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

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

Nano-sized TiO 2 photocatalytic water-splitting technology has great potential for low-cost, environmentally friendly solar-hydrogen production to support the future hydrogen economy. Presently, the solar-to-hydrogen energy conversion efficiency is too low for the technology to be economically sound. The main barriers are the rapid recombination of photo-generated electron/hole pairs as well as backward reaction and the poor activation of TiO 2 by visible light. In response to these deficiencies, many investigators have been conducting research with an emphasis on effective remediation methods. Some investigators studied the effects of addition of sacrificial reagents and carbonate salts to prohibit rapid recombination of electron/hole pairs and backward reactions. Other research focused on the enhancement of photocatalysis by modification of TiO 2 by means of metal loading, metal ion doping, dye sensitization, composite semiconductor, anion doping and metal ion-implantation. This paper aims to review the up-to-date development of the above-mentioned technologies applied to TiO 2 photocatalytic hydrogen production. Based on the studies reported in the literature, metal ion-implantation and dye sensitization are very effective methods to extend the activating spectrum to the visible range. Therefore, they play an important role in the development of efficient photocatalytic hydrogen production.

A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production

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.

/pdf/a-review-on-the-visible-light-active-titanium-dioxide-2qg81s4yao.pdf

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

http://ntur.lib.ntu.edu.tw/bitstream/246246/93164/1/33.pdf

Novel BN supported bi-metal catalyst for oxydehydrogenation of propane

One of the major drawbacks in photoreduction of carbon dioxide (CO 2 ) into hydrocarbons is the high thermodynamic barrier involved, resulting in low photoreduction quantum efficiency (PQE). A novel twin photoreactor system has been developed to enhance the PQE of CO 2 reduction as a solution to this limitation. The twin photoreactor divides the oxygen (O 2 )-generating photocatalyst and the dual-function photocatalyst having both CO 2 reduction and hydrogen (H 2 ) production capabilities in two compartments by a membrane thus preventing the undesired reverse reaction. Herein, the dual-function photocatalyst can hydrogenate CO 2 via the produced H 2 , allowing the overall reaction to be more thermodynamically favorable. The charge balance was accomplished by the aid of IO 3 − /I − redox mediator in the twin photoreactor for shuttling electrons. Two visible-light photocatalysts, Pt/WO 3 (O 2 -generating photocatalyst) and GaN:ZnO–Ni/NiO (both CO 2 -reducing and H 2 -generating photocatalysts) were used. We found out that through the application of the twin photoreactor system under artificial sunlight (AM1.5G 300 W Xenon lamp), the PQE was enhanced more than 4-folds in comparison with that in the single photoreactor, an increase from 0.015% to 0.070%. A possible enhancing mechanism for twin photoreactor, in compare with the conventional single photoreactor, is also proposed based on the knowledge of species present during the photocatalytic reaction.

Photocatalytic water splitting and hydrogenation of CO2 in a novel twin photoreactor with IO3−/I− shuttle redox mediator

The light irradiation parameters, including the wavelength spectrum and intensity of light source, can significantly influence a photocatalytic reaction. This study examines the propylene photo-epoxidation over V-Ti/MCM-41 photocatalyst by using artificial sunlight (Xe lamp with/without an Air Mass 1.5 Global Filter at 1.6/18.5 mW·cm(-2)) and ultraviolet light (Mercury Arc lamp with different filters in the range of 0.1-0.8 mW·cm(-2)). This is the first report of using artificial sunlight to drive the photo-epoxidation of propylene. Over V-Ti/MCM-41 photocatalyst, the propylene oxide (PO) formation rate is 193.0 and 112.1 µmol·gcat (-1)·h(-1) with a PO selectivity of 35.0 and 53.7% under UV light and artificial sunlight, respectively. A normalized light utilization (NLU) index is defined and found to correlate well with the rate of both PO formation and C3H6 consumption in log-log scale. The light utilization with a mercury arc lamp is better than with a xenon lamp. The selectivity to PO remains practically unchanged with respect to NLU, suggesting that the photo-epoxidation occurs through the same mechanism under the conditions tested in this study.

https://ir.nctu.edu.tw:443/bitstream/11536/24194/1/000335255900001.pdf

Artificial sunlight and ultraviolet light induced photo-epoxidation of propylene over V-Ti/MCM-41 photocatalyst.

Novel dual-layer photoelectrode prepared by RF magnetron sputtering for photocatalytic water splitting

Titania and copper-loaded titania were synthesized by an improved sol-gel method using a homogeneous hydrolysis technique. Unlike the conventional sol-gel procedure that added water directly, the esterification of anhydrous butanol and glacial acetic acid provided the hydrolyzing water. In addition, acetic acid also served as a chelating ligand to stabilize the hydrolysis-condensation process and minimize the agglomeration of titania. Fourier transform infrared spectra confirmed the presence of bidental ligand. The sol was dried, then calcined at 500°C to remove organics and transformed to anatase titania. Transmission electron microscopy revealed that the titania particles were uniform, and the particle size ranged from 10 to 25 nm. The band gaps of TiO2 and Cu/TiO2 ranged from 3.01 to 3.17 eV based on the diffusive reflective ultraviolet-visible spectrometry. X-ray photoelectron spectroscopy analysis showed a positive shift of binding energy of Ti2p3/2 and a negative shift of Cu 2p3/2 in Cu/TiO2. The redistribution of electric charge is due to the Schottky barrier of Cu and TiO2.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S088429140005812X

Jeffrey C.S. Wu

Papers

Novel BN supported bi-metal catalyst for oxydehydrogenation of propane

Photocatalytic water splitting and hydrogenation of CO2 in a novel twin photoreactor with IO3−/I− shuttle redox mediator

Artificial sunlight and ultraviolet light induced photo-epoxidation of propylene over V-Ti/MCM-41 photocatalyst.

Novel dual-layer photoelectrode prepared by RF magnetron sputtering for photocatalytic water splitting

Sol-gel-derived photosensitive TiO 2 and Cu/TiO 2 using homogeneous hydrolysis technique