TiO_2光催化法去除饮用水中的有机卤代物

利用自制TiO2 光催化剂 ,对饮用水中常见的氯消毒副产物三氯甲烷等有机卤代物进行了光催化去除研究 ,实验表明 ,对于三氯甲烷浓度为 10 0 μg/L的 5 0ml废水 ,当催化剂的用量为 0 .4g ,光照时间 3.0h ,溶液中H+ 的浓度为 1×10 -9mol/L时 ,三氯甲烷的光催化去除率达 95 .0 %以上 .同时对光催化去除三氯甲烷的机理进行了探讨 ,证明了三氯甲烷的TiO2 光催化去除反应遵循一级反应速率公式 :lnC =- 0 .75t+4 .30 .     

构树叶制备介孔TiO2/SiO2复合材料的光催化性能及其动力学研究

以构树叶为生物模板和硅源,以钛酸四丁酯(TBOT)为前驱体,采用浸渍法制备了不同质量分数(w(TiO₂)=0、2.6%、4.0%、5.5%、7.0%和8.6%)的TiO₂/SiO₂复合材料.采用XRD、FTIR、SEM、XPS、TEM、BET、XRF、UV-Vis DRS等对复合材料进行了表征.结果表明,TiO₂/SiO₂复合材料主要由锐钛矿相TiO₂组成,形成了平均粒径为500 nm的纳米球.该材料具有典型的介孔结构,平均孔径为7.2 nm,比表面积为50.42 m~2/g.以罗丹明B作为模型,在紫外光照射下进行光催化降解实验来评价不同材料的光催化活性及进行动力学研究.实验结果表明,与w(TiO₂)=0催化剂相比,改变TiO₂质量分数所制备的TiO₂/SiO₂材料均表现出较强的光催化活性,其中掺杂w(TiO₂)=5.5%的催化剂具有最优的催化性能...     

铁掺杂TiO2纳米粒子光催化氧化庚烯的研究

采用新的合成路线制得掺铁TiO₂纳米粒子, 通过光催化降解庚烯研究其气固复相光催化性能, 用XRD, UV-vis和XPS等方法研究了掺铁TiO₂纳米粒子的晶体结构、 光吸收特性及表面化学形态. TiO₂纳米粒子掺杂Fe³⁺后, TiO₂的光吸收阈值发生红移, 向可见光区拓展; Fe³⁺掺杂浓度和焙烧温度对掺铁TiO₂纳米粒子的气 固复相光催化降解活性有很大影响, 实验结果表明, 掺铁量为0.5%(摩尔分数), 焙 烧温度300 ℃时光催化降解活性最好.     

过渡金属掺杂TiO2纳米片的制备及其增强光催化性能研究

以钛酸四丁酯(TBOT)为反应物前驱体,采用溶剂热法制备了一系列过渡金属(TM=Mn, Co, Ni, Cu, Zn)掺杂TiO₂(TM-TiO₂)纳米片状结构光催化材料.利用XRD,TEM,UV-Vis DRS,XPS等手段表征了材料的结构、形貌及光学特性.通过罗丹明B(RhB)降解实验测试了上述材料的光催化活性并讨论了光催化作用机理.实验结果表明：与纯TiO₂相比,TM-TiO₂的光催化活性明显增强,不同的TM掺杂浓度对TM-TiO₂光催化性能的影响存在一定的差异,其中Cu-TiO₂表现出相较于其他4种过渡金属离子掺杂TiO₂更优的光催化性能.TM-TiO₂光催化性能的提高得益于离子掺杂在TiO₂晶格中引起的局部晶格畸变增强了TiO₂的光吸收能力,同时有效促进了光生电子与空穴的分离.     

纳米TiO2@酵母碳球对盐酸四环素的吸附-光催化协同效应及响应面优化

通过生物自组装法制备得到纳米TiO₂@酵母碳球复合光催化材料,采用扫描电子显微镜和X-射线衍射仪对样品进行表征。以盐酸四环素作为目标污染物,分析了TiO₂负载量对样品光催化性能的影响,同时对酵母碳球与纳米TiO₂之间的吸附-光催化协同效应进行了分析和评价。实验结果表明：纳米TiO₂在酵母碳球表面的负载显著地提升了纳米TiO₂@酵母碳球的光催化性能,当纳米TiO₂与酵母质量比为1：1时,所制备的TiO₂@酵母碳球对盐酸四环素的光催化效果最佳,具有较好的吸附-光催化协同效应。响应面优化实验表明：当反应温度为40.2℃,pH为5.89,催化剂、盐酸四环素的浓度比为0.76时,体系对盐酸四环素的光催化降解率达到90.86%。     

NO2对光催化降解庚烯的作用

以TiO₂/SiO₂为光催化剂, 在紫外光作用下, 讨论了NO₂存在时, 庚烯在TiO₂/SiO₂上的吸附和光催化降解作用. 通过GC-MS和FT-IR, 分别测定了3种不同体系的反应产物, 从而推测出可能的反应机理. 实验结果表明, TiO₂/SiO₂对庚烯的最大吸附量M_max=3.10　 mg, 当存在NO₂（44.64 μmol/L）时M_max=3.80　mg. 在光催化降解庚烯的反应中, 当NO₂加入量较大(NO₂≥89.28 μmol/L)时, 庚烯降解反应速率加快, 但矿化度比无 NO₂时的小.     

载钛羟基磷灰石对水中EE2光催化降解规律及途径研究

以 17α-乙炔雌二醇(EE2)为目标污染物, 以载钛羟基磷灰石(TiHAP)为催化剂, 对比研究TiHAP和TiO₂对EE2的光催化规律、影响因素及机理, 分析光催化降解的中间产物及降解途径。实验结果表明, TiHAP薄膜对EE2的降解速率高于TiO₂薄膜; 随着Fe³⁺浓度增加, TiHAP降解EE2的速率没有明显变化, TiO₂降解EE2的速率则先增加后减小; 随着富里酸(FA) 浓度的增加, TiHAP降解EE2的速率减小, 而TiO₂降解EE2的速率升高。用LC-MSⁿ对TiHAP光催化降解EE2过程中产生的中间产物进行分析, 在中性pH条件下共确定9种降解产物, 比同样pH值下以TiO₂为催化剂检出的产物种类多, 推断其降解的主要途径是苯环羟基化、开环羧基化以及脱羧等一系列反应。     

纳米TiO2光催化降解乙酸

以廉价无机盐为原料, 采用溶胶-凝胶法制备纳米TiO₂光催化剂, 研究其对乙酸的光催化降解过程. 考察了TiO₂光催化剂处理温度、 用量、 反应液pH值、 污染物初始浓度、 共存离子等因素对光催化降解乙酸的影响, 获得了较好的光催化效果.     

复合催化剂SO42--H3PW12O40/TiO2(P123)的制备及其光催化降解二硝基甲苯

 采用溶胶-凝胶与溶剂热相结合的方法制备了系列介孔复合光催化剂SO₄^2--H₃PW₁₂O₄₀/TiO₂ （P123）,并对其进行了表征和分析。N₂吸附表面分析及扫描电镜（SEM）图片显示,复合催化剂的粒径明显减小,比表面积高达211m²/g,是TiO₂的5 倍。紫外漫反射吸收光谱（UV-Vis）显示,与TiO₂相比,复合催化剂的吸收光谱发生了明显的红移,且吸收强度明显增强。运用L₁₆（4⁵）的正交实验设计探讨了H₃PW₁₂O₄₀负载量、模板剂P123 的添加量、溶液初始pH 值、催化剂加入量以及H₂SO₄浓度5 个因素对二硝基甲苯（DNT）降解性能的影响,并对正交实验结果进行了直观分析和方差分析。结果表明,该降解过程符合L-H 表观一级反应动力学,在催化剂用量为1.2g/L、H₃PW₁₂O₄₀负载量为20%、模板剂P123 的加入量为2g、溶液初始pH 为2、H₂SO₄的浓度为1mol/L 条件下,经氙灯光源辐照4h 后,DNT 的降解率达到98.7%,DNT 降解的半衰期为0.7162h,取得了良好的光催化效果。     

溶剂热法制备TiO2/g-C3N4及其光催化性能

采用溶剂热法合成了可见光响应的TiO₂/g-C₃N₄复合光催化剂,并对TiO₂/g-C₃N₄进行质子化处理。通过X射线衍射（XRD）、氮气吸附-脱附BET法、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、傅里叶红外光谱（FT-IR）、紫外-可见漫反射（UV-vis DRS）和荧光光谱（PL）等方法对样品进行了表征,并以甲基橙（MO）光催化降解为模型反应,考察了可见光下制备的样品的光催化性能。结果表明,多孔TiO₂纳米晶与g-C₃N₄形成具有"芝麻饼"形貌的复合结构;TiO₂/g-C₃N₄复合光催化剂的光吸收带边扩展到465 nm,较TiO₂出现明显红移;TiO₂与g-C₃N₄能带匹配耦合,有效地抑制了电子与空穴的复合;质子化处理过程能够提高可见光区吸收强度和电子的传导能力,增强了TiO₂的光催化活性。     

Modification of TiO2 nanotubes arrays by CdS and their photoelectrocatalytic hydrogen generation properties

In order to realize hydrogen generation under visible light, novel CdS/TiO2 nanotubes arrays are developed by electrochemical anodizaUon of Ti in 0.15 mol/L NHTF ＋ 0.08 mol/L H2C2O4 electrolyte. The diameter of the nanotube is 80-100 nm and the length is approximately 550 nm. The CdS nano-particles are deposited on the TiO2 nanotubes arrays by chemical bath deposition （CBD） in the ammonia-thiourea system. A 300 W Xe lamp is used as the light source, CdS/TiO2 nanotube arrays are used as the photoanode with the application of 1.0 V bath voltage, and 0.1 mol/L Na2S ＋ 0.04 mol/L Na2SO3 solution is used as the electrolyte, then the rate of photoelectrocatalytic hydrogen generation is 245.4 μL/（h·cm^2）. This opens new perspectives for photoelectrocatalytic hydrogen generation by using CdS/TiO2 nanotubes arrays.     

CdS光化学修饰介孔TiO2及其增强的可见光催化活性

[目的]提高介孔TiO₂材料的光催化活性。[方法]采用蒸发诱导自组装法(EISA),以四氯化钛和钛酸丁酯为钛源,嵌段共聚物P123(EO₂₀PO₇₀EO₂₀)为模板剂,制备介孔TiO₂。用光化学修饰法将CdS掺进介孔TiO₂中,合成对可见光有较好响应的复合材料,并利用X射线衍射(XRD)、透射电镜(TEM)、原子吸收分光光度法(AAS)和光催化等手段对样品进行表征。[结果]XRD和TEM结果表明成功合成有序的六方介孔材料;AAS确定复合材料中Cd的含量为0.96mg/g;光催化于500 W氙灯下以2×10^-5mol/L次甲基蓝(MB)为模型污染物,结果显示CdS/TiO₂复合材料的可见光催化活性明显提高。[结论]光化学修饰法制备的介孔CdS/TiO₂复合材料可增强其可见光催化活性。     

Fe_2O_3/TiO_2复合纳米管阵列的制备及其可见光催化性能研究

在氟化铵-乙二醇体系中,采用阳极氧化法在铁基体上制备Fe_2O_3纳米管阵列,然后以氟钛酸铵为钛源,利用水热法在Fe_2O_3纳米管阵列上负载TiO_2纳米片,制得Fe_2O_3/TiO_2复合纳米管阵列,利用SEM、EDS、XRD、TEM、UV-Vis等手段,对所制Fe_2O_3/TiO_2纳米管阵列的表面形貌、物相结构及光催化性能进行表征,并分析Fe_2O_3/TiO_2纳米结构对亚甲基蓝的可见光降解能力。结果表明,Fe_2O_3/TiO_2复合纳米管阵列具有良好的可见光响应;NH_4F浓度为0.4%、水热反应3h制备的Fe_2O_3/TiO_2复合结构具有最佳的光催化性能,对亚甲基蓝的降解率可达90%。     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.     

Preparation and photocatalytic activity of Cu-doped TiO2/SiO2

Cu²⁺-doped nanostructured TiO₂-coated SiO₂ (TiO₂/SiO₂) particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO₂ colloids were synthesized by the sol-gel method using TiOSO₄ as a precursor. The experimental results showed that TiO₂ nanopowders on the surface of SiO₂ particles were well distributed and compact. The amount of TiO₂ increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550°C. The 2-layer coated TiO₂ particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu²⁺-doped TiO₂/SiO₂ was higher than that of undoped TiO₂/SiO₂. The optimum dopant content was about 0.10wt%.     

银掺杂多孔氧化钛光催化甲基橙降解反应条件的探究

利用溶胶-凝胶法结合光还原法制备Ag掺杂多孔TiO_2光催化剂,以甲基橙的降解效果为评价标准,考查了光照降解时间、光催化剂用量、甲基橙溶液初始浓度、溶液pH值对光催化剂催化降解甲基橙的影响。结果表明,本方法制备的光催化剂无论是在紫外光还是可见光下均具有优良的光催化性能:在浓度为10 mg/L的甲基橙溶液中,4 g/L光催化剂,紫外光照射80 min,甲基橙可实现100%完全降解;相同催化条件下,可见光照100 min,甲基橙完全降解;当反应溶液pH=2时,紫外光和可见光都可在20 min内实现甲基橙的完全降解。     

Degradation of 2, 4-D acid using Mn2+ as catalyst under UV irradiation

In this paper, the oxidative degradation of 2, 4-dichlorophenoxyacetic acid (2, 4-D) using Mn²⁺/H₂O₂ reagent under UV irradiation was studied. The results show that 2, 4-D was degraded more completely in Mn²⁺/H₂O₂ solution than traditional Fenton solutions. The effects of the concentration of Mn²⁺, H₂O₂ and pH were also investigated. And under the optimal condition of 1.48×10⁻⁴ mol/L, 8.99×10⁻⁵ mol/L and pH 3.38, the formation of ·OH was the most, both the decomposition rate of H₂O₂ and the degradation rate of 2, 4-D were the fastest. In addition, the photoreaction process was monitored using spin-trapping electron paramagnetic resonance (EPR), and the results indicated that the oxidative process was predominated mainly by the hydroxyl radical (·OH) gennerated in the system. Biography: HUANG Yingping (1964–), Professor, Ph. D., research direction: pollution ecology and water pollution control.     

Vegetation evolution on the central Chinese Loess Plateau since late Quaternary evidenced by elemental carbon isotopic composition

There are many controversial issues in loess studies such as natural vegetation types on the Chinese Loess Plateau during the historical periods and the spatial and temporal evolution of C3/C4 plants. Elemental carbon isotopic composition （δ^13Cec） in the loess section may offer new evidence for these problems. Elemental carbon （EC） is produced by incomplete combustion of vegetation, and its carbon isotopic composition has a very small difference from that of the formal vegetation, then δ^13Cec can be used as a record to recover the changes of vegetation. Elemental carbon was extracted by applying the oxidation method from the Ioess-paleosol sequence in the central Chinese Loess Plateau, and its car- bon isotope composition was analyzed by the isotope mass spectrometer. The results showed that the vegetation in this region was a mixed type of C3 and C4 plants, dominated with C3 plants in most of the time. Since late Quaternary, C3/C4 plants may not follow a simple glacial-interglacial cycle mode on the Chinese Loess Plateau, but showing fluctuations. C3 plants increased gradually in L4 period, and more C3 plants occurred during $3 period, and C4 plants increased again during L3-- L2 periods, after that, Cs plants dominated again during S1 --S0 periods. During periods of paleosol development, C3 plants were abundant in S3 and S1, and there were more Ca plants in S2 and SO. During periods of loess sedimen- tation, there were more C3 plants in L4 and L1, and there were more C4 plants in L3 and L2. On the orbital timescale, the vegetation variations revealed by δ^13Cec record are consistent with the results of pollen data and also similar to the results obtained by organic carbon isotopic composition since the last glacial period.     

铕掺杂TiO2粉末的制备及其可见光光催化性能研究

以钛酸四正丁酯为原料,采用水热法制备铕掺杂TiO2粉末,对铕掺杂TiO2粉末的可见光光催化性能进行研究,并通过XRD、SEM分析对其进行表征。结果表明,铕掺杂TiO2粉末没有改变晶相结构,铕掺杂后使TiO2粉末由不规则形状转变为实心球状,且提高了TiO2粉末的光催化性能。模拟太阳光实验发现,铕掺杂TiO2粉末可明显提高其可见光光催化的降解能力,当辐照度为500W/m2、时间为240min时,其降解率达到78%。