铂铈共掺杂纳米TiO2的制备、表征及光催化性能

以钛酸四丁酯为前驱体，过氧化氢为氧化剂，采用简单易行的低温氧化法制备出晶粒尺寸较小（平均尺寸25nm）的二氧化钛纳米粒子。通过贵金属Pt掺杂TiO2（Pt-TiO2）、稀土元素Ce掺杂TiO2（Ce-TiO2）和Pt、Ce共掺杂TiO2（Pt／Ce-TiO2）的掺杂的方法对二氧化钛进行改性。通过XRD，XPS，TEM，紫外漫反射等表征手段对制备的样品进行表征。通过可见光下降解罗丹明B来测试其光催化活性。实验结果表明，由ce掺杂的TiO2光催化剂对有机污染物的最大降解能力略大于Pt掺杂的TiO2，2种元素进行共同掺杂时对应的TiO2光催化剂降解能力最大。     

掺Ni^2＋的TiO2颗粒光催化性能的研究

通过溶胶．凝胶法制备掺杂Ni^2＋的纳米TiO2，并用XRD和TEM进行了表征，发现Ni^2＋的掺杂减小了TiO2颗粒的粒径，Ni2＋／TiO2晶型为锐钛型。通过对目标物罗丹明B的光催化降解实验，发现Ni^2＋的掺杂提高了TiO2的光催化活性，其降解罗丹明B的反应遵从一级反应动力学方程，Ni^2＋惨杂量为1．2％时的光催化活性最高。     

Ce掺杂纳米TiO2光催化剂的制备及降解甲醛的研究

介绍了溶胶-凝胶法制备Ce离子掺杂纳米TiO2的工艺流程。采用X射线衍射（XRD）、紫外可见分光光度法（UV-Vis）等方法表征了Ce掺杂TiO2的相组成、紫外可见漫反射率与掺杂量的关系。结果表明，掺杂的TiO2在520℃．650℃焙烧2h呈锐钛矿结构，在520℃焙烧2h的TiO2的晶粒尺寸大约为20nm，而掺杂Ce后其晶粒尺寸均减小，大约为12nm。UV-Vis吸光度分析表明，掺Ce后吸收带边明显发生红移，但随着Ce掺杂浓度的增大，其对可见光的吸收影响不大。光催化降解反应表明，未掺杂Ce的TiO2反应2h后对甲醛的没有降解作用，而Ce掺杂TiO2反应2h后甲醛降解率达15％。     

可见光下H2La2Ti3O10／TiO2光催化降解有机染料的研究

通过固相反应、离子交换、粒子插入等一系列反应合成一种层状纳米光催化复合材料H2La2Ti3O10／TiO2。可见光照射下，对选定的染料模型——甲基橙溶液(20mg／L)、汽巴克隆黄(100mg／L)、依利尼尔红(100mg／L)溶液做光降解实验。结果表明，在可见光照射下，H2La2Ti3O10／TiO2均能对溶液中甲基橙、汽巴克隆黄、依利尼尔红有效降解，光照30min后，其对溶液中甲基橙、汽巴克隆黄、依利尼尔红的降解率分别可达60．4％、60．7％和72．0％，而标准TiO2(P-25)仅为6．2％、10．6％和12．3％。     

纳米TiO2薄膜在不同陶瓷表面的负载及其光催化性能研究

利用2种不同表面处理的陶瓷作为载体，用溶胶凝胶法在其表面进行了纳米TiO2光催化薄膜的负载。采用X射线衍射法（XRD）、X射线光电于能谱仪（XPS）和扫描电镜（SEM）对薄膜的粒径、横断面及表面组成进行了表征和分析，结果表明，TiO2的平均粒径约为15nm，釉面陶瓷TiO2薄膜分布均匀，膜厚约为300nm；无釉陶瓷TiO2薄膜分布不均，膜层不明显；2种载体中的一些基质离子在TiO2薄膜有渗透。苯酚的降解实验表明，以2种不同表面处理的陶瓷为载体的TiO2薄膜对苯酚的降解均符合一级反应动力学，就催化活性而言，TiO2／釉面陶瓷〉TiO2／无釉陶瓷，分析认为基质渗透的Ca^2＋有降低TiO2光催化活性的作用；该薄膜对实际生产多菌灵废水具有催化降解作用。重复降解实验20次，TiO2／釉面陶瓷和TiO2／无釉陶瓷对苯酚的去除率仅分别降低9％和6％。     

纳米TiO_(2-x)N_x催化剂的制备及其活性研究

以钛酸丁酯为前驱物、无水乙醇作溶剂、二乙醇胺作为抑制剂,采用溶胶-凝胶法制备TiO2溶胶,在NN3气流中直接进行热处理,制备一系列不同焙烧温度的淡黄色的掺氮纳米TiO2粉体.经XRD、UV-Vis和FTIR分析表明,实验制得的TiO2-xNx在350、400、450、500和550℃热处理3 h后仍为锐钛型;450℃保温3 h掺氮样品具有最佳的紫外-可见光响应,其吸收边红移至720 nm左右.罗丹明B的可见光降解实验及产物分析表明,掺氮样品具有良好的可见光催化活性.     

纳米TiO2-xNx催化剂的制备及其活性研究

以钛酸丁酯为前驱物、无水乙醇作溶剂、二乙醇胺作为抑制剂,采用溶胶-凝胶法制备TiO2溶胶,在NN3气流中直接进行热处理,制备一系列不同焙烧温度的淡黄色的掺氮纳米TiO2粉体。经XRD、UV-Vis和FTIR分析表明,实验制得的TiO2-xNx在350、400、450、500和550℃热处理3 h后仍为锐钛型;450℃保温3 h掺氮样品具有最佳的紫外-可见光响应,其吸收边红移至720 nm左右。罗丹明B的可见光降解实验及产物分析表明,掺氮样品具有良好的可见光催化活性。     

复合纳米Fe2O3/TiO2可见光催化降解邻甲酚溶液的研究

以复合纳米Fe2O3／TiO2作为催化剂,日光色镝灯为光源,研究了邻甲酚溶液的可见光降解。考察了催化剂制备方法、催化剂使用量、溶液pH、催化剂重复使用等条件对可见光降解的影响。实验结果表明,1％Fe2O3／TiO2（n）对邻甲酚溶液的可见光降解效果最优,比Ti02（p25）的降解率提高了2．6倍。在实验条件下,可见光降解3h,邻甲酚溶液的浓度去除率达95．4％,TOC去除率为72．3％。在较宽的浓度范围内,邻甲酚的反应服从一级动力学反应方程,随着浓度的增大,反应速率常数不断降低。     

臭氧与TiO2/UV协同降解对氯苯酚

利用O3／UV、TiO2／UV和O3／TiO2／UV降解对氯苯酚表明，臭氧与TiO2／UV具有明显的协同作用，如在本实验条件下降解5min后，上述3者对对氯苯酚的去除率分别为55％、10％和77%。O3／TiO2／UV协同作用的本质是由于臭氧能带走二氧化钛光致电子空穴对中的电子，从而产生了更多的羟基自由基，加速了有机物的降解。     

Ce掺杂纳米TiO2光催化剂的制备及降解甲醛的研究

介绍了溶胶-凝胶法制备Ce离子掺杂纳米TiO2的工艺流程.采用X射线衍射(XRD)、紫外可见分光光度法(UV-Vis)等方法表征了Ce掺杂TiO2的相组成、紫外可见漫反射率与掺杂量的关系.结果表明,掺杂的TiO2在520℃、650℃焙烧2 h呈锐钛矿结构,在520℃焙烧2 h的TiO2的晶粒尺寸大约为20 nm,而掺杂Ce后其晶粒尺寸均减小,大约为12nm.UV-Vis吸光度分析表明,掺Ce后吸收带边明显发生红移,但随着Ce掺杂浓度的增大,其对可见光的吸收影响不大.光催化降解反应表明,未掺杂Ce的TiO2反应2 h后对甲醛的没有降解作用,而Ce掺杂TiO2反应2 h后甲醛降解率达15%.     

固定化催化剂TiO2膜光催化降解三氯乙醛的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果,探讨了TiO2膜光催化降解三氯乙醛的机理,考察了溶液pH值和三氯乙醛初始浓度埘TiO2膜光催化降解三氯乙醛的影响,并研究了固定化催化剂TiO2膜光催化降解三氯乙醛的动力学.结果表明,固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果良好,当三氯乙醛初始浓度为2.25 mg/L时,在紫外光照时间3 h下,三氯乙醛的降解率高达100%.在相司紫外光照时间下,三氯乙醛的光催化降解率随着三氯乙醛初始浓度的增大而下降.在溶液pH=6.5时,三氯乙醛的降解效率最高.固定化催化剂TiO2膜光催化降解三氯乙醛的反应遵循一级反应动力学,反应速率常数随三氯乙醛初始浓度的增大而减小.     

UV–visible light-activated Ag-decorated,monodisperse TiO2 aggregates for treatment of the pharmaceutical oxytetracycline

Noble metal Ag-decorated, monodisperse TiO₂ aggregates were successfully synthesized by an ionic strength-assisted, simple sol–gel method and were used for the photocatalytic degradation of the antibiotic oxytetracycline (OTC) under both UV and visible light (UV–visible light) irradiation. The synthesized samples were characterized by X-ray diffraction analysis (XRD); UV–vis diffuse reflectance spectroscopy; environmental scanning electron microscopy (ESEM); transmission electron microscopy (TEM); high-resolution TEM (HR-TEM); micro-Raman, energy-dispersive X-ray spectroscopy (EDS); and inductively coupled plasma optical emission spectrometry (ICP-OES). The results showed that the uniformity of TiO₂ aggregates was finely tuned by the sol–gel method, and Ag was well decorated on the monodisperse TiO₂ aggregates. The absorption of the samples in the visible light region increased with increasing Ag loading that was proportional to the amount of Ag precursor added in the solution over the tested concentration range. The Brunauer, Emmett, and Teller (The BET) surface area slightly decreased with increasing Ag loading on the TiO₂ aggregates. Ag-decorated TiO₂ samples demonstrated enhanced photocatalytic activity for the degradation of OTC under UV–visible light illumination compared to that of pure TiO₂. The sample containing 1.9 wt% Ag showed the highest photocatalytic activity for the degradation of OTC under both UV–visible light and visible light illumination. During the experiments, the detected Ag leaching for the best TiO₂-Ag photocatalyst was much lower than the National Secondary Drinking Water Regulation for Ag limit (0.1 mg L^?1) issued by the US Environmental Protection Agency.     

Solar light–driven photocatalytic degradation and mineralization of beta blockers propranolol and atenolol by carbon dot/TiO2 composite

Herein improved solar light–driven photocatalytic degradation and mineralization of two emerging pollutants as well as recalcitrant beta blockers propranolol (PR) and atenolol (AT) have been demonstrated by metal-free carbon dot/TiO₂ (CDT) composite. Hydrothermally synthesized TiO₂ has been decorated with electrochemically synthesized carbon dots (CDs) and was well characterized by various analytical techniques viz. XRD, FTIR, Raman, XPS, UV–visible DRS, FESEM, and TEM. The optimized CDT composite, 2CDT (2 mL carbon dot/TiO₂), showed?~?3.45- and?~?1.75-fold enhancement in the photodegradation rate as compared to pristine TiO₂ for PR and AT respectively in 1 hour of irradiation along with complete degradation of PR and AT after 3 hours of irradiation. 2CDT exhibited 76% and 80% mineralization of PR and AT in contrast with 62% and 47% observed by pristine TiO₂. Further, the major reaction intermediates formed after degradation have been identified by HPLC/MS analysis, confirming more than 99% reduction of the parent compound for both PR and AT. Reusability of the optimized catalyst also showed successful degradation up to 3 cycles, showing reduction abilities of 97%, 95%, and 94% for 1st, 2nd, and 3rd cycle respectively. The enhanced degradation and mineralization efficiency of the 2CDT composite could be attributed to the excellent photosensitizer and electron reservoir properties of the CD along with upconverted photoluminescence behavior. The present study unlocks the possibility of using metal-free, facile CDT composite for effective degradation and mineralization of widely used beta blockers and other pharmaceuticals.

     

Effect of matrix on the electrochemical characteristics of TiO2 nanotube array-based PbO2 electrode for pollutant degradation

A series of lead dioxide electrodes developed on titania nanotube arrays with different matrix were fabricated by electrodeposition. Before the deposition of PbO₂, the matrix of this anode was electrochemically reduced in (NH₄)₂SO₄ solution and/or pre-deposited with certain amounts of copper. To gain insight into these pretreatments, the PbO₂ electrodes were characterized by SEM, LSV, and XRD, and their electrocatalytic activities for pollutant degradation were compared using p-nitrophenol (p-NP) as a model. It was confirmed that the electrochemical reduction with (NH₄)₂SO₄ resulted in the partial conversion of TiO₂ into Ti₄O₇ and Ti₅O₉, which increased the conductivity of PbO₂ anode, but decreased its electrochemical activity, while the Ti/TNTs*-Cu/PbO₂ electrode with both pretreatments possessed the highest oxygen evolution overpotential of 2.5 V (vs. SCE) and low substrate resistance. After a 180-min treatment on this electrode, the removal efficiency of p-NP reached 82.5 % and the COD removal achieved 42.5 % with the energy consumption of 9.45 kWh m^?3, demonstrating the best performance among these electrodes with different matrices. Therefore, this titania nanotube array-based PbO₂ electrode has a promising application in the industrial wastewater treatment.     

Fe_3O_4@SiO_2/TiO_2核壳结构纳米颗粒降解TNT溶液

针对TNT炸药废水具有成分复杂、排放量大、有毒等特点,立足于炸药废水在排放前的降解处理,研究开发一种基于核壳结构Fe3O4@SiO2/TiO2纳米颗粒的高效、可控回收、无二次污染且成本低的光催化降解方法。利用高温碳还原法和溶胶凝胶法制备了具有核壳结构的Fe3O4@SiO2/TiO2纳米颗粒。XRD分析表明,内核Fe3O4呈现磁铁矿特征,表面覆盖的纳米TiO2为锐钛矿型。磁滞回线测试结果显示,复合颗粒的饱和磁化强度为46.5 emu/g,N2吸附-解吸分析结果表明,该颗粒具有典型的介孔结构。使用Fe3O4@SiO2/TiO2纳米颗粒在紫外光下对含TNT废水进行降解,降解率达到81.9%,且颗粒的回收率达到88.4%,为实现高效、可控回收、无二次污染光催化-吸附降解TNT奠定了基础。     

碳纳米管/二氧化钛/壳聚糖催化薄膜光催化活性及苯降解机理

通过X-射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)和紫外可见光漫反射谱(UV-vis)对碳纳米管/二氧化钛/壳聚糖复合薄膜的晶体结构和形貌进行表征,以室内空气典型污染物气相苯为模型反应物,研究碳纳米管/二氧化钛/壳聚糖催化薄膜的光催化活性及其对苯的光降解机理。结果表明,制备的碳纳米管/二氧化钛/壳聚糖催化薄膜所具有的良好催化活性归功于碳纳米管、二氧化钛和壳聚糖三者的协调效应;气相苯光降解产生的主要中间产物是乙酸乙酯和十一烷,以及少量的丙烯醛、4-羰基-甲基-苯乙酮、十二烷烃、2,4,-二叔丁基苯酚、二十一烷烃。根据红外光谱分析与GC/MS分析结果,进一步提出了气相苯的降解机理过程。     

Study on particulates and volatile organic compounds removal with TiO2 nonwoven filter prepared by electrospinning

In this study, polyvinyl alcohol (PVA) and titania (TiO₂) Degussa P-25 were mixed to generate TiO₂ nonwoven filters using electrospinning. The wires of titanium dioxide and the nonwoven binding titania nanofibers were formed using 14 kV voltage and a distance of 15 cm. A single-factor experimental method was used to investigate the effects of parameters such as initial concentration, retention time, and light source on acetone removal by nonwoven binding titania nanofibers. Furthermore, the effects of parameters such as gas pressure, particle size, initial concentration, and retention time on the removal of particulates were also assessed. The results showed that the degradation efficiency increased with decreasing initial concentrations and increasing retention time. The best operational conditions during this study for the removal of acetone using the TiO₂ nonwoven filters were a retention time of 100 sec, initial acetone concentration of 250 ppm, and ultraviolet (UV) light source of 254 nm. Under those conditions, 99% acetone removal efficiency was obtained. In addition, 90% particulate matter removal efficiency was reached when the particulate size was greater than 200 nm and the reaction time was longer than 5 minutes. The prepared TiO₂/nanofiber has good performance for volatile organic compounds (VOCs) and particulate removal at the same time.

Implications: In this study, polyvinyl alcohol (PVA) and titania (TiO₂) Degussa P-25 were mixed to generate TiO₂ nonwoven filters using electrospinning. The results showed that the optimum operating conditions for the removal of acetone using the TiO₂ nonwoven filters were a retention time of 100 sec, initial acetone concentration of 250 ppm, and UV light source of 254 nm. Under those conditions, 99% acetone removal efficiency was obtained.     

Photoassisted and photocatalytic degradation of sulfur mustard using TiO2 nanoparticles and polyoxometalates

The decomposition of highly toxic chemical warfare agent, sulfur mustard (bis(2-chloroethyl) sulfide or HD), has been studied by homogeneous photolysis and heterogeneous photocatalytic degradation on titania nanoparticles. Direct photolysis degradation of HD with irradiation system was investigated. The photocatalytic degradation of HD was investigated in the presence of TiO₂ nanoparticles and polyoxometalates embedded in titania nanoparticles in liquid phase at room temperature (33?±?2 °C). Degradation products during the treatment were identified by gas chromatography–mass spectrometry. Whereas apparent first-order kinetics of ultraviolet (UV) photolysis were slow (0.0091 min^?1), the highest degradation rate is obtained in the presence of TiO₂ nanoparticles as nanophotocatalyst. Simultaneous photolysis and photocatalysis under the full UV radiation leads to HD complete destruction in 3 h. No degradation products observed in the presence of nanophotocatalyst without irradiation in 3 h. It was found that up to 90 % of agent was decomposed under of UV irradiation without TiO₂, in 6 h. The decontamination mechanisms are often quite complex and multiple mechanisms can be operable such as hydrolysis, oxidation, and elimination. By simultaneously carrying out photolysis and photocatalysis in hexane, we have succeeded in achieving faster HD decontamination after 90 min with low catalyst loading. TiO₂ nanoparticles proved to be a superior photocatalyst under UV irradiation for HD decontamination.     

均相催化强化US/FCME协同体系降解硝基苯

考察了NaCl、AlCl3、Na2SiO3、CuSO44种均相催化剂对超声波(US)/铁炭微电解(FCME)协同体系降解硝基苯的催化效果,结果表明,CuSO4的催化效果最好,在体系反应液初始pH为3.0,混合填料投加量为5.0 g/L(铁炭质量比为1∶1),CuSO4投加量为800 mg/L时,体系对硝基苯的降解率达到99.2%,但溶液COD值仅下降了24.6%,矿化效果一般,红外光谱分析表明降解体系的主要中间产物为苯胺。     

组合阳极联合气体扩散阴极电催化降解苯胺

采用气体扩散电极为阴极，钛基氧化物（Ti／SnO2-Sb2O5-IrO2）和金属铁构成组合阳极，构建了新型电化学氧化体系用于降解有机污染物。利用该氧化体系，在不同实验条件下考察了苯胺降解的效果与降解过程的相关规律。结果表明，阴极电位、铁阳极通电时间以及苯胺初始浓度均显著影响苯胺的降解效果。当阴极电位为-0．7V，pH3．0，铁阳极通电时间20min时，电化学处理200mg／L苯胺480min，TOC的去除效率达到80．4％，矿化电流效率（MCE）为8．6％，显示了该氧化体系具有良好的有机物降解能力。此外，苯胺降解过程中氨氮和硝态氮浓度的变化表明，苯胺分子中的氮主要转化为NH4和NO3^-。