Degradation of bisphenol A in aqueous solution by H2O2-assisted photoelectrocatalytic oxidation

A series of titanium dioxide (TiO(2)/Ti) film electrodes were prepared from titanium (Ti) metal mesh by an improved anodic oxidation process and were further modified by photochemically depositing gold (Au) on the TiO(2) film surface as Au-TiO(2)/Ti film electrodes. The morphological characteristics, crystal structure and photoelectroreactivity of both the TiO(2)/Ti and Au-TiO(2)/Ti electrodes were studied. The experiments confirmed that the gold modification of TiO(2) film could enhance the efficiency of e(-)/h(+) separation on the TiO(2) conduction band and resulted in the higher photocatalytic (PC) and photoelectrocatalytic (PEC) activity under UV or visible illumination. To further enhance the TiO(2) PEC reaction, a reticulated vitreous carbon (RVC) electrode was applied in the same reaction system as the cathode to electrically generate H(2)O(2) in the aqueous solution. The experiments demonstrated that such a H(2)O(2)-assisted TiO(2) PEC reaction system could achieve a much better performance of BPA degradation in aqueous solution due to an interactive effect among TiO(2), Au, and H(2)O(2). It may have good potential for application in water and wastewater treatment in the future.     

Fabrication of TiO2/Ti electrode by laser-assisted anodic oxidation and its application on photoelectrocatalytic degradation of methylene blue

A TiO2/Ti mesh electrode by laser calcination was prepared in this article. The resulting TiO2 film was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS), and it illuminated that the prepared electrode mainly consisted of anatase TiO2 nanoparticles on its surface and exhibited a superior photocatalytic activity. The photodegradation of methylene blue (MB) using the proposed electrode under different experimental conditions was investigated in terms of both UV absorbance at 664 nm and chemical oxygen demand (COD) removal. The electrical bias applied in photoelectrocatalytic (PEC) oxidation was also studied. The experimental results showed that under the optimal potential of +0.50 V (versus SCE), UV absorbance and COD removal during the photodegradation of MB by the proposed TiO2/Ti mesh electrode were 97.3% and 87.0%, respectively. Through the comparison between photocatalytic (PC) oxidation and photoelectrocatalytic (PEC) oxidation, it was found that PEC oxidation was a convenient and effective way to mineralize the organic matters and that laser-treated photoelectrode exceeded the oven-treated one.     

Preparation and photoelectrocatalytic activity of ZnO nanorods embedded in highly ordered TiO(2) nanotube arrays electrode for azo dye degradation

In this article, the ZnO nanorods embedded in highly ordered TiO(2) nanotube arrays (ZnO/TiO(2) NR/Ts) electrodes were fabricated through two steps: (1) electrosynthesis of TiO(2) nanotube arrays (TiO(2) NTs) in HF solution by anodization method; (2) followed by cathodic electrodeposition of ZnO embedded in the TiO(2) nanotube arrays. The morphological characteristics and structures of ZnO/TiO(2) NR/Ts electrodes were examined by field-emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD) analysis, and UV-vis spectra. The linear-sweep photovoltammetry response on the ZnO/TiO(2) NR/Ts electrode was presented and the photocurrent was dramatically enhanced on the ZnO/TiO(2) NR/Ts electrode, comparing with that on bare TiO(2) NTs electrode. The photocatalytic and photoelectrocatalytic activity of ZnO/TiO(2) NR/Ts electrode was evaluated in degradation of methyl orange (MO) in aqueous solution.     

湿法碳氮硫共掺杂TiO2的制备及其光催化活性

以全硫碳酸铵为掺杂剂,采用湿法由硫酸钛出发制得碳氮硫共掺杂TiO2,通过XRD和XPS对掺杂TiO2进行了表征,并对掺杂TiO2的光催化活性进行了考察。结果表明,微波辅助加热制备的掺杂TiO2中,C元素部分替位取代了TiO2晶格中的Ti 4+;N元素以两种掺杂形式存在,即进入TiO2晶格替位取代O2-产生掺杂和通过化学吸附进入晶格间隙产生掺杂;S元素主要提供S 2p形成S6+取代Ti 4+进入晶格进行掺杂;以甲基橙溶液为对象进行光催化降解,当掺杂量α为1.6、500℃焙烧2h时,掺杂TiO2表现出较高的可见光催化活性,光照70min使浓度为20mg/L的甲基橙溶液的降解率达到99.64%,明显提高了纳米TiO2的光催化活性。     

P(MMA-AN)/TiO2复合粒子的制备及光催化性能

采用原位乳液聚合方法制备了基于共价键结合的P(MMA-AN)/TiO2复合粒子,红外光谱和热失重分析结果表明P(MMA-AN)在TiO2表面接枝率为15.9%。以甲基橙溶液为目标污染物,研究了P(MMA-AN)/TiO2复合粒子和TiO2对甲基橙的吸附和光催化降解甲基橙溶液的性能,结果表明:两种粒子对甲基橙的吸附都很少;在相同时间内,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解性能优于TiO2,紫外光照180 min后,P(MMA-AN)/TiO2复合粒子对甲基橙溶液的降解率达到了88%,而TiO2仅为74%。     

The combination of rotating disk photocatalytic reactor and TiO2 nanotube arrays for environmental pollutants removal

A combined photocatalytic system on one single TiO(2)-nanotube (TNT)/Ti photocatalyst, which was indeed the functional combination of photon-efficient thin-film and conventional bulk-phase photocatalysis processes, was effectively developed in rotating disk photocatalytic reactor for environmental purification applications. The TNT/Ti rotating disk, of uniform size and well-aligned, was successfully prepared by direct anodic oxidation on a dominantly large surface area of 38 cm(2), compared to the typical 1 cm(2) in available literature. To estimate the potentials of combined photocatalytic system for environmental applications, the degradation of rhodamine B was carried out under the optimized conditions, a substrate removal efficiency of nearly 90% and a mineralization efficiency of 56% were observed for initial 20 mg/L solution after 3 h treatment. Compared with the combined photocatalytic system on TiO(2) nanoparticle disk, a significant improvement in substrate removal efficiency of about 25-40% was observed on TNT/Ti disk. It was confirmed that the main degradation of rhodamine B occurred on the upper half of TNT/Ti disk above the heavily colorized sample solution, which was attributed to the superior UV utilization efficiency and the resultant high interfacial photoactivity.     

硫掺杂TiO2/Ti光电极制备及其可见光光电催化性能

为了提高TiO2/Ti光电极在可见光下的光电催化活性,采用阳极氧化法制备了一种新型的硫掺杂TiO2/Ti光电极.采用扫描电子显微镜、X射线衍射、X射线荧光光谱等技术对光电极进行了表面形貌、结晶形态、晶粒尺寸、硫的掺杂量和价态以及吸光性能表征.研究表明:硫掺杂TiO2/Ti光电极的最佳制备条件为:成膜电压160V、电流密度100mA/cm2、Na2SO3质量浓度750mg/L;所制备的光电极具有良好的光电催化氧化降解邻苯二甲酸二甲酯活性,并能有效地矿化其中间产物;与TiO2/Ti电极相比,硫的掺杂可以显著提高其在可见光下的光电催化性能.     

F掺杂TiO2纳米管阵列的可见光催化活性和电子结构

采用电化学阳极氧化法,在纯Ti表面一步制得原位生长的F掺杂TiO2纳米管阵列.对煅烧后样品进行扫描电镜(SEM)、X射线多晶衍射(XRD)表征.结果表明,所得TiO2纳米管排列整齐、平均管径约40 nm,平均管长约700 nm.XPS蚀刻分析发现,少量F原子以F-Ti-O键的形式掺杂进了TiO2晶格,同时产生活性物质T...     

Surface modification of nanometer size TiO2 with salicylic acid for photocatalytic degradation of 4-nitrophenol

The efficiency of photocatalytic reactions was limited by the wide band-gap of TiO(2) and the high degree of electron-hole recombination inherent in photocatalytic process, as well as by the limited adsorption capability of photocatalysts. In order to increase the overall efficiency, the surface of nanometer size TiO(2) was simply and fast modified by chemical adsorption in saturated solution of salicylic acid. A stable, light yellow surface complex was formed quickly, which has obvious absorption in the region from 320 to 420 nm. Through surface modification, the adsorption efficiency of 4-nitrophenol by TiO(2) was enhanced from 42 to 84%. The photocatalytic efficiency was tested on the degradation of 4-nitrophenol. The influences of catalyst and its dosage, pH value, and 4-nitrophenol concentration on the degradation were investigated. Under such photodegradation conditions as initial pH 4.0, 4-nitrophenol 5 mg l(-1), catalyst 100 mg, and irradiation time 160 min with 160 W high-pressure mercury lamp, the degradation efficiency of 4-nitrophenol by TiO(2) was increased from 39.5 to 79.3% after surface modification, and furthermore, the degradation efficiency could be enhanced to 91.1% if the concentration of 4-nitrophenol was not more than 1 mg l(-1). Compared with the pure TiO(2), surface modification led not only to improve the surface coverage of 4-nitrophenol, but also to increase the light utilization. Both of these factors were crucial for the photocatalytic activity of heterogeneous photocatalysis, especially for photodegradation of aromatic pollutants.     

Photocatalytic activity of heterostructures based on TiO2 and halloysite nanotubes

A one-step solvothermal method was used to prepare TiO(2)/halloysite composites. TiO(2) nanoparticles were deposited on the platform of the halloysite nanotubes (HNTs). XRD, FT-IR, FE-SEM, and TEM were applied to investigate the structures and morphologies of the resultant samples. The as-prepared TiO(2)/HNTs photocatalyst exhibits pH sensibility on the degradation of methanol and a higher photocatalytic activity on the degradation of acetic acid. The combination of the photocatalytic property of TiO(2) and the unique structure of halloysite endowed this material with a bright perspective in degradation of organic pollutant.     

Titanium dioxide-mediated heterogeneous photocatalytic degradation of terbufos: parameter study and reaction pathways

The photocatalytic degradation of terbufos in aqueous suspensions was investigated by using titanium dioxide (TiO(2)) as a photocatalyst. About 99% of terbufos was degraded after UV irradiation for 90 min. Factors such as pH of the system, TiO(2) dosage, and presence of anions were found to influence the degradation rate. Photodegradation of terbufos by TiO(2)/UV exhibited pseudo-first-order reaction kinetics, and a reaction quantum yield of 0.289. The electrical energy consumption per order of magnitude for photocatalytic degradation of terbufos was calculated and showed that a moderated efficiency (E(EO)=71 kWh/(m(3)order)) was obtained in TiO(2)/UV process. To obtain a better understanding of the mechanistic details of this TiO(2)-assisted photodegradation of terbufos with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) technique. The probable photodegradation pathways were proposed and discussed.     

Ce掺杂TiO2薄膜电极光电催化降解甲基橙

用溶胶-凝胶法制备了泡沫镍负载TiO2及Ce离子掺杂TiO2薄膜电极,并以其为工作电极,建立了三电极光电催化体系。通过对水溶液中甲基橙的降解实验,考察了催化剂热处理温度、涂敷层数、外加电压、铈掺杂等因素对薄膜催化剂光催化性能的影响,结果表明,泡沫镍是光催化剂的优良载体;经500℃处理所得催化剂主要为锐钛矿相,催化活性最好;外加适当电压,有助于光催化降解;Ce的掺杂有易于TiO2催化活性的改善;外加适当电压有助于甲基橙的光催化降解。研究证明,500℃为铈掺杂TiO2薄膜的最佳热处理温度,外加一定电压、涂敷3层、掺杂n(Ce)/n(Ti)=2%的铈时催化剂的活性最高。     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: preparation and photocatalytic behavior of TiO2/Sr2CeO4

The paper demonstrates that the photocatalytic activity of TiO(2) towards the decomposition of gaseous benzene in a batch reactor can be greatly improved by loading TiO(2) on the surface of Sr(2)CeO(4). The research investigates the optimum loading amount of TiO(2) on Sr(2)CeO(4) in enhancing the photocatalytic activity of TiO(2). The prepared photocatalyst was characterized by XRD, UV-vis diffuse reflectance and XPS analyses. TiO(2) is loaded on Sr(2)CeO(4) at 773K. TiO(2)/Sr(2)CeO(4) absorbs much more visible light than TiO(2). The XPS spectrum shows that there are Ti, O, C, Sr elements on the surface of the TiO(2)/Sr(2)CeO(4), and that the binding energy value of Ti2p transfers to a lower value. TiO(2)/Sr(2)CeO(4) demonstrates 2.0 times the photocatalytic activity of pure TiO(2). Based upon these observations, the mechanistic role of Sr(2)CeO(4) in the photocatalytic oxidation reaction has been suggested.     

复合电沉积制备SnO2/TiO2薄膜及其光电催化性能

为了寻求廉价、高效和稳定的光催化剂,用复合电沉积技术在紫铜片上制备了Sn/TiO2薄膜,经300℃热氧化使之形成SnO2/TiO2复合电极.利用SEM,XRD对薄膜进行了表征,以甲基橙为模型化合物,对复合电极的光催化和光电催化性能进行了测定.研究表明:该薄膜由0.3~1μm的颗粒构成,每个颗粒又由纳米晶粒形成;电极具有多孔结构,膜中的SnO2以两种不同的晶体结构存在;在薄膜质量相等的情况下,SnO2/TiO2薄膜的光催化活性是纯TiO2粒子膜的2.87倍;外加一定偏压下,其催化性能大幅度提高.     

Studies on photodegradation of two commercial dyes in aqueous phase using different photocatalysts

The present study involves the photocatalytic degradation of Methyl Orange (MO) and Rhodamine 6G (R6G), employing heterogeneous photocatalytic process. Photocatalytic activity of various semiconductors such as titanium dioxide (TiO(2)), zinc oxide (ZnO), stannic oxide (SnO(2)), zinc sulphide (ZnS) and cadmium sulphide (CdS) has been investigated. An attempt has been made to study the effect of process parameters viz., amount of catalyst, concentration of dye and pH on photocatalytic degradation of MO and R6G. The experiments were carried out by irradiating the aqueous solutions of dyes containing photocatalysts with UV and solar light. The rate of decolorization was estimated from residual concentration spectrophotometrically. Similar experiments were carried out by varying pH (2-10), amount of catalyst (0.25-2.0g/l) and initial concentration of dye (5-200mg/l). The experimental results indicated that the maximum decolorization (more than 90%) of dyes occurred with ZnO catalyst and at basic pH and the maximum adsorption of MO was noticed at pH 4 and of R6G at pH 10. The percentage reduction of MO and R6G was estimated under UV/solar system and it was found that COD reduction takes place at a faster rate under solar light as compared to UV light. In case of R6G, highest decolorizing efficiency was achieved with lower dose of catalyst (0.5g/l) than MO (1g/l) under similar conditions. The performance of photocatalytic system employing ZnO/solar light was observed to be better than ZnO/UV system.     

Photocatalytic decompositions of gaseous HCHO over Ag/TiO2 nanotube arrays

TiO2 nanotube arrays prepared by electrochemical anodization method attract considerable interest as a practical air purifier, as the nanotube arrays may form a TiO2 film with a porous surface and straight gas diffusion channel. Here, the TiO2 and Ag/TiO2 nanotube arrays with different Ag amount are used to degrade gaseous HCHO pollutants. The photocatalytic results confirm that the HCHO-degrading efficiency of the TiO2 nanotube arrays may vary with the amount of Ag nanoparticles, and the Ag amount within a certain range significantly improves the degradation rate of HCHO molecules. The main final product after HCHO degradation is detected to be CO2. Ag nanoparticles effectively act as electron trappers prohibiting the recombination of photo-excited electrons and holes, hence increasing the photocatalytic efficiency. However, excessive Ag nanoparticles form new recombination center of photo-excited electrons and holes to decrease the photocatalytic efficiency.     

Super-long aligned TiO2/carbon nanotube arrays

5?mm long aligned titanium oxide/carbon nanotube (TiO(2)/CNT) coaxial nanowire arrays have been prepared by electrochemically coating the constituent CNTs with a uniform layer of highly crystalline anatase TiO(2) nanoparticles. While the presence of the TiO(2) coating was confirmed by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and x-ray diffraction, the resultant TiO(2)/CNT coaxial arrays were demonstrated to exhibit minimized recombination of photoinduced electron-hole pairs and fast electron transfer from the long TiO(2)/CNT arrays to external circuits. This, in conjunction with the aligned macrostructure, facilitates the fabrication of TiO(2)/CNT arrays for various device applications, ranging from photodetectors to photocatalytic systems. Thus, the millimeter long TiO(2)/CNT arrays represent a significant advance in the development of new macroscopic photoelectronic nanomaterials attractive for a variety of device applications beyond those demonstrated in this study.     

TiO2纳米颗粒的制备、光催化性能及羟基自由基研究

采用聚丙烯酰胺凝胶法制备了TiO2纳米颗粒,利用X射线衍射、扫描电子显微镜和紫外．可见光漫反射光谱分别研究了不同煅烧温度对样品晶相、颗粒形貌和带隙的影响．以甲基橙（M0）为目标降解物,在紫外光照射下考察了制得的TiO2样品的光催化性能．研究结果表明,500℃煅烧制备的样品光催化性能最好;随着催化剂用量的增加,MO降解率呈现先增大后减小的趋势,最佳催化剂用量为4．0g／L;在pH值不太高时（≤7．2）,M0降解率随pH值的升高呈下降趋势．以香豆素为探测剂．采用荧光光谱检测催化剂在紫外光照射下产生羟基自由基（·OH）的情况,研究了煅烧温度、催化剂用量和溶液pH值对·0H产率的影响．研究结果还表明,·OH产率与MO降解率的变化规律基本一致,表明·0H可能是TiO2光催化降解有机染料的主要活性物种．     

TiO2／海泡石催化剂的光催化降解性能

以钛酸四丁酯为前驱体,采用水解．沉淀法制备纳米TiO2,再将其负载于海泡石上制得TiO2/海泡石催化剂,用X射线衍射和扫描电子显微镜对载体催化剂的形貌及晶型进行了分析．以紫外光为光源,在水溶液中以环境激素邻苯二甲酸二乙酯（DEP）为降解底物进行光催化性能的研究．结果表明：催化剂的用量和TiO2的负载量对光催化降解速率都有影响．其中TiO2/海泡石催化剂的用量起主要作用,更能影响其光催化速度及DEP的降解．当催化剂用量为4g/L、TiO2负载量为30％时,TiO2/海泡石催化剂的催化效果较好．     

TiCl3、TiCl4共水解制备金红石相氧化钛粉体

通过TiCl3、TiCl4共同水解可以制备出金红石相的氧化钛粉体．改变原料浓度可以控制产物的形貌，较高浓度下得到300—500nm的球状颗粒，由许多细小晶粒组成；较低浓度下得到纳米针状颗粒．提高TiCl3的浓度可以使晶粒尺寸有所减小．