Photoinduced reactivity of titanium dioxide

Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy

The photocatalytic degradation of azo dyes containing different functionalities has been reviewed using TiO2 as photocatalyst in aqueous solution under solar and UV irradiation. The mechanism of the photodegradation depends on the radiation used. Charge injection mechanism takes place under visible radiation whereas charge separation occurred under UV light radiation. The process is monitored by following either the decolorization rate and the formation of its end-products. Kinetic analyses indicate that the photodegradation rates of azo dyes can usually be approximated as pseudo-first-order kinetics for both degradation mechanisms, according to the Langmuir–Hinshelwood model. The degradation of dyes depend on several parameters such as pH, catalyst concentration, substrate concentration and the presence of electron acceptors such as hydrogen peroxide and ammonium persulphate besides molecular oxygen. The presence of other substances such as inorganic ions, humic acids and solvents commonly found in textile effluents is also discussed. The photocatalyzed degradation of pesticides does not occur instantaneously to form carbon dioxide, but through the formation of long-lived intermediate species. Thus, the study focuses also on the determination of the nature of the principal organic intermediates and the evolution of the mineralization as well as on the degradation pathways followed during the process. Major identified intermediates are hydroxylated derivatives, aromatic amines, naphthoquinone, phenolic compounds and several organic acids. By-products evaluation and toxicity measurements are the key-actions in order to assess the overall process.

TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations A review

Semiconductor-mediated photocatalysis has received tremendous attention as it holds great promise to address the worldwide energy and environmental issues. To overcome the serious drawbacks of fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, many strategies have been developed in the past few decades and the most widely used one is to develop photocatalytic heterojunctions. This review attempts to summarize the recent progress in the rational design and fabrication of heterojunction photocatalysts, such as the semiconductor–semiconductor heterojunction, the semiconductor–metal heterojunction, the semiconductor–carbon heterojunction and the multicomponent heterojunction. The photocatalytic properties of the four junction systems are also discussed in relation to the environmental and energy applications, such as degradation of pollutants, hydrogen generation and photocatalytic disinfection. This tutorial review ends with a summary and some perspectives on the challenges and new directions in this exciting and still emerging area of research.

Semiconductor heterojunction photocatalysts: design, construction, and photocatalytic performances

Optical generation of hot electrons in metallic structures and its potential as an alternative to conventional electron–hole separation in semiconductor devices are reviewed. The possibilities for realizing high conversion efficiencies with low fabrication costs are discussed along with challenges in terms of the materials, architectures and fabrication methods

Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices

Ag/AgBr/TiO2 was prepared by the deposition-precipitation method and was found to be a novel visible light driven photocatalyst. The catalyst showed high efficiency for the degradation of nonbiodegradable azodyes and the killing of Escherichia coli under visible light irradiation (lambda>420 nm). The catalyst activity was maintained effectively after successive cyclic experiments under UV or visible light irradiation without the destruction of AgBr. On the basis of the characterization of X-ray diffraction, X-ray photoelectron spectroscopy, and Auger electron spectroscopy, the surface Ag species mainly exist as Ag0 in the structure of all samples before and after reaction, and Ag0 species scavenged hVB+ and then trapped eCB- in the process of photocatalytic reaction, inhibiting the decomposition of AgBr. The studies of ESR and H2O2 formation revealed that *OH and O2*- were formed in visible light irradiated aqueous Ag/AgBr/TiO2 suspension, while there was no reactive oxygen species in the visible light irradiated Ag0/TiO2 system. The results indicate that AgBr is the main photoactive species for the destruction of azodyes and bacteria under visible light. In addition, the bactericidal efficiency and killing mechanism of Ag/AgBr/TiO2 under visible light irradiation are illustrated and discussed.

Ag/AgBr/TiO2 visible light photocatalyst for destruction of azodyes and bacteria

A plasmonic photocatalyst Ag−AgI supported on mesoporous alumina (Ag−AgI/Al2O3) was prepared by deposition−precipitation and photoreduction methods. The catalyst showed high and stable photocatalytic activity for the degradation and mineralization of toxic persistent organic pollutants, as demonstrated with 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), and trichlorophenol (TCP) under visible light or simulated solar light irradiation. On the basis of electron spin resonance, cyclic voltammetry analyses under a variety of experimental conditions, two electron transfer processes were verified from the excited Ag NPs to AgI and from 2-CP to the Ag NPs, and the main active species of O2•− and excited h+ on Ag NPs were involved in the photoreaction system of Ag−AgI/Al2O3. A plasmon-induced photocatalytic mechanism was proposed. Accordingly, the plasmon-induced electron transfer processes elucidated the photostability of Ag−AgI/Al2O3. This finding indicates that the high photosensitivity of noble metal N...

Plasmon-Induced Photodegradation of Toxic Pollutants with Ag−AgI/Al2O3 under Visible-Light Irradiation

Oxygen-doped graphitic carbon nitride (O-CN) was fabricated via a facile thermal polymerization method using urea and oxalic acid dihydrate as the graphitic carbon nitride precursor and oxygen source, respectively. Experimental and theoretical results revealed that oxygen doping preferentially occurred on the two-coordinated nitrogen positions, which create the formation of low and high electron density areas resulting in the electronic structure modulation of O-CN. As a result, the resultant O-CN exhibits enhanced catalytic activity and excellent long-term stability for peroxymonosulfate (PMS) activation toward the degradation of organic pollutants. The O-CN with modulated electronic structure enables PMS oxidation over the electron-deficient C atoms for the generation of singlet oxygen (1O2) and PMS reduction around the electron-rich O dopants for the formation of hydroxyl radical (•OH) and sulfate radical (SO4•-), in which 1O2 is the major reactive oxygen species, contributing to the selective reactivity of the O-CN/PMS system. Our findings not only propose a novel PMS activation mechanism in terms of simultaneous PMS oxidation and reduction for the production of nonradical and radical species but also provide a valuable insight for the development of efficient metal-free catalysts through nonmetal doping toward the persulfate-based environmental cleanup.

Electronic Structure Modulation of Graphitic Carbon Nitride by Oxygen Doping for Enhanced Catalytic Degradation of Organic Pollutants through Peroxymonosulfate Activation.

Chun Hu

Papers

Ag/AgBr/TiO2 visible light photocatalyst for destruction of azodyes and bacteria

Plasmon-Induced Photodegradation of Toxic Pollutants with Ag−AgI/Al2O3 under Visible-Light Irradiation

Electronic Structure Modulation of Graphitic Carbon Nitride by Oxygen Doping for Enhanced Catalytic Degradation of Organic Pollutants through Peroxymonosulfate Activation.

Degradation of Acid Orange 7 using magnetic AgBr under visible light: the roles of oxidizing species.

Removal of phosphate by mesoporous ZrO2.