含钛高炉渣制光催化剂降解水中2,4-二氯酚的研究

以攀钢含钛高炉渣为原料制备了光催化剂,并将其用于降解水中2,4-二氯酚,研究了光催化剂投加量、光照强度、反应物浓度、反应时间对2,4-二氯酚降解率的影响。结果表明:高炉渣制光催化剂对2,4-二氯酚具有良好的光催化效果,在催化剂投加量为0.3g/L,光照时间为2h的条件下,浓度为50mg/L的2,4-二氯酚的降解率达到了77.1%。通过反应的动力学分析,确立出高炉渣制光催化剂对水中2,4-二氯酚的降解反应为一级反应。对2,4-二氯酚的光催化降解产物进行分析发现,苯环上的C—Cl键被光催化剂产生的羟自由基·OH氧化断裂,氯取代基成为游离Cl-存在于溶液中,2,4-二氯酚被·OH降解生成中间小分子有机产物,这些小分子有机物再进一步被光催化降解。     

膜载Fe~(3+)/TiO_2光催化降解4-氟苯甲酸的研究

用自制半导体纳米Fe3+/TiO2玻璃薄膜,在高压汞灯下进行了光催化降解4-氟苯甲酸的研究。结果表明,反应光强、催化剂用量、pH值、溶解氧含量等反应条件改变对光催化降解效率具有显著的影响,光催化降解4-氟苯甲酸反应为一级动力学方程。     

四环素光催化降解特性与选择性研究

研究了盐酸四环素的光催化降解行为,结果表明四环素光催化降解反应符合一级反应动力学方程,吸附过程为整个光催化降解的控制步骤,推断四环素的主要降解途径是吸附在二氧化钛(TiO2)表面发生光催化氧化反应.同时,通过对四环素与磺胺甲唑或阿莫西林混合样品的降解实验表明,改变pH、TiO2投加量等因素,两种抗生素的降解表现出了明显的选择性.     

硅胶负载TiO2光催化降解吡啶

以硅胶为载体，钛酸四丁酯为原料，用溶胶-凝胶法制备负载型TiO2，在UV-TiO2体系中对吡啶(PD)进行光催化降解，并研究了降解体系的紫外吸收光谱和pH值对光催化降解体系的影响。结果表明：负载型TiO2光催化剂加入量为60mg／40ml，吡啶的光催化降解反应符合一级动力学方程；吡啶中氮转化成氨氮。碱性条件下的降解率高于酸性条件下的降解率；TiO2负载后利用率提高了6倍左右。     

Fe3+、Ce3+掺杂TiO2光催化降解气相二苯并呋喃

以气相二苯并呋喃为研究对象,考察了在TiO2、Ce3+/TiO2和Fe3+/TiO2 3种不同光催化剂作用下,反应物初始浓度、湿度、气体循环速率和光强等因素对间歇式光催化反应速率的影响,并建立了估算和测定二苯并呋喃光催化反应常数和Langmuir吸附常数的数学模型和方法.结果表明,Fe3+和Ce3+掺杂修饰TiO2光催化剂后,提高了对二苯并呋喃的光催化降解活性,其中Fe3+/TiO2光催化活性最高;随着二苯并呋喃初始浓度的增大,其光催化降解速率也随之增大;适量的水蒸气存在可以促进二苯并呋喃的降解,但当水蒸气过量后,反而阻碍二苯并呋喃光催化降解;随着气体循环速率加快和光强的增大,二苯并呋喃光催化降解初始速率也随之增大;TiO2、Ce3+/TiO2和Fe3+/TiO2光催化降解二苯并呋喃反应速率常数k分别为34.54×10-5、36.23×10-5和37.95×10-4mg.(min.m2)-1.     

活性炭负载纳米TiO2对腐殖酸光催化降解动力学

采用溶胶-凝胶法制备了以颗粒活性炭(GAC)为载体的纳米TiO2/AC复合催化剂,并将其用于腐殖酸的光催化降解.动力学研究表明,TiO2/AC光催化降解腐殖酸过程可用Langmuir-Hinshelwood(L-H)动力学模式表示.L-H表观反应速率常数KLH=0.1124mg·L-·1min-1,吸附平衡常数K*=0.3402L·mg-1.活性炭负载TiO2对腐殖酸的光催化降解过程,体现了活性炭与TiO2的协同作用,活性炭的吸附作用提高了光催化反应速率.     

邻-氯酚在TiO_2膜上光催化降解及反应动力学特征

以钛酸四丁酯为原料采用Sol Gel法制备了玻璃负载TiO2 膜光催化剂 ,应用XRD表征了不同实验条件下薄膜中TiO2 的晶相结构和粒度。分析了不同层数TiO2 膜的光催化活性和溶液 pH值对邻 氯酚 (2 CP)的影响。结果表明 :处理温度为 50 0℃时不同厚度薄膜中TiO2 均为锐钛矿晶型 ,粒径 8～ 33nm ,5层涂膜光催化活性最高。在高 pH值和低pH值区域 2 CP ,在TiO2 膜上的光催化降解速率较大。 2 CP初始浓度 (C0 )与反应速率 (r0 )的关系符合Langmuir Hinshelwood方程 ,当C0 ≤ 0 .6mmol·L- 1 时 ,降解反应可用一级动力学模式来描述。     

TiO2光催化降解水中内分泌干扰物17β-雌二醇

以低压汞灯为光源,采用间歇式光氧化反应器,研究了17β-雌二醇(E2)在纳米TiO2(Degussa P-25)悬浆体系中的光催化降解.考察了溶液pH、E2初始浓度、TiO2光催化剂投加量、UV光强、H2O2、O2对E2光催化降解的影响.结果表明,TiO2光催化工艺可以有效地去除水中的E2,E2的光降解过程符合一级反应动力学模型;TiO2投加量为200 mg/L时,在14 W低压汞灯照射下,初始浓度为400 μg/L的E2在自来水中的光降解一级反应速率常数为0.018 min-1,E2的光催化降解速率常数与其初始浓度、TiO2光催化剂的用量、溶液的pH值、UV光强等因素有关;外加H2O2、O2可以影响催化剂的光降解效率.     

微波辅助光催化降解兽药环丙氨嗪

利用微波光催化实验装置研究了水溶液中兽药环丙氨嗪的光催化降解,探讨了添加微波无电极灯(EDL)对降解反应的促进作用.结果表明,环丙氨嗪在微波辅助1.0g/L TiO2光催化体系中反应20min降解率可达99.6%,检测到的主要降解产物为三聚氰胺.环丙氨嗪在pH3.0~9.0范围内的微波辅助光催化降解率都高于99%;增加TiO2用量和EDL数量均显著提高其降解率.外源添加NO3-离子明显降低了环丙氨嗪的降解率,主要由于NO3-对紫外光的强吸收和在TiO2表面带正电的空穴位的吸附作用.     

TiO2薄膜降解印染废水的反应动力学研究

采用液相沉积法制备了石英砂负载纳米TiO2薄膜,对实际印染废水的光降解反应动力学进行了研究.结果表明:实际印染废水的光催化降解可用Langmuir-Hinshelwood 方程来描述,即浓度较高时,光催化降解符合零级动力学方程;浓度较低时,光催化降解在零级和一级反应之间.不同的pH值和H2O2投加量对反应的级数也有重要的影响,外加H2O2对光催化降解有极大的促进作用.     

Immobilization of self-assembled pre-dispersed nano-TiO2 onto montmorillonite and its photocatalytic activity

The immobilization of pre-dispersed Ti O_2 colloids onto the external surface of the clay mineral montmorillonite(Mt) was accomplished and regulated via a self-assembly method employing the cationic surfactant cetyltrimethylammonium bromide(CTAB). The role of CTAB in the synthesis process was investigated by preparing a series of Ti O_2-CTAB-Mt composites(TCM) with various CTAB doses. The results indicated that a uniform and continuous Ti O_2 film was deposited on the external surface of montmorillonite in the composite synthesized with 0.1 wt.% of CTAB, and the TCM nano-composites showed much higher values for specific surface area, average pore size and pore volume than the raw montmorillonite clay. Then, the formed TCM materials were applied in photocatalytic degradation of 2,4-dichlorophenol(2,4-DCP) in aqueous solution. The degradation efficiency reached as high as 94.7%. Based on the degradation intermediates benezoquinone, fumaric acid and oxalic acid identified by LC–MS analysis, a mechanism for the photocatalytic oxidation of 2,4-DCP on Ti O_2/Mt nano-composites is proposed.     

Immobilization of self-assembled pre-dispersed nano-TiO2 onto montmorillonite and its photocatalytic activity

The immobilization of pre-dispersed TiO₂ colloids onto the external surface of the clay mineral montmorillonite (Mt) was accomplished and regulated via a self-assembly method employing the cationic surfactant cetyltrimethylammonium bromide (CTAB). The role of CTAB in the synthesis process was investigated by preparing a series of TiO₂-CTAB-Mt composites (TCM) with various CTAB doses. The results indicated that a uniform and continuous TiO₂ film was deposited on the external surface of montmorillonite in the composite synthesized with 0.1 wt.% of CTAB, and the TCM nano-composites showed much higher values for specific surface area, average pore size and pore volume than the raw montmorillonite clay. Then, the formed TCM materials were applied in photocatalytic degradation of 2,4-dichlorophenol (2,4-DCP) in aqueous solution. The degradation efficiency reached as high as 94.7%. Based on the degradation intermediates benezoquinone, fumaric acid and oxalic acid identified by LC–MS analysis, a mechanism for the photocatalytic oxidation of 2,4-DCP on TiO₂/Mt nano-composites is proposed.     

Cr3+掺杂对TiO2薄膜光催化活性的影响

采用溶胶-凝胶法制备了TiO2粉末和以釉面瓷砖为载体的TiO2薄膜,讨论了不同Cr3+掺杂浓度对TiO2光催化活性的影响,并采用UVVIS对其光学性能进行了检测.结果表明,Cr3+掺杂和釉面瓷砖的交互作用能够显著提高TiO2薄膜的光催化活性,最佳掺杂浓度为6.04×1017个·cm-3,且随着TiO2光催化活性的提高,薄膜的吸收带边发生了明显的红移,提高了可见光的利用率.     

RGO/TiO2光催化降解2,4-二氯苯氧乙酸研究

通过Hummers法及紫外光/热还原工艺制得还原氧化石墨烯(RGO),采用溶胶-凝胶-煅烧法,以RGO和钛酸酊脂为前驱体制备出RGO/TiO2光催化复合材料,并利用XRD、FT-IR等对其进行了表征.对RGO/TiO2光催化降解性能的研究发现,复合光催化剂RGO/TiO2对2,4-二氯苯氧乙酸(2,4-D)的光催化降解活性显著优于纯TiO2,并且发现负载量和pH值对光催化降解性能有较大的影响:RGO/TiO2投加量为1.2g·L~(-1)、RGO负载量2%、pH为3、初始浓度为50 mg·L~(-1)反应12 h,2,4-D去除率达到98.75%;2,4-D降解率随着RGO/TiO2投加量的增大先增大后减小;RGO/TiO2对2,4-D的降解为脱氯还原和催化氧化过程,产生氯酚、苯酚等中间产物.     

Simulated-sunlight-activated photocatalysis of Methylene Blue using cerium-doped SiO2/TiO2 nanostructured fibers

Cerium-doped SiO₂/TiO₂ nanostructured fibers were fabricated by electrospinning technology. The prepared fibers were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Using the fibers as catalysts, photocatalytic degradation of Methylene Blue (MB) aqueous solution was carried out under simulated sunlight. The 0.2% Ce doping proved to be the optimal concentration for the doping of TiO₂/SiO₂, compared to other Ce-doped molar concentrations. The 0.2% Ce-doped SiO₂/TiO₂ fibers exhibited higher photocatalytic activity than industrial Degussa P25 and the samples doped with only Ce or SiO₂. The reasons for improving the photocatalytic activity were also discussed. Several operational parameters were studied, which showed that the photocatalytic efficiency of MB was influenced by parameters such as the initial dye concentration, the initial pH, inorganic anions, and so on. In addition, the influences of an electron acceptor and a radical scavenger suggested that OH was the dominant photooxidant during the photocatalytic process. The reuse evaluation of the fibers indicated that their photocatalytic activity had good stability.     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.     

Pd/TiO2对水体中2,4-二氯酚的催化加氢脱氯研究

分别采用沉淀-沉积法和浸渍法合成了Pd/TiO2催化剂,采用透射电镜(TEM)、X射线衍射(XRD)和电感耦合等离子体发射光谱(ICP-AES)对材料进行了表征,并对2,4-二氯酚的催化加氢脱氯反应进行了研究.结果表明,2种方法制备的催化剂在加氢脱氯反应中均具有较好的效果,沉淀-沉积法制备的催化剂活性更高,当反应物初始浓度为3.11 mmol.L-1,pH为12,催化剂用量为50 mg时,45 min内2,4-二氯酚可以完成脱氯过程.酸性条件有利于反应的进行.当催化剂用量在15～80 mg时,反应初活性没有明显变化,因此催化反应过程不受传质阻力的影响.当反应物初始浓度在0.62～3.11 mmol.L-1时反应初活性随浓度的提高显著增加,但进一步增加反应物的浓度时初活性没有明显提高,因此2,4-二氯酚在催化剂上的加氢脱氯行为符合Langmuir-Hinshelwood模型,表明2,4-二氯酚的加氢脱氯受表面吸附所控制.     

WC/TiO2纳米复合界面光催化剂制备及其光催化降解酚类污染物研究

设计并制备了新型WC/TiO2纳米复合界面光催化剂应用于酚类污染物的光催化降解反应中.采用X射线衍射(XRD)和扫描电子显微镜(SEM)技术分析了WC/TiO2纳米复合界面光催化剂的晶型和表面形貌.结果显示锐钛矿型TiO2纳米颗粒均匀地分散在WC纳米球表面并很好地构筑了WC/TiO2界面.研究了不同WC负载比例的WC/TiO2光催化剂在模拟太阳光照射下降解苯酚的光催化性能.结果表明:WC/TiO2复合界面的形成可以有效地提高TiO2光催化降解性能;其中,3%WC/TiO2(质量分数)光催化降解苯酚的活性最高.利用紫外-可见光谱(UV-Vis)和高效液相色谱-质谱联用技术(HPLC-MS)分析了WC/TiO2纳米复合界面光催化剂降解苯酚的中间产物,提出了苯酚在WC/TiO2界面上可能的降解机理.     

Fabrication and photoelectrocatalytic properties of nanocrystalline monoclinic BiVO4 thin-film electrode

Monoclinic bismuth vanadate(BiVO4) thin film was fabricated on indium-tin oxide glass from an amorphous heteronuclear complex via dip-coating.After annealation at 400,500,and 600°C,the thin films were characterized by X-ray diffraction,field emission scanning electron microscopy,X-ray photoelectron spectroscopy,and UV-Vis spectrophotometry.The BiVO4 particles on the ITO glass surface had a monoclinic structure.The UV-Visible diffuse reflection spectra showed the BiVO4 thin film had photoabsorption propertie...