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0．98mg／L时，反应2．5h后的降解率为86％。     

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。     

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射线光电子能谱仪(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15 nm,釉面陶瓷TiO2薄膜分布均匀,膜厚约为300 nm;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Ca2 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%.     

SO_4~（2-）/TiO_2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。     

TiO2膜降解水中污染物的稳定性考察与再生方法研究

针对实际水处理中对催化剂性能的要求,以光催化降解苯酚溶液作为探针反应,考察了玻璃纤维网上负载的TiO2膜催化剂长期使用条件下的稳定性,研究了催化剂在自来水中使用失活后的再生方法.结果表明,经过50次使用之后,膜催化剂120 min反应对苯酚的降解率从100%下降至83%,总体上看,所制催化剂还是具有相当好的稳定性;在反应器中用蒸馏水浸泡配合光催化反应对TiO2膜催化剂进行原位再生是一种可行的再生途径.     

TiO2纳米管的水热合成表征及其光催化性能研究

采用水热化学反应的方法制备了TiO2纳米管,并采用TEM、XRD等分析手段对TiO2纳米管的形貌和晶相进行了表征,对比了管与粉的光催化性能.结果表明,采用该方法制得的TiO2纳米管的管径小、管形均匀,TiO2纳米管的光催化性能明显高于TiO2纳米粉.     

纳米二氧化钛的改性及光催化氧化烷烃研究

催化剂的表面结构是影响催化反应的重要因素之一.利用原位红外(In-situ FT-IR)、X射线衍射(XRD)和紫外-可见漫反射(UV-Vis DRS)等现代物理技术考察了热处理改性对纳米 TiO2的表面结构、晶相结构、粒子大小、比表面积和吸光性能的影响,采用In-situ FT-IR光谱着重研究了纳米TiO2催化剂上环己烷光催化降解机制及催化剂的结构特性与催化反应之间的相关性.研究表明,400 ℃条件下热处理纳米TiO2具有最佳光催化活性,适宜的表面结构、晶相结构、吸光能力及晶化度是纳米TiO2光催化剂高催化活性的主要原因.借助In-situ FT-IR光谱,观察到环己烷氧化的主要产物是CO2和H2O,同时捕捉到了中间产物CO以及乙酸,提出了环己烷光催化降解的可能机理.     

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.     

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％。     

可见光响应的碘掺杂TiO2光催化剂的制备及其作用机理

以钛酸四丁酯为前驱物制备了碘掺杂TiO2催化剂(I-TiO2),考察了碘掺杂量、水解水量、水解温度和煅烧温度对催化剂物理化学性质与光催化活性的影响。X射线衍射(XRD)结果显示,I-TiO2由锐钛矿相和金红石相组成。在可见光照射下,通过降解水溶液中的苯酚评价了I-TiO2催化剂的光催化性能。结果表明,在水解温度为20℃,水解水量为300 mL,煅烧温度为400℃,碘钛比(摩尔比)为20%的制备条件下,催化剂显示了最优的光催化活性。通过向反应体系中引入自由基捕获剂及降低溶解氧,证实光催化降解苯酚主要由光生空穴或吸附的羟基自由基引发。     

Performance of photocatalytic reactors using immobilized TiO2 film for the degradation of phenol and methylene blue dye present in water stream

TiO2 thin film photocatalyst was successfully synthesized and immobilized on glass reactor tube using sol-gel method. The synthesized TiO2 coating was transparent, which enabled the penetration of ultra-violet (UV) light to the catalyst surface. Two photocatalytic reactors with different operating modes were tested: (a) tubular photocatalytic reactor with re-circulation mode and (b) batch photocatalytic reactor. A new proposed TiO2 synthesized film formulation of 1 titanium isopropoxide: 8 isopropanol: 3 acetyl acetone: 1.1 H2O: 0.05 acetic acid (in molar ratio) gave excellent photocatalytic activity for degradation of phenol and methylene blue dye present in the water. The half-life time, t1/2 of photocatalytic degradation of phenol was 56 min at the initial phenol concentration of 1000 microM in the batch reactor. In the tubular photocatalytic reactor, 5 re-circulation passes with residence time of 2.2 min (single pass) degraded 50% of 40-microM methylene blue dye. Initial phenol concentration, presence of hydrogen peroxide, presence of air bubbling and stirring speed as the process variables were studied in the batch reactor. Initial methylene blue concentration, pH value, light intensity and reaction temperature were studied as the process variables in the tubular reactor. The synthesized TiO2 thin film was characterized using SEM, XRD and EDX analysis. A comparative performance between the synthesized TiO2 thin film and commercial TiO2 particles (99% anatase) was evaluated under the same experimental conditions. The TiO2 film was equally active as the TiO2 powder catalyst.     

TiO2膜降解水中污染物的稳定性考察与再生方法研究

针对实际水处理中对催化剂性能的要求，以光催化降解苯酚溶液作为探针反应，考察了玻璃纤维网上负载的TiO₂膜催化剂长期使用条件下的稳定性，研究了催化剂在自来水中使用失活后的再生方法。结果表明，经过50次使用之后，膜催化剂120 min反应对苯酚的降解率从100%下降至83%，总体上看，所制催化剂还是具有相当好的稳定性；在反应器中用蒸馏水浸泡配合光催化反应对TiO₂膜催化剂进行原位再生是一种可行的再生途径。     

Simultaneous photocatalytic reduction of Cr(VI) and oxidation of phenol over monoclinic BiVO4 under visible light irradiation

BiVO4 powder with monoclinic structure was prepared and used as a visible-light catalyst simultaneously for the photooxidation of phenol and the photoreduction of Cr(VI). The photocatalytic efficiency was found to be rather low for either single phenol solution or single Cr(VI) solution. However, the photocatalytic reduction of Cr(VI) and photocatalytic oxidation of phenol proceed more rapidly for the coexistence system of phenol and Cr(VI) than for the single process, showing synergetic effect between the oxidation and reduction reactions. For the simultaneous photocatalytic reduction-oxidation process, the first-order kinetic constant of phenol degradation was 0.0314 min-1, being about six times higher than that for the photocatalytic process of single phenol. This result reveals the feasibility of using Cr(VI) as the electron scavenger of mBiVO4-mediated photocatalytic process of phenol degradation, and gives us an enlightenment to employ other semiconductor with a better visible light response but with a more positive band edge to efficiently degrade organic pollutants. This is the first report for simultaneous photocatalytic reduction of Cr(VI) and removal of phenol under visible light irradiation using photocatalyst mBiVO4.     

Photocatalytic degradation of phenol using Ag core-TiO<Subscript>2</Subscript> shell (Ag@TiO<Subscript>2</Subscript>) nanoparticles under UV light irradiation

Ag@TiO₂ nanoparticles were synthesized by one pot synthesis method with postcalcination. These nanoparticles were tested for their photocatalytic efficacies in degradation of phenol both in free and immobilized forms under UV light irradiation through batch experiments. Ag@TiO₂ nanoparticles were found to be the effective photocatalysts for degradation of phenol. The effects of factors such as pH, initial phenol concentration, and catalyst loading on phenol degradation were evaluated, and these factors were found to influence the process efficiency. The optimum values of these factors were determined to maximize the phenol degradation. The efficacy of the nanoparticles immobilized on cellulose acetate film was inferior to that of free nanoparticles in UV photocatalysis due to light penetration problem and diffusional limitations. The performance of fluidized bed photocatalytic reactor operated under batch with recycle mode was evaluated for UV photocatalysis with immobilized Ag@TiO₂ nanoparticles. In the fluidized bed reactor, the percentage degradation of phenol was found to increase with the increase in catalyst loading.     

负载型TiO2固定相光催化降解含酚废水的试验研究

以20W紫外灯为光源,研究了将TiO2粉末负载在硅胶颗粒上,对含酚废水进行光催化降解.由试验得出光催化反应过程中的工艺条件,在此基础上添加H2O2、Fe3+、Cu2+,反应1 h后,苯酚的降解率达95%以上.     

PCDD/DF formations by the heterogeneous thermal reactions of phenols and their TiO2 photocatalytic degradation by batch-recycle system

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.     

Combined biological and photocatalytic treatment for the mineralization of phenol in water

Phenol is degraded by biological treatment, however mineralization requires long time. To decrease the time and operational cost necessary for the mineralization of phenol, an optimum operation condition of the combined biological–photocatalytical treatment was investigated. The mineralization of phenol (50 mg l⁻¹) was conducted in a flow-type biomembrane tank combined with a batch-type TiO₂-suspended photocatalytic reactor. Phenol was degraded biologically to the concentration of 6.8 mg l⁻¹, an effective concentration for further photocatalytic treatment. After the biological treatment, the biotreated phenol was treated photocatalytically to complete the mineralization of phenol. The combined treatment shortened the mineralization time compared to the biological treatment and electric cost compared to the photocatalytic treatment only. The combined treatment may be suitable for a short-time mineralization of phenol in wastewater.