The remarkable achievement by Fujishima and Honda (1972) in the photo-electrochemical water splitting results in the extensive use of TiO 2 nanomaterials for environmental purification and energy storage/conversion applications. Though there are many advantages for the TiO 2 compared to other semiconductor photocatalysts, its band gap of 3.2 eV restrains application to the UV-region of the electromagnetic spectrum ( λ  ≤ 387.5 nm). As a result, development of visible-light active titanium dioxide is one of the key challenges in the field of semiconductor photocatalysis. In this review, advances in the strategies for the visible light activation, origin of visible-light activity, and electronic structure of various visible-light active TiO 2 photocatalysts are discussed in detail. It has also been shown that if appropriate models are used, the theoretical insights can successfully be employed to develop novel catalysts to enhance the photocatalytic performance in the visible region. Recent developments in theory and experiments in visible-light induced water splitting, degradation of environmental pollutants, water and air purification and antibacterial applications are also reviewed. Various strategies to identify appropriate dopants for improved visible-light absorption and electron–hole separation to enhance the photocatalytic activity are discussed in detail, and a number of recommendations are also presented.

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Visible-light activation of TiO2 photocatalysts: Advances in theory and experiments

Concerns with the environmental and health risk of widely distributed, commonly used nanoparticles are increasing. Nanosize titanium dioxide (TiO2) is used in air and water remediation and in numerous products designed for direct human use and consumption. Its effectiveness in deactivating pollutants and killing microorganisms relates to photoactivation and the resulting free radical activity. This property, coupled with its multiple potential exposure routes, indicates that nanosize TiO2 could pose a risk to biological targets that are sensitive to oxidative stress damage (e.g., brain). In this study, brain microglia (BV2) were exposed to a physicochemically characterized (i.e., dispersion stability, particle size distribution, and zeta potential) nanomaterial, Degussa P25, and cellular expressions of reactive oxygen species were measured with fluorescent probes. P25's zeta potentials, measured in cell culture media and physiological buffer were -11.6 +/- 1.2 mV and -9.25 +/- 0.73 mV, respectively. P25 aggregation was rapid in both media and buffer with the hydrodynamic diameter of stable P25 aggregates ranging from 826 nm to 2368 nm depending on the concentration. The biological response of BV2 microglia to noncytotoxic (2.5-120 ppm) concentrations of P25 was a rapid (<5 min) and sustained (120 min) release of reactive oxygen species. The time course of this release suggested that P25 not only stimulated the immediate "oxidative burst" response in microglia but also interfered with mitochondrial energy production. Transmission electron microscopy indicated that small groups of nanosized particles and micron-sized aggregates were engulfed bythe microglia and sequestered as intracytoplasmic aggregates after 6 and 18 h exposure to P25 (2.5 ppm). Cell viability was maintained at all test concentrations (2.5-120 ppm) over the 18 h exposure period. These data indicate that mouse microglia respond to Degussa P25 with cellular and morphological expressions of free radical formation.

Titanium Dioxide (P25) Produces Reactive Oxygen Species in Immortalized Brain Microglia (BV2): Implications for Nanoparticle Neurotoxicity†

Magnetic ferrospinel MFe 2 O 4 (M = Co, Cu, Mn, and Zn) prepared in a sol–gel process was introduced as catalyst to generate powerful radicals from peroxymonosulfate (PMS) for refractory di-n-butyl phthalate (DBP) degradation in the water. Various catalysts were described and characterized, and the catalytic activities in PMS oxidation system were investigated. Most important of all, the mechanism of different catalysts in the catalytic PMS solution was illustrated. The results showed that the incorporation of CoFe 2 O 4 had the highest catalytic performance in PMS oxidation for DBP degradation. All catalysts presented favorable recycling and stability in the repeated batch experiment. The catalytic process showed a dependence on initial pH, and an uncharged surface of the catalyst was more profitable for sulfate radical generation. H 2 -TPR and CVs analysis indicated that the sequence of the catalyst's reducibility in PMS solution was CoFe 2 O 4  > CuFe 2 O 4  > MnFe 2 O 4  > ZnFe 2 O 4 , which had a close connection with the activity of metal ion in A site of the catalysts. The surface hydroxyl sites played an important role in the catalytic process, and its quantity determined the degradation of DBP. Moreover, the reactive species in PMS/MFe 2 O 4 system were identified as sulfate radical and hydroxyl radical. The promotion of these radical's reaction was due to the fact that a balance action in the process of M 2+ /M 3+ , O 2− /O 2 , occurred, and at the same time, PMS was catalyzed.

Sulfate radicals induced from peroxymonosulfate by magnetic ferrospinel MFe2O4 (M = Co, Cu, Mn, and Zn) as heterogeneous catalysts in the water

Highly photocatalytically active silver-modified ZnO has been prepared and the effect of silver modification was studied. The structural and optical properties were characterized by X-ray diffraction, Fourier transform IR, differential scanning calorimetry, BET surface area, Raman, UV−vis, and photoluminescence spectroscopy. The photocatalytic activity of these materials was studied by analyzing the degradation of an organic dye, rhodamine 6G (R6G), and it is found that 3 mol % silver-modified ZnO at 400 °C shows approximately four times higher rate of degradation than that of unmodified ZnO and a three times higher rate than that of commercial TiO2 photocatalyst Degussa P-25. It was also noted that the photocatalytic activity for the modified ZnO sample was five times higher than the unmodified sample using sunlight. The effect of silver in enhancing the photocatalytic activity has been studied by analyzing the emission properties of both ZnO and silver-modified ZnO in the presence (emission increases) a...

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A Highly Efficient Ag-ZnO Photocatalyst: Synthesis, Properties, and Mechanism

In the future, solar energy, along with other renewable resources, could play a key role in mass production of fine chemicals. It could also potentially solve environmental problems, as demonstrated by recent developments in the use of solar energy, such as solar photocatalysis. The solar photocatalytic technology has been demonstrated to be effective for: • Treating groundwater, drinking water, industrial wastewater, and air and soil pollution, • Water disinfection, and • Industrial production of fine chemicals. This report summarizes the current status of solar photocatalysis and identifies future opportunities for research and industry in this field, including recent relevant bibliography. The main commercial solar photocatalytic applications are described, included the technologies based on sunlight for antifogging and self-cleaning of coating materials, glass, and concrete. An overview of several different solar photoreactors and the main operating process parameters are also provided. For the estimation of capital costs, it is suggested the use of appropriate “figures of merit”. The present review would be of interest for researchers, technologists, engineers, and industrialists.

Solar photocatalysis: Materials, reactors, some commercial, and pre-industrialized applications. A comprehensive approach

In a previous paper [J. Mater. Sci. 38 (2003) 823] we have described the preparation and characterization of conventional alkoxide sol–gel derived TiO2 films [J. Mater. Sci. 23 (1988) 2259] and of TiO2 powder enriched alkoxide sol–gel derived films. The powder films were prepared on flat stainless steel substrates and on glass beads. These films were characterized for various parameters like particle size, crystal phase, pore size, thickness and mechanical properties. In our current study, the photocatalytic activities of these sol–gel derived TiO2 films were studied utilizing a quartz batch reactor. The quartz batch reactor was characterized for parameters like mixing, recycle, aeration and UV radiation flux, and the TiO2 coated substrates were used as the photocatalyst. The activities of the catalyst films were evaluated by measuring the degradation rate of 4-chlorobenzoic acid used as a model organic pollutant. Immobilized TiO2 powder films on stainless steel containing a mixture of anatase and rutile phases were found to be more effective than films that were substantially composed of anatase phase particles. The activity of glass beads coated with TiO2 powder was compared to the activity of commercially available TiO2 catalyst beads. While the activity of the commercially available TiO2 catalyst beads was higher there was significant attrition of the TiO2 catalyst film. The films on the glass beads possessed better mechanical properties than the commercial catalyst beads and their activity can be significantly improved by optimizing the film synthesis process parameters.

Evaluating the activities of immobilized TiO2 powder films for the photocatalytic degradation of organic contaminants in water

Assisted-photocatalytic degradation of the pesticide precursor 4-chlorobenzoic acid (4-CBA) in water was investigated using different TiO 2 powders and near-UV radiation. Experiments were performed at pH=3.0 and at different TiO 2 loadings, solution ionic strengths, and concentrations of hydrogen peroxide as an oxidant additive. Dark adsorption equilibrium studies revealed that surface area, ionic strength, and catalyst heterogeneity influenced the adsorption capacity and adsorption mechanism. This was attributed to the type and concentration of adsorption sites and the electrostatic interactions in the solution-semiconductor interface. However, the rates of the photocatalytic reactions were not significantly affected by an increase in the ionic strength by a factor of 50. On the other hand, the reaction rate was a strong function of catalyst crystallinity and loading. This suggested that the reactions were mostly controlled by the rate of formation of the oxidizing species rather than the extent of electric double layer (EDL) compression. Addition of hydrogen peroxide up to 248 mg/l resulted in an increase of the reaction rates with a corresponding increase in photonic efficiency by ≈20%. Above this concentration, hydrogen peroxide either did not enhance or caused a significant inhibition of the mineralization rates.

Effect of ionic strength and hydrogen peroxide on the photocatalytic degradation of 4-chlorobenzoic acid in water

The effect of hydrogen peroxide on the photocatalytic degradation of organic contaminants in water was investigated using a TiO2-rotating disk photocatalytic reactor (RDPR) operated in a continuous-mode and at steady state. The experiments were performed at pH 3.0, in the presence of near-UV radiation, and using 4-chlorobenzoic acid (4-CBA) as a model non-volatile organic contaminant at influent concentration of 300 μmol l−1. Experiments were performed at concentrations of hydrogen peroxide in the range 0–10.74 mmol l−1. Addition of hydrogen peroxide at small concentrations (

Effect of hydrogen peroxide on the destruction of organic contaminants-synergism and inhibition in a continuous-mode photocatalytic reactor

Thick films of TiO2 were prepared on glass and stainless steel substrates using an alkoxide sol-gel process modified by addition of Degussa P-25 powder. The prepared films were characterized by SEM, EDS, XRD and other methods. The TiO2 films obtained from the powder modified sol were compared to films obtained from the alkoxide sol-gel without modification. The films obtained from the modified sol-gel were about ten times thicker for a single dip coating/heat treatment cycle than the films obtained from the sol without powder addition. The prepared thick films were smooth and free of macrocracking, fracture or flaking. The grain size of these films was uniform and in the range 100–150 nm and the films were a mixture of anatase and rutile TiO2. The films obtained from the powder modified sol on the stainless steel substrate were also much harder compared to the films obtained from sols without modification and displayed excellent adhesion to the substrate.

Titania powder modified sol-gel process for photocatalytic applications

The photocatalytic degradation of a model non-volatile chlorinated aromatic compound 4-chlorobenzoic acid (4-CBA) was investigated as a function of disk angular velocity, contaminant concentration, and incident light intensity using a rotating disk photocatalytic reactor (RDPR). The study was designed to investigate the effect of all three parameters on the degradation rate as well as their importance on unveiling the existence of mass transfer limitations in the liquid phase under specific conditions. The results showed that the reaction rate increased with disk angular velocity in accordance with a saturation-type dependency. In the range of 2–6 rpm the degradation rate increased almost linearly with disk angular velocity. Above 6 rpm, however, the influence of disk angular velocity was not significant. The initial increase in the reaction rate with disk angular velocity was attributed to the longer time available per rotation resulting in higher down flow of liquid carried by the disk and to the increase in the overall mass transfer coefficient. The rates of 4-CBA acid decomposition and Cl− mineralization at 6 rpm as a function of initial 4-CBA concentration followed Langmuir–Hinshelwood kinetics. At 6 rpm, the rates of 4-CBA degradation followed a linear dependency with incident light intensity. This was attributed to the existence of low local values of incident light intensity on the illuminated disk. With respect to the effect of these three parameters on the degradation rate, the obtained results suggested the absence of significant mass transfer limitations at disk angular velocities higher than 6 rpm. The latter was verified by additional calculations of the Damkohler (Da) number based on dimensionless analysis. The Da number was found to decrease significantly with disk angular velocity and at high disk angular velocities (ω>15 rpm), Da was much lower than 0.1, even when the concentration of the contaminant in the bulk was extremely small (i.e. 1 μmol/l).

Oxidation of organic contaminants in a rotating disk photocatalytic reactor: reaction kinetics in the liquid phase and the role of mass transfer based on the dimensionless Damköhler number

Jean-Michel Laı̂né

Papers

Evaluating the activities of immobilized TiO2 powder films for the photocatalytic degradation of organic contaminants in water

Effect of ionic strength and hydrogen peroxide on the photocatalytic degradation of 4-chlorobenzoic acid in water

Effect of hydrogen peroxide on the destruction of organic contaminants-synergism and inhibition in a continuous-mode photocatalytic reactor

Titania powder modified sol-gel process for photocatalytic applications

Oxidation of organic contaminants in a rotating disk photocatalytic reactor: reaction kinetics in the liquid phase and the role of mass transfer based on the dimensionless Damköhler number