Photocatalytic Degradation of Organic Pollutants Under Visible Light Irradiation

Several TiO₂-based photocatalytic systems that have considerable visible light response have been developed, such as the photodegradation of organic pollutants on sensitized TiO₂ by visible light, construction of visible-light-active novel TiO₂ photocatalysts by matrix or surface modification. In this paper, we review briefly our recent progress in the TiO₂ photocatalytic degradation of organic pollutants by visible light, some related work by other groups is also involved.     

Effect of Thermal Treatment on the Photocatalytic Activity in Visible Light of TiO<Subscript>2</Subscript>-W Flame Spray Synthesised Nanopowders

Effect of W doping as well as a thermal treatment on the structural and photocatalytic properties of TiO₂ produced by flame spray synthesis (FSS) were the subject of investigation. Structural properties were studied by means of X-ray diffraction (XRD), BET adsorption isotherm and transmission electron microscopy (TEM). The surface condition was investigated by X-ray photoelectron spectroscopy (XPS) and differential scanning calorimetry (DSC) and differential thermal and thermogravimetric analysis (DTA-TGA). The photocatalytic properties were studied by optical measurements and photodecomposition of methylene blue under visible irradiation. It was found that the photoactivity in the visible region was enhanced significantly by the W-doping as well as by additional thermal treatment of those nanopowders. The obtained TiO₂-W nanopowders exhibited higher performance under visible light than P25.     

具有可见光催化活性的TiO2系光催化剂研究进展

由于受激发波长的限制，TiO2只能利用太阳能中不足5％的紫外光。本文较为详细NTiO2可见光催化剂的制备、性能及应用进行了综述。研究表明，通过金属及非金属离子掺杂改性、离子注入以及染料光敏化等方法可以将TiO2光催化反应红移到可见光区域进行。     

Photocatalytic degradation of trichloroethylene over TiO<Subscript>2</Subscript>/SiO2 in an annulus fluidized bed reactor

The effects of superficial gas velocity (Ug), wavelength and intensity of ultraviolet (UV) light, oxygen and H₂O concentration on the photocatalytic degradation of TCE (Trichloroethylene) over TiO₂/SiO₂ catalyst have been determined in an annulus fluidized bed photoreactor. The key factor in determining the performance of the annulus fluidized bed photoreactor is found to be an optimum superficial gas velocity (Ug) that provides the optimum UV lighttransmit through the proper size of bubbles in the photoreactor. The degradation efficiency of TCE increases with light intensity but decreases with wavelength of the UV light and H₂O concentration in the fluidized bed of TiO₂/silica-gel photocatalyst. The optimum concentration of O₂ for TCE degradation is found to be approximately 10%. The annulus fluidized bed photoreactor is an effective tool for high TCE degradation with efficient utilization of photon energy. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Photocatalytic Generation of H<Subscript>2</Subscript> Gas from Neat Ethanol over Pt/TiO<Subscript>2</Subscript> Nanotube Catalysts

TiO₂ nanotubes promoted with Pt metal were prepared and tested to be the photocatalytic dehydrogenation catalyst in neat ethanol for producing H₂ gas (C₂H₅OHC₃CHO +H₂). It was found that the ability to produce H₂, the liquid phase product distribution and the catlyst stability of these promoted nano catalysts all depended on the Pt loading and catalyst preparation procedure. These Pt/TiO₂ catalysts with TiO₂ nanotubes washed with diluted H₂SO₄ solution produced 1, 2-diethoxy ethane (acetal) as the major liquid phase product, while over those washed with diluted HCl solution or H₂O, acetaldehyde was the major liquid phase product.     

Synthesis,Characterization and Photocatalytic Activity of New Photocatalyst ZnBiSbO4 under Visible Light Irradiation

In this paper, ZnBiSbO₄ was synthesized by a solid-state reaction method for the first time. The structural and photocatalytic properties of ZnBiSbO₄ had been characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, transmission electron microscope and UV-visible spectrometer. ZnBiSbO₄ crystallized with a pyrochlore-type structure and a tetragonal crystal system. The band gap of ZnBiSbO₄ was estimated to be 2.49 eV. The photocatalytic degradation of indigo carmine was realized under visible light irradiation with ZnBiSbO₄ as a catalyst compared with nitrogen-doped TiO₂ (N-TiO₂) and CdBiYO₄. The results showed that ZnBiSbO₄ owned higher photocatalytic activity compared with N-TiO₂ or CdBiYO₄ for the photocatalytic degradation of indigo carmine under visible light irradiation. The reduction of the total organic carbon, the formation of inorganic products, SO₄²⁻ and NO₃⁻, and the evolution of CO₂ revealed the continuous mineralization of indigo carmine during the photocatalytic process. One possible photocatalytic degradation pathway of indigo carmine was obtained. The phytotoxicity of the photocatalytic-treated indigo carmine (IC) wastewater was detected by examining its effect on seed germination and growth.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> hollow spheres and their activity in methylene blue photodecomposition

PSA [poly-(styrene-methyl acrylic acid)] latex particle has been taken into account as template material in SiO₂ hollow spheres preparation. TiO₂-doped SiO₂ hollow spheres were obtained by using the appropriate amount of Ti(SO₄)₂ solution on SiO₂ hollow spheres. The photodecomposition of the MB (methylene blue) was evaluated on these TiO₂-doped SiO₂ hollow spheres under UV light irradiation. The catalyst samples were characterized by XRD, UV-DRS, SEM and BET. A TiO₂-doped SiO₂ hollow sphere has shown higher surface area in comparison with pure TiO₂ hollow spheres. The 40 wt% TiO₂-doped SiO₂ hollow sphere has been found as the most active catalyst compared with the others in the process of photodecomposition of MB (methylene blue). The BET surface area of this sample was found to be 377.6 m²g⁻¹. The photodegradation rate of MB using the TiO₂-doped SiO₂ catalyst was much higher than that of pure TiO₂ hollow spheres.     

Dye sensitized CO<Subscript>2</Subscript> reduction over pure and platinized TiO<Subscript>2</Subscript>

TiO₂ thin and thick films promoted with platinum and organic sensitizers including novel perylene diimide dyes (PDI) were prepared and tested for carbon dioxide reduction with water under visible light. TiO₂ films were prepared by a dip coating sol–gel technique. Pt was incorporated on TiO₂ surface by wet impregnation [Pt(on).TiO₂], or in the TiO₂ film [Pt(in).TiO₂] by adding the precursor in the sol. When tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate was used as sensitizer, in addition to visible light activity towards methane production, H₂ evolution was also observed. Perylene diimide derivatives used in this study have shown light harvesting capability similar to the tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate.     

Ag@AgCl-TiO2-粉煤灰微珠复合光催化剂的制备及其可见光光催化性能

采用离子交换法在粉煤灰微珠(FMS)表面沉积Ag@AgCl纳米颗粒,制备Ag@AgCl-FMS复合基底,采用水解-沉淀工艺,以TiCl4为钛源在复合基底表面再包覆纳米TiO2薄膜,经500℃煅烧2 h后得到Ag@AgCl- FMS-TiO2复合光催化剂. 对材料微观形貌、晶体结构、可见光光催化性能进行了表征与测试. 结果表明,复合基底表面包覆的TiO2薄膜均匀完整. 500℃煅烧后的物相为90%锐钛矿型TiO2和10%金红石型TiO2. 复合催化剂料在Ag@AgCl等离子共振效应的作用下,表现出明显的可见光响应,经可见光照射80 min后对甲基橙的降解率达99%,5次重复使用对甲基橙的降解率保持在85%.     

Enhancement of the photoelectric performance of dye-sensitized solar cells using Ag-doped TiO<Subscript>2</Subscript> nanofibers in a TiO<Subscript>2</Subscript> film as electrode

For high solar conversion efficiency of dye-sensitized solar cells [DSSCs], TiO₂ nanofiber [TN] and Ag-doped TiO₂ nanofiber [ATN] have been extended to be included in TiO₂ films to increase the amount of dye loading for a higher short-circuit current. The ATN was used on affected DSSCs to increase the open circuit voltage. This process had enhanced the exit in dye molecules which were rapidly split into electrons, and the DSSCs with ATN stop the recombination of the electronic process. The conversion efficiency of TiO₂ photoelectrode-based DSSCs was 4.74%; it was increased to 6.13% after adding 5 wt.% ATN into TiO₂ films. The electron lifetime of DSSCs with ATN increased from 0.29 to 0.34 s and that electron recombination was reduced.     

Facile Synthesis and Tensile Behavior of TiO<Subscript>2</Subscript> One-Dimensional Nanostructures

High-yield synthesis of TiO₂ one-dimensional (1D) nanostructures was realized by a simple annealing of Ni-coated Ti grids in an argon atmosphere at 950 °C and 760 torr. The as-synthesized 1D nanostructures were single crystalline rutile TiO₂ with the preferred growth direction close to [210]. The growth of these nanostructures was enhanced by using catalytic materials, higher reaction temperature, and longer reaction time. Nanoscale tensile testing performed on individual 1D nanostructures showed that the nanostructures appeared to fracture in a brittle manner. The measured Young’s modulus and fracture strength are ~56.3 and 1.4 GPa, respectively.     

Photoelectrocatalytic degradation of phenol using a TiO<Subscript>2</Subscript>/Ni thin-film electrode

As a new type of photoelectrode, TiO₂/Ni thin-film electrode was prepared by dip-coating technique. The structural and surface morphology of electrode was examined by X-ray diffraction (XRD) and scanning electron microscope (SEM). Effects of initial phenol concentration, pH value, number of film layers, voltage of electrical bias applied, variation of inorganic salt type and types of dissolved gas on the photoelectrocatalytic (PEC) degradation of phenol using ultraviolet (UV) illuminated TiO₂/Ni thin-film electrode were investigated. The mechanism of PEC degradation of phenol was also studied by analyzing reaction intermediates.     

Synergism Between Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Au/TiO<Subscript>2</Subscript> in the Low Temperature Oxidation of Propene

CO impedes the low temperature (<170 °C) oxidation of C₃H₆ on supported Pt. Supported Au catalysts are very effective in the removal of CO by oxidation, although it has little propene oxidation activity under these conditions. Addition of Au/TiO₂ to Pt/Al₂O₃ either as a physical mixture or as a pre-catalyst removes the CO and lowers the light-off temperature (T ₅₀) for C₃H₆ oxidation compared with Pt catalyst alone by ~54 °C in a feed of 1% CO, 400 ppm C₃H₆, 14% O₂, 2% H₂O.     

Characterization Of C60/Bi2TiO4F2 as a Potential Visible Spectrum Photocatalyst for The Depolymerization of Lignin

Effects of a photocatalyst, C₆₀-modified Bi₂TiO₄F₂, on pine kraft lignin under visible light irradiation were investigated, along with those of Bi₂TiO₄F₂ and C₆₀/TiO₂ as references. The influences of pH, C₆₀ mass fraction, and the initial lignin concentration on lignin conversion and yields of mono-phenolic products were investigated. Seven products were determined by GC/MS, including phenol, 2-methoxyphenol, 4-ethyl-2-methoxyphenol, 2-methoxy-4-vinylphenol, vanillin, acetovanillone, and homovanillic acid. The yields of products and lignin conversion were higher by C₆₀/Bi₂TiO₄F₂ than Bi₂TiO₄F₂ and C₆₀/TiO₂. C₆₀/Bi₂TiO₄F₂ and C₆₀/TiO₂ were more stable than Bi₂TiO₄F₂ upon repetitive recycling of catalyst. The effectiveness of C₆₀/Bi₂TiO₄F₂ declines 25%, whereas that of Bi₂TiO₄F₂ declines 56.4% after being recycled five times. FTIR and HRTEM indicated that the deactivation of photocatalysts might be caused by lignin adsorbed on the surface of photocatalysts and the change in the crystal structure.     

Photocatalytic degradation of methylene blue and acetaldehyde by TiO<Subscript>2</Subscript>/glaze coated porous red clay tile

Nanosized TiO₂ sol synthesized by sol-gel method was successfully coated on the porous red clay tile (PRC tile) with micrometer sized pores. PRC tile was first coated with a low-firing glaze (glaze-coated PRC tile) and then TiO₂ sol was coated on the glaze layer. A low-fired glaze was prepared at various blending ratios with frit and feldspar, and a blending ratio glazed at 700 °C was selected as an optimum condition. Then TiO₂ sol synthesized from TTIP was dip-coated on the glazed layer (TiO₂/glaze-coated PRC tile), and it was calcined again at 500 °C. Here, these optimum calcination temperatures were selected to derive a strong bonding by a partial sintering between TiO₂ sol particles and glaze layer. Photocatalytic activity on the TiO₂/glaze-coated PRC tile was evaluated by the extent of photocatalytic degradation of methylene blue and acetaldehyde. Methylene blue with the high concentration of 150 mg/l on the surface of TiO₂/glaze-coated PRC tile was almost photodegraded within 5 hours under the condition of average UV intensity of 0.275 mW/cm₂, while no photodegradation reaction of methylene blue occurred on the glaze-coated PRC tile without TiO₂. Another photocatalytic activity was also evaluated by measuring the extent of photocatalytic degradation of gaseous acetaldehyde. The photodegradation efficiency in TiO₂/glaze-coated PRC tile showed about 77% photocatalytic degradation of acetaldehyde from 45,480 mg/l to 10,536 mg/l after the UV irradiation of 14 hours, but only about 16% in the case of the glaze-coated PRC tile.     

Electrochemical treatment of ammonia in wastewater by RuO<Subscript>2</Subscript>–IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti electrodes

This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO₂–IrO₂–TiO₂/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH₄⁺-N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities     

可见光光催化剂CdIn_2S_4的制备及应用研究进展

可见光光催化是当前的热点课题。近年来,由于CdIn2S4对可见光有较强吸收且具有良好的稳定性而备受关注,是极具发展潜力的新型可见光光催化材料。本文对CdIn2S4的制备方法及其在光催化降解染料方面的应用进行整理总结,以期为进一步开展相关研究提供参考。     

Photocatalytic activities and specific surface area of TiO<Subscript>2</Subscript> films prepared by CVD and sol-gel method

The photocatalytic activity of CVD grown films shows significant, non-linear (sigmoid-like) dependency on the film thickness. However, the photocatalytic activity of sol-gel grown film is almost independent of the film thickness. The specific surface area of sol-gel grown films is very small, regardless of the film thickness. Conversely, the specific surface area of CVD grown films indicates significant thickness dependency. The specific area and photocatalytic activity were found to show very similar dependencies on the film thickness.     

A photocatalytic performance of TiO<Subscript>2</Subscript> photocatalyst prepared by the hydrothermal method

Anatase phase nanocrystalline TiO₂ powders were prepared by hydrothermal method with the TTIP (titanium tetra isopropoxide) at 200 oC in a stirred autoclave system. The effects of synthesis conditions on the physical properties of catalyst were investigated by using XRD, SEM, DLS, DSC and BET. The TiO₂ powders obtained from the optimum condition showed uniform spherical shape, crystalline structure, submicron size with a sharp size distribution and few agglomerates. The optimum synthesis conditions were obtained within the covered experimental ranges. The photocatalytic activity of TiO₂ powders prepared by the hydrothermal method was tested for photooxidation of methyl orange.     

Fabrication of Porous TiO<Subscript>2</Subscript> Hollow Spheres and Their Application in Gas Sensing

In this work, porous TiO₂ hollow spheres with an average diameter of 100 nm and shell thickness of 20 nm were synthesized by a facile hydrothermal method with NH₄HCO₃ as the structure-directing agent, and the formation mechanism for this porous hollow structure was proved to be the Ostwald ripening process by tracking the morphology of the products at different reaction stages. The product was characterized by SEM, TEM, XRD and BET analyses, and the results show that the as-synthesized products are anatase phase with a high surface area up to 132.5 m²/g. Gas-sensing investigation reveals that the product possesses sensitive response to methanal gas at 200°C due to its high surface area.