Photocatalytic degradation of azo dyes by nitrogen-doped TiO2 nanocatalysts

This study examined the photocatalytic degradation of three azo dyes, acid orange 7 (AO7), procion red MX-5B (MX-5B) and reactive black 5 (RB5) using a new type of nitrogen-doped TiO2 nanocrystals. These newly developed doped titania nanocatalysts demonstrated high reactivity under visible light (lambda>390 nm), allowing more efficient usage of solar light. The doped titania were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Experiments were conducted to compare the photocatalytic activities of nitrogen-doped TiO2 nanocatalysts and commercially available Degussa P25 powder using both UV illumination and solar light. It is shown that nitrogen-doped TiO2 after calcination had the highest photocatalytic activity among all three catalysts tested, with 95% of AO7 decolorized in 1 h under UV illumination. The doped TiO2 also exhibited substantial photocatalytic activity under direct sunlight irradiation, with 70% of the dye color removed in 1h and complete decolorization within 3 h. Degussa P25 did not cause detectable dye decolorization under identical experimental conditions using solar light. The decrease of total organic carbon (TOC) and evolution of inorganic sulfate (SO4(2-)) ions in dye solutions were measured to monitor the dye mineralization process.     

SO2-4/TiO2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明:随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温(<550℃)焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时(>550℃)SO42-在TiO2表面是桥式配位吸附。     

制备条件对不同玻璃材料负载TiO_2活性影响研究

以光催化降解苯酚为探针反应,通过正交实验,系统研究了胶液配比、涂覆次数和焙烧温度等条件对以溶胶-凝胶法分别在普通钠钙玻璃和磨砂玻璃上制备TiO2光催化性能的影响,并利用环境扫描电镜（ESEM）对TiO2催化膜形貌进行了分析。研究表明,在普通钠钙玻璃片上负载TiO2催化膜的影响因素主次顺序为：硝酸体积〉涂覆次数〉焙烧温度〉V乙醇∶V酞酸丁酯,在选定实验条件下的最优条件为：涂覆次数为4次;焙烧温度=450℃;V乙醇∶V酞酸丁酯∶V硝酸（1∶4）：V水=400∶40∶1∶4。在磨砂玻璃片上负载TiO2催化膜的的影响因素主次顺序为：涂覆次数〉硝酸体积〉焙烧温度〉V乙醇：V酞酸丁酯,在选定实验条件下的最优条件为：涂覆次数为4次;焙烧温度=500℃;V乙醇∶V酞酸丁酯∶V硝酸（1∶4）∶V水=400∶40∶2∶4。通过扫描电镜可以观察到在普通钠钙玻璃片和磨砂玻璃片表面均附着一层白色的TiO2薄膜,颗粒粒径在100 nm左右。磨砂玻璃比普通钠钙玻璃负载更多的催化剂,磨砂玻璃基TiO2活性更高。磨砂玻璃是一种非常有前景的TiO2催化剂载体材料。     

TiO2/β-SiC foam-structured photoreactor for continuous wastewater treatment

Introduction

This study of photocatalytic degradation of wastewater was carried out in alveolar cell ??-SiC foam-structured photocatalytic reactors working in a recirculation mode. The immobilization of TiO2 on ??-SiC foams was efficiently obtained through a sol?Cgel technique in acidic conditions.

Discussion

In order to optimize degradation yields obtained by the foam-structured prototype reactor for the photocatalytic water treatment, the operating conditions of the photoreactor have been investigated and the efficiency of the process was evaluated by measuring the photocatalytic degradation of Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl-urea)) under UV irradiation. Kinetic studies were carried out by investigating the influence of different parameters controlling the reaction (TiO2 loading and ??-SiC foam cell size). The ageing of TiO2/??-SiC foam photocatalytic materials and the mineralization (TOC, Cl?, NO3? and NH4+) of Diuron were investigated.     

TiO₂ supported over SBA-15: an efficient photocatalyst for the pesticide degradation using solar light

Photocatalytic degradation and mineralization of pesticides are studied over TiO(2) supported mesoporous SBA-15 composite system using solar light. TiO(2) is immobilized over SBA-15 by solid sate dispersion method. The catalysts are characterized by XRD, surface area, UV-Vis diffused reflectance spectra, SEM and TEM. The detailed photocatalytic degradation studies are carried out over TiO(2), SBA-15 and different TiO(2) wt% supported SBA-15. The activity evaluation parameters such as catalyst amount, pH, and pollutant initial concentration are studied taking isoproturon as a model compound and established conditions for pesticide degradation. The optimum degradation is achieved over 10 wt% TiO(2)/SBA-15 within 30 min and the reaction is following pseudo-first order kinetics. The isoproturon mineralization is monitored with TOC reduction and it takes around 9h for disappearance. The commercial pesticide solutions containing imidacloprid and phosphamidon are also successfully degraded over these composites with the established conditions. The data indicates that 10 wt% TiO(2)/SBA-15 composite is an effective and highly active system for the pesticide degradations.     

纳米TiO2光催化氧化去除水中痕量双氯芬酸的研究

以TiCl4为前驱体,采用水解法经不同温度煅烧制备了具有不同理化性能的纳米TiO2光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、物理吸附仪、紫外—可见光漫反射吸收光谱(UV-Vis DRS)等手段对纳米TiO2的晶相结构、粒径、孔径分布以及禁带宽度等进行了表征。以蒸馏水配制的双氯芬酸溶液为目标物,进行了纳米TiO2光催化氧化去除双氯芬酸的活性测试,研究了纳米TiO2的理化性能与光催化氧化活性之间的关系。结果表明,经400℃煅烧制得的纳米TiO2样品具有最高的光催化氧化活性,其在紫外光照射60min下对双氯芬酸的去除率为98%左右,比单独紫外光照射高出85百分点。纳米TiO2光催化氧化去除双氯芬酸的反应近似一级反应动力学模型,其中经400℃煅烧制得的纳米TiO2光催化氧化去除双氯芬酸的表观反应速率常数为0.054 54min-1,是普通商用TiO2的2倍左右,与德国Degussa P-25TiO2的光催化氧化活性最相近。     

Photocatalytic degradation of isoproturon herbicide over TiO2/Al-MCM-41 composite systems using solar light

The present investigation covers immobilization of TiO2 using a simple solid state dispersion technique over mesoporous Al-MCM-41 support for the treatment of isoproturon herbicide. Catalysts are characterized by XRD, X-ray photo electron spectroscopy (XPS), surface area, UV-Vis diffused reflectance spectra (DRS), SEM and TEM. A detailed photocatalytic degradation study of isoproturon under solar light in aqueous suspensions is reported. The 10 wt% TiO2/Al-MCM-41 composite system found to be optimum with high degradation activity. The reaction follows pseudo-first order kinetics. The parameters like TiO2 loading over Al-MCM-41, amount of catalyst, concentration of substrate, pH effect, durability of the catalyst, activity comparison of TiO2 and Al-MCM-41 supported system are studied. The mineralization of isoproturon is monitored by TOC. Based on the degradation products detected through LC-MS, a plausible degradation mechanism is proposed. The data indicates that TiO2/Al-MCM-41 composite system is an effective photocatalyst for treatment of isoproturon in contaminated water.     

Enhanced photocatalytic reduction reaction over Bi(3+)-TiO(2) nanoparticles in presence of formic acid as a hole scavenger

A series of Bi(3+)-doped TiO(2) (Bi(3+)-TiO(2)) catalysts with a doping concentration up to 2wt% were prepared by a sol-gel method. The prepared photocatalysts were characterized by different means to determine their chemical composition, surface structure and light absorption properties. The photocatalytic activity of different Bi(3+)-TiO(2) catalysts was evaluated in the photocatalytic reduction of nitrate in aqueous solution under UV illumination. In the experiments, formic acid was used as a hole scavenger to enhance the photocatalytic reduction reaction. The experiments demonstrated that nitrate was effectively degraded in aqueous Bi(3+)-TiO(2) suspension by more than 83% within 150min, while the pH of the solution increased from 3.19 to 5.83 due to the consumption of formic acid. The experimental results indicate that the presence of Bi(3+) in TiO(2) catalysts substantially enhances the photocatalytic reaction of nitrate reduction. It was found that the optimal dosage of 1.5wt% Bi(3+) in TiO(2) achieved the fastest reaction of nitrate reduction under the experimental condition. Bismuth ions deposit on the TiO(2) surface behaves as sites where electrons accumulate. Better separation of electrons and holes on the modified TiO(2) surface allows more efficient channeling of the charge carriers into useful reduction and oxidation reactions rather than recombination reactions. Two intermediate products of nitrite and ammonia during the reaction were also monitored to explore the possible mechanisms of photoluminescence quenching and photocatalytic reduction in the context of donor-acceptor interaction with electron trapping centers.     

Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.     

Photocatalytic degradation of lignin using Pt/TiO2 as the catalyst

Photocatalytic degradation of lignin was studied with the use of catalysts TiO(2) and Pt/TiO(2). The influence of several experimental parameters, i.e. pH, catalyst dosage and illumination on lignin degradation was investigated. The results showed that application of UV irradiation alone has almost no effect on the reduction of dissolved organic carbon (DOC) and American Dye Manufacture Institute value (ADMI). However, the addition of TiO(2) and Pt/TiO(2) reduced the original DOC (251 mg l(-1)) by more than 40% within 30 min of treatment and the reaction can be simulated with pseudo-first order kinetics. Rapid degradation of lignin was observed in acidic solution using either TiO(2) or Pt/TiO(2) as the catalyst compared to high pH cases. The content of Pt in the Pt/TiO(2) catalyst is 1%. In addition, too much catalyst addition has not increased the DOC and ADMI reduction proportionally. The investigation also indicated that the photocatalytic degradation rates could be enhanced 1-6 times faster after doping TiO(2) with Pt in different pH cases. A modified Nernst type model was adopted to simulate the decoloring process using TiO(2) and Pt/TiO(2) based on the profiles of oxidation reduction potential during the photocatalytic reaction. The developed equation can be used to predict the color removal efficiency of lignin wastewater by the photocatalytic process.     

石英棒负载TiO2光催化膜的制备、表征与降解性能

利用浸涂法在石英光导棒上制得了TiO2光催化膜.用扫描电镜(SEM)、X射线衍射(XRD)等方法对膜的形貌和晶相组成进行了表征,以苯酚为模型污染物考察了膜的活性.结果表明,所制得的TiO2膜催化剂主要由锐钛矿和金红石2种晶相组成;光催化降解苯酚的效果明显优于直接光解;当苯酚初始浓度为0.98 mg/L时,反应2.5 h后的降解率为86%.     

Preparation of a titanium dioxide photocatalyst codoped with cerium and iodine and its performance in the degradation of oxalic acid

A novel class of visible light-activated photocatalysts was prepared by codoping TiO(2) with cerium and iodine (Ce-I-TiO(2)). The particles were characterized using the Brunauer-Emmett-Teller method, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and UV-Visible light absorption. Particles of Ce-I-TiO(2) had greater photoabsorption in the 400-800 nm wavelength range than iodine-doped TiO(2) (I-TiO(2)). The effects on the photocatalytic degradation of oxalic acid under visible light or UV-Visible light irradiation were investigated. The photocatalytic activity of Ce-I-TiO(2) calcined at 673 K was significantly higher than that of Ce-I-TiO(2) calcined at 773 K and I-TiO(2) calcined at 673 K in aqueous oxalic acid solution under visible light or UV-Visible light irradiation. Under visible light irradiation, oxalic acid was first adsorbed on the surface of the catalysts rather than reacted with free radicals in the bulk solution, and then oxidized by (·)OH(ads) to CO(2), which was verified by studying the effects of nitrogen purging and scavengers, as well as by gas chromatography/mass spectrometry.     

Photocatalytic production of hydrogen in single component and mixture systems of electron donors and monitoring adsorption of donors by in situ infrared spectroscopy

The photocatalytic production of hydrogen using aqueous Pt/TiO2 suspension has been investigated in single component and mixture systems of electron donors (pollutants). The reaction systems consisted of oxalic acid, formic acid and formaldehyde, respectively. The adsorption of these donors on TiO2 was also monitored by in situ attenuated total reflection infrared spectroscopy (ATRIR). In the single component systems, the efficiency order of electron donors is as follows: H2C2O4 > HCOOH > HCHO. The order is consistent with the order of adsorption affinity of the electron donors on TiO2 determined by ATRIR, which suggests a link between the strength of surface interaction and the efficiency of photocatalytic hydrogen evolution. In the binary mixture systems, competitive inhibition kinetics is observed. When a donor adsorbed strongly on TiO2 in a state of saturated adsorption in a binary system, the overall rate of the hydrogen evolution is consistent with that of decomposition of the donor, and the system can be treated as a single component system.     

Effect of ZnFe2O4 doping on the photocatalytic activity of TiO2

The photocatalytic oxidation of the organic pollutants with the TiO2 as photocatalyst has been widely studied in the world, and many achievements have been got. The degradation of pollutants is highly related with the photocatalytic activity of TiO2. It is demonstrated that doping ions or oxides to TiO2 is one way to enhance the photocatalytic activity of TiO2. In this paper, the ZnFe2O4-doped TiO2 nanoparticles were prepared from butyl titanate by a sol-gel method and characterized by means of X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that when TiO2 was doped with ZnFe2O4, its particle size will decrease and its crystal structure will partly transform from anatase to rutile. The photocatalytic activity of the elaborated powders was studied following the degradation of Rhodamine B. The results showed that doping ZnFe2O4 to TiO2 will enhance the photocatalytic activity of TiO2 and that ZnFe2O4-doped TiO2 in the coexistence of anatase and rutile has higher efficiency for the degradation of Rhodamine B than that in the anatase phase alone. Also the different role of O2 in the direct photolysis and photocatalysis of Rhodamine B was discussed.     

TiO2胶体光催化降解罗丹明B染料

TiO2胶体从钛氧有机物水解制备,表征的方法有:X射线衍射光谱(XRD)、激光散射粒径分布、傅立叶变换红外光谱(FT-IR)、X射线光电子谱(XPS)和透射电子显微镜(TEM)。利用罗丹明B染料分子作为探针分子研究TiO2胶体的光催化活性,分析了pH、催化剂用量、外加氧化剂(H2O2)用量及罗丹明B初始浓度对TiO2胶体光催化活性的影响。结果表明:制备的TiO2胶体粒子平均粒径为13.8 nm(激光散法测定),光催化降解罗丹明B染料的反应属于一级动力学反应,可以用Langmuir-Hinshewood模型加以描述,反应速率常数k1为0.08413 mg/(L.min),平衡吸附常数k2为1.5305 L/mg;在pH为6,TiO2胶体用量为0.04%,H2O2(含量30%)用量为0.2%(V/V),光照度为69.6μW/cm2时,5 h后罗丹明B染料的降解率可达到99%以上;相似的条件,0.2%的P25 TiO2粉体光催化处理染料水时,罗丹明B的降解率为90%。纳米TiO2胶体不仅可以提高罗丹明B的光催化降解率,还具有用量少,可有效降低水处理成本的特点。     

Photocatalytic degradation of pentachlorophenol on TiO2 sol-gel catalysts

The photocatalytic degradation of pentachlorophenol (PCP) in aqueous solution was investigated using TiO2 catalysts. The samples were prepared by the sol-gel method using different gelation pH and different calcination temperatures. The solids were characterized by specific surface area, X-ray diffraction, UV-Vis absorbance, FTIR and pentachlorophenol adsorption. The catalytic activity of the solids was evaluated in a conventional photoreactor at 298 K using 30 ppm of pentachlorophenol. It was found that the reaction follows a first-order reaction and the kinetic constant values change slightly with the pH of gelation and more significantly with the calcination temperature.     

模拟室内环境下掺杂TiO_2纳米晶体的光催化性能

采用环境测试舱模拟可见光下的室内环境,以甲醛气体的光催化降解为探针反应,评价了通过溶胶-凝胶法分别制备的8种（银Ag、铜Cu、铁Fe、钨W、铈Ce、镧La、硫S和氯C l）掺杂TiO2纳米晶体的光催化活性及对甲醛气体的去除效果。用X射线衍射、激光粒度分析和紫外-可见分光光谱表征了掺杂钠米TiO2的微晶尺寸、晶体结构与光学性能。结果表明,Cu掺杂可以提高TiO2对氧的吸附能力,减少纳米粒子表面光生电子与光生空穴的复合,使TiO2的光吸收带边发生红移且有利于对可见光的吸收,从而使Cu掺杂TiO2在模拟室内环境下光催化甲醛气体的能力得到明显提高。     

碘掺杂Ti02可见光光催化性能研究

在低于100℃温度条件下，采用溶胶一凝胶法以钛酸正丁酯为钛源，碘酸钾为碘源，制备了I掺杂纳米TiO2催化剂（I-TiO2），运用x-射线衍射（XRD）、透射电镜（TEM）及x-射线光电子能谱（XPS）等对催化剂进行表征，结果表明，TiO2及I-TiO2催化剂均为锐钛矿，I吸附并包裹在TiO2表面或以间隙进入的形式存在，并未进入TiO2晶格。通过在可见光照射下（A〉420nm）以罗丹明B（RhodamineB，RhB）的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能，结果表明，掺杂比为n1：n^ti=0．05：l，焙烧温度为400℃，降解介质条件pH=7时，l-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱（IR），总有机碳（TOC）跟踪测定，比较了TiO2掺杂前后降解RhB和对氯苯酚（4-CP）的光催化特性差异；同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种，表明在可见光下，I-TiO2光催化体系中产生·OH高活性氧化物种从而氧化降解目标化合物。     

CdS-TiO2/MWCNTs结构表征及其光催化性能

采用溶胶-凝胶法,制备了多壁碳纳米管（MWCNTs）负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜（TEM）、比表面分析（BET）、X射线衍射（XRD）和紫外-可见吸收光谱（UV-vis）等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明：纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。     

Photocatalytic degradation of cellulose bleaching effluent by supported TiO2 and ZnO

A cellulose bleaching effluent (E1) was degraded in batch conditions by photocatalysis using TiO2 and ZnO supported on glass Raschig rings. The effluent was completely decolourised and the total phenol content was reduced by 85% after 120 min treatment with both catalysts. Partial mineralization of the organic matter was confirmed by total organic carbon (TOC) reduction, approximately 50%. The residual organic matter shows a low acute toxicity as compared to the initial values and AOX values are strongly reduced after the photocatalytic oxidation. Molecular mass distribution showed that high molecular mass compounds were almost completely degraded.