Studies of several systems with air electrode electro-synthesizing H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the spot for degrading aniline in aqueous

A gas diffusion electrode (air electrode) with a high current efficiency of electro-synthesizing H₂O₂ using O₂ in air was prepared. The several systems with air electrode as cathode of electro-synthesizing H₂O₂ on the reaction spot for degrading aniline in aqueous—electro-Fenton system, photo-excitation electro-H₂O₂ system and photo-electro-Fenton system, were developed. The rates of decomposition of H₂O₂ and mineralization of aniline were experimentally measured respectively under different conditions, and the results indicated there has an excellent parallel relation between decomposition rate of H₂O₂ and mineralization rate of aniline. Especially, photo-electro-Fenton system, where H₂O₂ is decomposed the fastest, is the best system of oxidizing and degrading organic toxicants. Compared photo-electro-Fenton system with photo-Fenton system, important role is revealed in the interface of air electrode. In this paper, the mineralization mechanism of aniline in the photo-electro-Fenton system was also discussed. Foundation item: Supported by the National Natural Science Foundation of China (200710026) and Foundation of Environmental Sciences Academy of Jiangsu Province. Biography: Cao xiao-yu (1979-), male, Master candidate, research direction: Electrochemistry     

The characteristic of electrochemical oxidation of aniline on SnO2/Ti electrode

The characteristic of electrochemical oxidation of aniline on SnO₂/Ti electrode is studied. The results indicate that SnO₂/Ti electrode dopedF plays a wonderful role in the oxidation of aniline comparing with Pt electrode. The kinetics factors that influence the oxidation rate of aniline on the SnO₂/Ti electrode are determined by the dissolving of the film on the electrode. The dissolving of the film consisted of intermediate products on the electrode is the slow step. The effects of aniline concentration, pH in aniline solution and the current density (i) on the rate of aniline oxidation, the complexity of intermediate products and the basic category of the intermediate products consisted of the film are introduced. Foundation item: Supported by the National Natural Science Foundation of PRC(10971023) Biography: Wany Yu-ling (1975-), female, Master, research direction: photochemical catalysis and electochemical catalysis.     

Preparation of Zn-doped TiO2 nanotubes electrode and its application in pentachlorophenol photoelectrocatalytic degradation

Zn-doped titanium oxide （TiO2） nanotubes electrode was prepared on a titanium plate by direct anodic oxidation and immersing method in sequence. Field emission scanning electron microscopy （FESEM） showed that the Zn-doped TiO2 nanotubes were well aligned and organized into high density uniform arrays with diameter ranging from 50 to 90 nm. The length and the thickness were about 200 and 15 nm respectively. TiO2 anatase phase was identified by X-ray diffraction （XRD）. X-ray photoelectronspectroscopy （XPS） indicated that Zn ions were mainly located on the surface of TiO2 nanotubes in form of ZnO clusters. Compared with TiO2 nanotubes electrode, about 20 nm red shift in the spectrum of UV-vis absorption was observed. The degradation of pentachlorophenol （PCP） in aqueous solution under the same condition （initial concentration of PCP： 20 mg/L; concentration of Na2SO4：0.01 mol/L and pH： 7.03） was carried out using Zn-doped TiO2 nanotubes electrode and TiO2 nanotubes electrode. The degradation rates of PCP using Zn-doped TiO2 nanotubes electrode were found to be twice and 5.8 times as high as that using TiO2 nanotubes electrode by UV radiation （400 μw/cm^2） and visible light radiation （4500 μw/cm^2）, respectively. 73.5% of PCP was removed using Zn-doped TiO2 nanotubes electrode against 45.5% removed using TiO2 nanotubes electrode in 120 min under UV radiation. While under visible light radiation, the degradation efficiency of PCP was 18.4% using Zn-doped TiO2 nanotubes electrode against 3.2% using TiO2 nanotubes electrode in 120 min. The optimum concentration of Zn doping was found to be 0.909%. The PCP degradation efficiencies of the 10 repeated experiments by Zn-doped TiO2 nanotubes electrode were rather stable with the deviation within 3.0%.     

Performances improvement of eosin Y sensitized solar cells by modifying TiO2 electrode with silane-coupling reagent

Chemical fixing of xanthene dye （eosin Y） on the surface of TiO2 electrode was carried out by modifying the electrode with silane-coupling reagent to obtain stable dye-sensitized TiO2 electrode. Such silane modification can not only evidently enhance the stability of dye-sensitized TiO2 electrode but also improve the energy conversion efficiency of the assembled cells by increasing short-circuit photocurrent （Jsc） and open-circuit photovoltage （Voc）. It was found that the improvements of cell performances differ depending on the composition of the electrolyte. The optimum cell of the cell performance was achieved in the electrolyte with 0.5 mol/L TBAI/0.05 mol/L 12/EC：PC（3：1 w/w）, yielding Jsc of 4.69 mA. cm-2, Voc of 0,595 V, fill factor （FF） of 0.64 and ηof 1,78%, Different spectroscopic techniques including UV-Vis spectra, fluorescence spectra, EIS and dark current measurements were employed to derive reasonable analysis and explanations.     

碳纳米管/纳米 TiO2-聚苯胺复合膜电极的电化学制备及表征

在含有0.2 mol/L苯胺的0.5 mol/L　H₂SO₄溶液中, 采用循环伏安法(CV), 以扫描速度50 mV/s, 扫描电位-0.1~0.9 V,在碳纳米管/纳米TiO₂(CNT/nanoTiO₂)膜电极上实现了苯胺的电化学聚合, 用电化学阻抗谱（EIS）和CV法对制备的碳纳米管/纳米TiO₂聚苯胺(CNT/nanoTiO₂ PAn)复合膜电极的电化学性质进行了表征, 从扫描电镜对膜层的微观形貌观察发现, 这种在纳米基体上聚合得到的聚苯胺膜层呈疏松、 多孔的纳米纤维网状结构, 同时具有良好的导电性, 不同于在普通金属基体上聚合得到的颗粒状聚苯胺膜.     

新型复合电极及其光催化反应的研究

介绍了具有合成H2O2和光催化性能的双功能新型复合电极,双功能复合电极是将TiO2/C光催化剂负载在具有合成H2O2性能的新型载体上形成的,实现了光化学氧化与光催化氧化在同一电极／溶液界面上的联合作用,实验结果表明,空气电极工作电流密度对偶氮染料分子活性艳红（K－2BP）的氧化降解速度有影响,i＝15mA/cm^2,速度达到最大。实验发现偶氮染料分子在复合电极表面的吸附量与反应速度密切相关。文中讨论了复合电极的作用原理及其稳定性、偶氮染料分子的氧化降解过程。     

Preparation and characterization of in-site regenerated TiO<Subscript>2</Subscript>-ACFs photocatalyst

In-site regenerated titanium dioxide-activated carbon fibers (TiO₂-ACFs) photocatalyst was prepared by the sol-gel method. Detailed surface and structural characterization of the TiO₂-ACFs photocatalyst was carried out. The photoactivity of TiO₂-ACFs under ultraviolet irradiation was compared with original ACFs and pure TiO₂ by the degradation of methylene blue aqueous solution. The degradation efficiency by the TiO₂ (5wt%)-ACFs sample is much higher than that by TiO₂ and ACFs. The results show that the photocatalysis by TiO₂-ACFs is a six-step process. The adsorption-transfer-photocatalysis rate of TiO₂-ACFs is higher than the adsorption-photocatalysis rate of TiO₂, so the photocatalysis rate of the TiO₂-ACFs system is higher than that of TiO₂ photocatalyst.     

Photoelectrochemical synergetic degradation of Acid Orange II with TiO2 modified β-PbO2 electrode

Electrochemically assisted photocatalysis is an effective approach to improve photocatalytic efficiency. In this paper, modified β-PbO2 electrode was prepared by TiO2 co-deposition and characterized by SEM and XRD. Then 2.0g TiO2 modified β-PbO2 electrode (2.0 g TiO2 involved in the 200 mL co-deposition solution) was used in electrochemically assisted photocatalytic degradation of Acid Orange II and the influence of initial pH values was investigated when the potential applied across the electrodes was 1.5 V. When the potential applied was 2.5 V, the difference of the degradation process and the final products were studied. The results indicated that 2.0 g TiO2 modified β-PbO2 electrode was different from the unmodified one in that the β-PbO2 crystals became finer and the electrode became more compact and more uniform. The synergetic effect in electrochemically assisted photocatalytic degradation of Acid Orange Ⅱ was observed and degradation efficiency and TOC removal were the highest at initial solution pH 2.0. By UV-visible spectral analysis, it was proved that photoelectrochemical synergetic degradation of Acid Orange Ⅱ went through the step of producing main product maleic acid for the solution at the initial pH 2.0 within 2 h, but the degradation was slow for the solution at the initial pH 12.0.     

TiO<Subscript>2</Subscript>@MgO core-shell film: Fabrication and application to dye-sensitized solar cells

In this study,TiO2@MgO core-shell film was obtained by using a simple chemical bath deposition method to coat a thin MgO film around TiO2 nanoparticles. The core-shell configuration was characterized by X-ray diffractometer (XRD),scanning elec-tron microscopy (SEM),energy dispersive X-ray spectroscopy (EDX),and high-resolution transmission electron microscopy (HRTEM). Lattice fringes were observed for the TiO2 particles,and the MgO shell showed an amorphous structure,revealing a clear distinction between the core and shell materials. Applying the core-shell film as photoanode to the dye-sensitized solar cells (DSSCs),it shows a superior performance compared to the pure TiO2 electrode. Under the illumination of simulated sunlight (75 mW-cm-2),the short circuit photocurrent (Jsc),the open circuit photovoltage (Voc),and the fill factor (fF) are 8.80 mA-cm-2,646 mV,and 0.69,respectively,and the conversion efficiency (η) in-creased by 21.8% (from 4.32% to 5.26%) when dipping for opti-mum condition.     

Fabrication and Photocatalytic Characteristics of TiO2 Films on Silicon Substrates

Silicon ( 111 ) and Silicon (100) have been employed for fabrication of TiO2 films by metal organic chemical vapor deposition (MOCVD). Titanium (Ⅳ) isopropoxide (Ti[O (C3H7)4 ])was used as a precursor. The as-deposited TiO2 films have been characterized with Field emission scanning electron microscopy (FE-SEM), X ray diffraction (XRD) and atomic force microscopy (AFM). The photocatalytic properties were investigated by decomposition of aqueous orange Ⅱ. The crystalline and structural properties of TiO2 film had crucial influences on the photodegradation efficiency. For MOCVD in-situ deposited films on Si substrates, thephotoactivities varied following a shape of “M”: At lower (350 ℃ ) middle (500 ℃) and higher (800 ℃) temperature of deposition, relative lower photodegradation activities have been observed. At 400 ℃ and 700 ℃ of deposition, relative higher efficiencies of degradation have been obtained, because one predominant crystallite orientation could be obtained as deposition at those two temperatures, especially a single anatase crystalline TiO2 film could be obtained at 700 ℃ growth.     

Photoelectrical performance of nanocrystalline TiO2 film electrode sensitized by Ru(II)-bipyridine complexes

Two kinds of Ru(II)-bipyridine complexes,cis-di(thiocyanate)bis(2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium(II) andcis-di(thiocyanate)bis(2, 2′-bipyridyl-3, 3′-dicarboxylate) ruthenium(II), were utilized as the sensitizers to the nanocrystalline TiO₂ film electrodes. Study shows that the two dyes have quite different sensitization properties due to the strong steric effect of carboxyl groups. In addition, the pretreatment to nanocrystalline TiO₂ film electrodes with TiCl₄ was investigated, which is an effective way to improve the photoelectric conversion performances of sensitized TiO₂ electrodes.     

Preparation and magnetic properties of CoFe2O4/TiO2 composite films

Using （Ti（OC4H9）4） and metal chlorates as starting materials, CoFe2O4/TiO2 composite films were prepared by sol-gel method. The effects of heat treatment temperature and pH of the precursor on microstructure and magnetic properties were studied. The phase structure of the samples was examined by X-ray diffraction. The microstructure was examined by scanning electron microscope, atomic force microscope and polarized microscope. The magnetic property was measured by vibrating sample magnetometer. The results show that the crystals of different phases grow up independently. CoFe2O4 is uniformly embedded into the TiO2 matrix in the prepared composite films, and the growth of composite films is dependent on the heat treatment temperatures and PH of the precursor. The average size of CoFe2O4 crystal is 19 nm in Nanocomposite film prepared when the heat treatment temperature is 800℃ and the pH of the precursor is between 2 and 3. The magnetism of the composite films is enhanced as the heat treatment temperature increases.     

光源对TiO_2光催化剂性能的影响

采用阳极氧化法制备了 Ti O2 /Ti薄膜半导体光电极 ,并测试了该电极在 2 5 4 nm和365 nm两种光源照射下苯酚的转化过程。实验表明 :2 5 4 nm波长光源下苯酚的降解以均相光氧化反应为主 ;365 nm波长的光照下 ,以多相光催化反应为主 ,电极上加偏压能明显提高反应速率。在三电极体系中 ,用频响分析系统测试了光电极的交流阻抗图谱 ( EIS) ,分析 EIS图谱所得的结论与上述结论一致     

空气电极负载TiO2的新型复合电极的研究（Ⅱ）

本文介绍了具有合成H2O2和光催化性能的双功能新型复合电极.双功能复合电极是将TiO2/C光催化剂负载在具有合成H2O2性能的新型载体上形成的.当反应器工作时,复合电极中的TiO2/C光催化层表面进行着光催化反应,在载体的三相界面上进行着O2的2电子还原生成H2O2的电化学反应(O2+2H++2e→H2O2),电流效率达82%(i=15mA/cm2),为@OH自由基的生成提供了物质源,而且氧的2电子还原反应电位使其表面的TiO2获得相对于平带电位约+0.5v的阳极偏压,改善了TiO2的光催化活性.实验结果表明,TiO2负载量与反应速度密切相关;空气电极合成H2O2的速率受电流密度和pH值的影响.     

水热法制备TiO2-ZnO纳米棒分级结构及其光电性能研究

为了增加光电极光生电子传输通道并提高其光敏剂的负载能力,采用两步水热法制备了一种新颖的TiO_2-ZnO纳米棒分级结构。采用水热法在FTO导电玻璃基底上生长TiO_2纳米棒有序阵列膜,通过浸泡提拉在TiO_2纳米棒上包覆一层ZnO溶胶,经烧结形成ZnO种子层;再次采用水热法于TiO_2纳米棒上生长ZnO纳米棒,形成TiO_2-ZnO纳米棒分级结构,通过旋涂辅助连续离子反应分别在TiO_2纳米棒阵列和TiO_2-ZnO纳米棒分级结构中沉积光敏剂CdS纳米晶,形成CdS/TiO_2纳米棒复合膜和CdS/TiO_2-ZnO纳米分级结构复合膜。利用SEM,TEM,XRD、紫外-可见吸收光谱、瞬态光电流图谱等表征和测试手段,对样品的形貌、结构、光吸收和光电性能进行了表征和测试。结果表明,与单纯的TiO_2纳米棒阵列相比,TiO_2-ZnO分级结构可以沉积更多的CdS光敏剂,CdS/TiO_2-ZnO纳米分级结构复合膜的光吸收性能和瞬态光电流均明显优于CdS/TiO_2纳米复合薄膜。凭借优异的光电性能,TiO_2-ZnO分级结构在太阳电池光阳极材料中具有很好的应用前景。     

Fe_2O_3/TiO_2复合纳米管阵列的制备及其可见光催化性能研究

在氟化铵-乙二醇体系中,采用阳极氧化法在铁基体上制备Fe_2O_3纳米管阵列,然后以氟钛酸铵为钛源,利用水热法在Fe_2O_3纳米管阵列上负载TiO_2纳米片,制得Fe_2O_3/TiO_2复合纳米管阵列,利用SEM、EDS、XRD、TEM、UV-Vis等手段,对所制Fe_2O_3/TiO_2纳米管阵列的表面形貌、物相结构及光催化性能进行表征,并分析Fe_2O_3/TiO_2纳米结构对亚甲基蓝的可见光降解能力。结果表明,Fe_2O_3/TiO_2复合纳米管阵列具有良好的可见光响应;NH_4F浓度为0.4%、水热反应3h制备的Fe_2O_3/TiO_2复合结构具有最佳的光催化性能,对亚甲基蓝的降解率可达90%。     

Studies of Several Systems with Air Electrode Electro-Synthesizing H_2O_2 on the Spot for Degr ading Aniline in Aqueous

0　ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｍｅｔｈｏｄｏｆｍｉｎｅｒａｌｉｚｉｎｇｏｒｇａｎｉｃｔｏｘｉｃａｎｔｓｉｎｔｈｅｗａｓｔｅｗａｔｅｒｂｙｇｅｎｅｒａｔｉｎｇ·ＯＨｒａｄｉｃａｌｓｈａｓｂｅｃｏｍｅｆｏｃｕｓｏｆｃｈｅｍｉｃａｌｔｈｅｏｒｉｅｓａｎｄｔｅｃｈｎｉｃａｌｒｅｓｅａｒｃｈｅｓｉｎｔｈｅｅｎｖｉｒｏｎｍｅｎｔｐｒｏｔｅｃｔｉｏｎ[1] .Ｂｅｃａｕｓｅ·ＯＨｒａｄｉｃａｌｉｓａｓｔｒｏｎｇｏｘｉｄｉｚｅｒｗｉｔｈｓｔａｎｄａｒｄｐｏｔｅｎｔｉａｌｏｆ2 .80Ｖ ,ｗｉｔｈｉｔ,ｔｈｅｓｔａｂｌｅ…     

Silicon field emission arrays coated with CN<Subscript>x</Subscript> thin films

Arrays of silicon micro-tips were made by etching the p-type (1 0 0) silicon wafers which had SiO₂ masks with alkaline solution. The density of the micro-tips is 2×10⁴ cm⁻². The Scanning Electron Microscope (SEM) photos showed that the tips in these arrays are uniform and orderly. The CN_x thin film, with the thickness of 1.27 μm was deposited on the silicon micro-tip arrays by using the middle frequency magnetron sputtering technology. The SEM photos showed that the films on the tips are smoothly without particles. Keeping the sharpness of the tips will benefit the properties of field emission. The X-ray photoelectron spectrum (XPS) showed that carbon, nitrogen and oxygen are the three major elements in the surfaces of the films. The percents of them are C: 69.5%, N: 12.6% and O: 17.9%. The silicon arrays coated with CN_x thin films had shown a good field emission characterization. The emission current intensity reached 3.2 mA/cm² at 32.8 V/μm, so it can be put into use. The result showed that the silicon arrays coated with CN_x thin films are likely to be good field emission cathode. The preparation and the characterization of the samples were discussed in detail. Foundation item: Supported by the National Natural Science Foundation of China (19975035) Biography: Chen Ming an (1978-), male, Ph. D candidate, research direction: novel functional materials film and ion beam modification of materials.     

Modification of TiO2 nanotubes arrays by CdS and their photoelectrocatalytic hydrogen generation properties

In order to realize hydrogen generation under visible light, novel CdS/TiO2 nanotubes arrays are developed by electrochemical anodizaUon of Ti in 0.15 mol/L NHTF ＋ 0.08 mol/L H2C2O4 electrolyte. The diameter of the nanotube is 80-100 nm and the length is approximately 550 nm. The CdS nano-particles are deposited on the TiO2 nanotubes arrays by chemical bath deposition （CBD） in the ammonia-thiourea system. A 300 W Xe lamp is used as the light source, CdS/TiO2 nanotube arrays are used as the photoanode with the application of 1.0 V bath voltage, and 0.1 mol/L Na2S ＋ 0.04 mol/L Na2SO3 solution is used as the electrolyte, then the rate of photoelectrocatalytic hydrogen generation is 245.4 μL/（h·cm^2）. This opens new perspectives for photoelectrocatalytic hydrogen generation by using CdS/TiO2 nanotubes arrays.     

Comparative study of oxidation ability between boron-doped diamond (BDD) and lead oxide (PbO<Subscript>2</Subscript>) electrodes

The electrochemical oxidation capabilities of two high-performance electrodes, the boron-doped diamond film on Ti (Ti/BDD) and the lead oxide film on Ti (Ti/PbO₂), were discussed. Hydroxyl radicals (·HO) generated on the electrode surface were detected by using p-nitrosodimethylaniline (RNO) as the trapping reagent. Electrochemical oxidation measurements, including the chemical oxygen demand (COD) removal and the current efficiency (CE), were carried out via the degradation of p-nitrophenol (PNP) under the galvanostatic condition. The results indicate that an indirect reaction, which is attributed to free hydroxyl radicals with high activation, conducts on the Ti/BDD electrode, while the absorbed hydroxyl radicals generated at the Ti/PbO₂ surface results in low degradation efficiency. Due to quick mineralization which combusts PNP to CO₂ and H₂O absolutely by the active hydroxyl radical directly, the CE obtained on the Ti/BDD electrode is much higher than that on the Ti/PbO₂ electrode, notwithstanding the number of hydroxyl radicals produced on PbO₂ is higher than that on the BDD surface.