of the most important and is supposed to be the prevalent defect in many metal oxides, which has been widely investigated both by theoretical calculations and experimental characterizations. Here, we give a short review on the existing strategies for the synthesis of defective TiO2 with oxygen vacancies, and the defect related properties of TiO2 including structural, electronic, optical, dissociative adsorption and reductive properties, which are intimately related to the photocatalytic performance of TiO2. In particular, photocatalytic applications with regard to defective TiO2 are outlined. In addition, we offer some perspectives on the challenge and new direction for future research in this field. We hope that this tutorial minireview would provide some useful contribution to the future design and fabrication of defective semiconductor-based nanomaterials for diverse photocatalytic applications.

Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications

Graphitic carbon nitride (g-C3N4), as an intriguing earth-abundant visible light photocatalyst, possesses a unique two-dimensional structure, excellent chemical stability and tunable electronic structure. Pure g-C3N4 suffers from rapid recombination of photo-generated electron–hole pairs resulting in low photocatalytic activity. Because of the unique electronic structure, the g-C3N4 could act as an eminent candidate for coupling with various functional materials to enhance the performance. According to the discrepancies in the photocatalytic mechanism and process, six primary systems of g-C3N4-based nanocomposites can be classified and summarized: namely, the g-C3N4 based metal-free heterojunction, the g-C3N4/single metal oxide (metal sulfide) heterojunction, g-C3N4/composite oxide, the g-C3N4/halide heterojunction, g-C3N4/noble metal heterostructures, and the g-C3N4 based complex system. Apart from the depiction of the fabrication methods, heterojunction structure and multifunctional application of the g-C3N4-based nanocomposites, we emphasize and elaborate on the underlying mechanisms in the photocatalytic activity enhancement of g-C3N4-based nanocomposites. The unique functions of the p–n junction (semiconductor/semiconductor heterostructures), the Schottky junction (metal/semiconductor heterostructures), the surface plasmon resonance (SPR) effect, photosensitization, superconductivity, etc. are utilized in the photocatalytic processes. Furthermore, the enhanced performance of g-C3N4-based nanocomposites has been widely employed in environmental and energetic applications such as photocatalytic degradation of pollutants, photocatalytic hydrogen generation, carbon dioxide reduction, disinfection, and supercapacitors. This critical review ends with a summary and some perspectives on the challenges and new directions in exploring g-C3N4-based advanced nanomaterials.

Graphitic carbon nitride based nanocomposites: a review

Nitrogen-doped titanium dioxide as visible-light-sensitive photocatalyst: designs, developments, and prospects.

The polyaniline (PANI)/TiO2 nanocomposites have been successfully synthesized via a hydrothermal method and followed by a low-temperature calcination treatment process. We find that such a PANI/TiO2 nanocomposite exhibits higher photocatalytic activity and stability than bare TiO2 and TiO2-xNx toward the liquid-phase degradation of methyl orange (MO) under both UV and visible light (420 nm < λ < 800 nm) irradiation. More noteworthy, the PANI/TiO2 photocatalyst still perform good activity toward MO and 4-chlorophenol (4-CP) under the longer wavelength of light (550 nm < λ < 800 nm). The total organic carbon (TOC) tests show that the mineralization rate of MO and 4-CP over PANI/TiO2 are apparently higher than bare TiO2 under the irradiation of both UV and visible light. The presence of synergic effect between PANI and TiO2 is believed to play an essential role in affecting the photoreactivity. At last, the roles of active species in the photocatalytic process are compared by using different types of active ...

Highly Efficient Photocatalytic Degradation of Organic Pollutants by PANI-Modified TiO2 Composite

Active species such as holes, electrons, hydroxyl radicals (•OH), and superoxide radicals (O2•–) involved in the photodegradation process of methyl orange (MO) over TiO2 photocatalyst were detected by several techniques. Using different types of active species scavengers, the results showed that the MO oxidation was driven mainly by the participation of O2•–, holes and •OH radicals. Characterized by the liquid chromatography/mass spectrometry, the transversion of the degradation products with the light irradiation time was first analyzed. Combined with the measurement of oxidation reduction potential, dissolved oxygen, conductivity, and pH values, the degradation process of MO on TiO2 under the effect of the active species was revealed. This was the first time that electrodes were introduced to track the degradation process in situ, and these parameters would be helpful to explain the degradation processes of other organic pollutants.

Evidence for the Active Species Involved in the Photodegradation Process of Methyl Orange on TiO2

Porous ZnIn2S4 microspheres have been successfully synthesized by means of a facile thermal solution method at 353 K. This method was a simple route that involved low temperature, no templates, no catalysts, no surfactants, or organic solvents. Scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, nitrogen sorption analysis, and a UV-vis spectrophotometer were used to characterize the products. The results demonstrated that the microspheres, which were composed of many ZnIn2S4 single crystal nanosheets, underwent the Oswald ripening and self-assembly processes. A morphology formation mechanism has been proposed and discussed. The porous ZnIn2S4 product showed an enhancing visible-light photocatalytic activity for methyl orange degradation. The as-grown architectures may have potential applications in solar energy conversion, environmental remediation, and advanced optical/electric nanodevices.

Low-temperature and template-free synthesis of ZnIn2S4 microspheres.

Great efforts have been made to develop efficient visible light activated photocatalysts in recent years. In this work, Ag 3 VO 4 /TiO 2 /graphene nanocomposite as a wide spectrum responsive photocatalyst was prepared first by a two-step process, which exhibited obviously increased visible light absorption and photocatalytic activity in degradation of organic pollutants including methyl orange and Rhodamine B, compared with Ag 3 VO 4 /TiO 2 and TiO 2 /GR nanocomposites. For Ag 3 VO 4 /TiO 2 /graphene nanocomposite, the introduction of graphene contributed to the uniform dispersion of Ag 3 VO 4 and TiO 2 nanoparticles on graphene sheets. The capacity of graphene in storing and shuttling electrons and the formation of heterojunction between Ag 3 VO 4 and TiO 2 facilitated together the enhancement of efficiency in the separation of photogenerated electron–hole pairs. Based on the results of photoelectrochemical measurement and the detection of active species in photocatalytic degradation process, the transfer of photogenerated carriers and photocatalytic degradation mechanism on Ag 3 VO 4 /TiO 2 /graphene nanocomposite were proposed and discussed in detail.

A high efficient photocatalyst Ag3VO4/TiO2/graphene nanocomposite with wide spectral response

In order to exploit efficient photosensitizers with appropriate electronic states to enhance the transfer of electrons, ZnxCd1-xS/TiO2 nanocomposites were first synthesized by a simple hydrothermal method. The samples were characterized by X-ray diffraction, transmission electron microscopy, diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, electron spin resonance, and photoluminescence techniques. The results showed that the composite of the two inorganic semiconductors largely enhanced the photosensitized degradation of rhodamine B (RhB) under visible light irradiation (420 nm<λ<800 nm). These photocatalytic reactions were driven mainly by the light absorption of RhB molecules and to a lesser extent by the excitation of ZnxCd1-xS. They were supposed to arise mainly from the electron transferred from the adsorbed dye in its singlet excited state to the conduction band of ZnxCd1-xS and TiO2. Such a heterogeneous photocatalytic reaction has much significance in the degradation of organic pollutants in ordinary photocatalysis.

Wenjuan Li

Papers

Highly Efficient Photocatalytic Degradation of Organic Pollutants by PANI-Modified TiO2 Composite

Evidence for the Active Species Involved in the Photodegradation Process of Methyl Orange on TiO2

Low-temperature and template-free synthesis of ZnIn2S4 microspheres.

A high efficient photocatalyst Ag3VO4/TiO2/graphene nanocomposite with wide spectral response

Novel approach to enhance photosensitized degradation of rhodamine B under visible light irradiation by the ZnxCd1-xS/TiO2 nanocomposites.