贵金属负载氧化石墨烯二氧化钛光催化消除甲硫醇三甲胺性能探究

利用沉积法将Ag、Pt、Pd等3种贵金属负载GO/TiO₂,利用X射线衍射、扫描电镜和X射线光电子能谱等对催化剂的结构、组成、形貌进行表征.将催化剂用于光催化动态和静态实验降解甲硫醇、三甲胺气体,考察不同贵金属的负载对催化效果的影响.结果表明,贵金属均匀沉积在GO/TiO₂上,减少了光生电子空穴对复合,与GO/TiO₂相比光催化效率得到显著提升.催化效果顺序为：Pd/GO/TiO₂>Pt/GO/TiO₂>Ag/GO/TiO₂>GO/TiO₂.     

基于弥散光纤的二氧化钛光催化反应器

以弥散光纤(SOF)作为基体、负载纳米二氧化钛膜制备光纤式反应器,可有效提高催化剂与降解物的接触面积,提高光的传输、利用效率,克服了传统固定床反应器的不足,应用新型的光纤式反应器催化降解4-氯苯酚,降解率达到95%.     

C-TiO_2/Ti-Cu_2O/Cu光催化燃料电池的性能

采用溶胶-凝胶法制备了C-TiO_2/Ti膜电极,其X-射线衍射(XRD)结果表明,C掺杂有效抑制了TiO_2催化剂由锐钛矿相向金红石相的转变.以C-TiO_2/Ti作为光催化燃料电池(PFC)的阳极,Cu_2O/Cu为阴极,考察了C-TiO_2/Ti的制备条件和染料初始浓度及p H值对PFC性能的影响,得到PFC的最佳性能:短路电流密度为0.084 m A·cm~(-2),开路电压为0.385 V,最大输出功率密度为5.91×10~(-3)m W·cm~(-2),填充因子(FF)为0.18,光催化处理20 mg·L~(-1)罗丹明B染料废水90 min,脱色率达到91.7%.处理过程中罗丹明B溶液的紫外-可见分光光谱表明,可见光区最大吸收波长略有蓝移,可见和紫外光区的光吸收均下降,说明分子遭到了破坏,并发生了矿化.     

铂掺杂二氧化钛的制备及光催化乳酸制氢的研究

采用溶胶-凝胶法和甲醛还原法制备了Pt/TiO2光催化剂,并采用XRD对其结构进行了表征.当焙烧温度为500℃时,制备的纳米二氧化钛为纯锐钛矿相;在二氧化钛表面沉积少量的铂对二氧化钛的晶相和粒径几乎没有影响,但可以使二氧化钛光催化的产氢性能提高近10倍.以乳酸为电子供体,对影响其光催化产氢的因素进行了详细地考察.研究结果表明,光催化分解乳酸产氢的最佳条件为焙烧温度500℃、焙烧时间2 h、载铂量0.8%、催化剂用量0.14 g·L-1和pH 1-2.     

蛋氨酸为硫源的硫掺杂二氧化钛的光催化活性

为改善二氧化钛的可见光催化活性,以蛋氨酸为硫源,在温和条件下采用溶胶-凝胶法制备了硫掺杂二氧化钛粉末。采用XRD、TEM、UV-Vis漫反射吸收光谱和XPS等方法对制备的样品进行表征,以甲基橙的光降解效果考察其可见光催化活性。结果显示：350~500℃所制备的硫掺杂二氧化钛均为锐钛矿相,600℃出现混晶,且硫的掺杂一定程度的抑制了粒径的增长和晶相的转变;硫以阳离子形式进入二氧化钛晶格中,引起光催化剂在可见光区的光吸收;掺杂样品表现出较好的可见光催化活性,且随煅烧温度的增加,催化活性逐渐降低。正交试验得出优化条件为：S/Ti物质的量配比为1.6%,煅烧温度为450℃,煅烧时间为3 h。     

磺胺甲噁唑在磷钨酸/二氧化钛复合膜上的光催化降解

以典型抗生素类药物磺胺甲噁唑(SMZ)为目标物,模拟太阳光下研究其在磷钨酸/二氧化钛(H3PW12O40/TiO2)复合膜上的光催化降解行为,并对其可能的降解机理进行探讨.通过一系列的条件实验确定H3PW12O40/TiO2复合膜光催化降解SMZ的最佳实验条件为:H3PW12O40掺杂量为7.7%、污染物初始浓度为50 mg·L-1、溶液pH值为5.5.此时,H3PW12O40/TiO2复合膜表现出最强的光催化活性,其动力学常数为0.453 h-1,为纯TiO2膜的3.0倍;模拟太阳光照射12 h后,复合膜对SMZ的矿化度可达66.6%,是纯TiO2膜的1.25倍.     

多孔陶瓷球负载纳米晶粒二氧化钛光催化剂的制备及光催化活性

以多孔陶瓷球为载体,采用溶胶-凝胶法在其表面进行纳米TiO2薄膜负载,制备了多孔陶瓷球负载纳米晶粒二氧化钛光催化剂,经X射线衍射法(XRD)等手段对其表征结果表明,复合载体经500℃焙烧后,TiO2以锐钛矿晶型存在。对催化剂降解活性艳蓝溶液的催化活性进行研究表明,催化剂在5 h内可完全降解活性艳蓝染料。     

TiO2-AC-PTFE光阳极的制备及光电催化降解苯酚

采用溶胶-凝胶法制备载钛活性炭,研究了钛酸丁酯、无水乙醇、去离子水、硝酸和活性炭的用量以及热处理温度对载钛活性炭的吸附性能和光催化性能的影响,优化载钛活性炭的制备条件,用载钛活性炭制备光阳极,以苯酚为目标污染物研究了光阳极的吸附性能、在紫外光照射下的光催化氧化性能、阳极电氧化性能和光电组合氧化性能.发现光阳极良好的吸附性能可以大幅度地提高苯酚的总去除率,光电组合氧化有明显的协同作用且宜在酸性条件下进行.     

固相合成钛酸钙的光催化性能

采用CaCO3和TiO2作为原料,在1400℃、2h条件下烧结得到CaTiO3.应用X射线衍射(XRD)、扫描电子显微镜(SEM)对高温处理后的混合物料进行了表征.以亚甲基蓝为降解物,研究了光照时间、pH值、溶液初始浓度、催化剂投加量对CaTiO3光催化性能的影响.实验结果表明,光照时间延长,亚甲基蓝降解率增加,但是亚甲基蓝被降解速率降低;碱性条件有利于CaTiO3对亚甲基蓝的光催化降解;CaTiO3对低浓度的亚甲基蓝溶液具有较高的光催化降解率;随着CaTiO3投加量增加,亚甲基蓝降解率增大,但是当CaTiO3投加量大于0.1g时,随着CaTiO3投加量的增加,亚甲基蓝的降解率几乎不变,甚至有所降低.     

不同消解方法对纳米二氧化钛浓度测定的影响

建立了氢氟酸硝酸微波消解-电感耦合等离子光谱法(ICP-OES)检测水中纳米二氧化钛浓度的分析方法.分析对比了国内外三大类纳米二氧化钛消解方法的回收率,考察了电感耦合等离子光谱仪(ICP-OES)测定钛离子的精密度.实验对比发现,过硫酸铵碱熔法回收率最低,加热板消解法的回收率低于微波消解法.在微波消解法中,以氢氟酸硝酸为消解剂时,回收率最高.因此,氢氟酸硝酸微波消解法最适合消解纳米二氧化钛;在选定条件下,钛的标准曲线在10—1000μg.L-1的范围内线性关系良好(最大误差<5%).RSD小于10%;检出限(MDL)和测定限(RQL)均低于1μg.L-1.加标回收率在119%—122%之间,满足标准的要求.因此,氢氟酸硝酸微波消解法结合ICP-OES,是一种较适合测定纳米二氧化钛浓度的方法.     

Comparison of photoelectrochemical properties of TiO2-nanotube-array photoanode prepared by anodization in different electrolyte

Self-organized, well-crystallized and high aspect-ratio TiO₂ nanotube arrays (TNAs) have been prepared by anodic oxidation in dimethyl sulfoxide (DMSO) containing 5 wt% HF at 40 V (vs. Pt). A 50 h anodization results in a nanotube arrays approximately 19.4 μm in length, referred as long tube. As a comparison, the short titania nanotube arrays, about 500 nm in length, was obtained by anodization in HF aqueous solution, referred as short tube. Different characterization techniques (viz. FESEM, TEM, XRD and DRS) are used to study the nanotubular microstructure. The morphology of the nanotube electrodes shows an evident influence on their photocatalytic (PC) and photoelectrochemical reactivity. The long tube reveals enhanced photocurrent response and PC degradation efficiency of organic compounds. The kinetic constant of PC degradation of methylic orange (MO) for long tube electrode is found 1.55 times as high as the short tube. A significant photoelectrochemcial synergetic effect in MO degradation was observed on the long tube electrode and the photoelectrocatalytic (PEC) degradation of MO on long tube is 27% higher than its PC process.     

二氧化钛/石墨烯复合光催化剂的制备及其对水中双酚A的降解

双酚A污染问题日益严峻,已经威胁到人类的健康.半导体光催化技术可以有效去除水体中双酚A污染.近年来,二氧化钛/石墨烯复合材料,因其优越的光催化性能受到广泛关注.尤其石墨烯等新型纳米碳基材料,有较大的比表面积和丰富的官能团,为二氧化钛的负载创造了良好的条件,其表面可以形成化学键,为双酚A的吸附降解提供了更多的活性位点.本文重点介绍了国内外二氧化钛/石墨烯复合材料的制备方法及各种制备方法的优缺点;讨论了二氧化钛/石墨烯复合材料对双酚A的降解效果及其降解机理;分析了二氧化钛/石墨烯复合材料的再生性能.最后总结这种材料在实际应用中存在的问题及其前景展望.     

纳米TiO2光催化降解有机磷农药的研究

通过实验,探讨了用纳米TiO2光催化处理有机磷农药模拟废水和实际应用的有机磷农药的可行性.实验表明,以测定不同时间PO43-的浓度来衡量有机磷的降解率,并以此来衡量有机磷农药及其中间产物降解的程度是合理的.光催化降解甲胺磷和水胺硫磷的结果,显示了有机磷农药的降解率与其结构有关.实际应用的有机磷农药也可用光催化降解.     

Structural effect on photocatalytic degradation of metallised azo dyes in aqueous TiO2 suspension

Three metallised azo dyes were investigated under TiO₂‐photocatalytic and photosensitised conditions in aqueous buffering solutions. The degradation follows apparent first‐order kinetics. The size and strength of intramolecular conjugation determine the light‐fastness of the investigated dyes. Compared with ¹O₂ produced in photosensitised process, the more powerful *OH radicals in TiCO₂ photocatalytic process are highly reactive towards the investigated azo dyes. And as a result, the TiO₂‐photocatalysis makes little less distinction in the degradation kinetic data of the azo dyes compared with the photosensitised degradation of them.     

TiO2-FeOOH/Mmt纳米复合材料的表面酸碱性质及光催化性能

本研究以蒙脱石(Mmt)为基底材料,利用自组装制备技术得到TiO_2-FeOOH/Mmt纳米复合材料,以亚甲基蓝为降解目标物,研究复合材料光催化降解性能.利用透射电子显微镜(TEM)、比表面积及孔隙分析仪(BET)和紫外-可见分光光度计(UV-Vis)对制备材料进行表征分析,结果表明由针铁矿和锐钛矿组成的复合材料带隙宽度减小且光响应范围得到拓宽.着重通过表面酸碱滴定实验,结合ProtoFit表面络合模型模拟软件,对光催化前后材料表面酸碱性质变化情况进行了分析,发现复合材料的lgK_a值并非单层材料的简单叠加,而是复合后发生了一定的表面化学作用形成新的表面酸碱性质.复合材料具有更大的表面位密度N_t及表面化合态≡XOH含量,能使材料在表面反应过程中提供更多的表面活性物质,产生更多的自由基,间接加快目标物降解速度.且复合材料铁循环强度更大,该循环能有利反应过程中电子的转移,并维持材料表面活性.这为后期进一步研究纳米复合材料光催化降解机理提供理论依据.     

Enhanced photocatalytic activity of electrospun TiO2/polyacrylonitrile membranes in a crossflow reactor using dual lights

Photocatalytic membranes reactors have become one of the most efficient technologies to treat polluted waters. However, a major drawback is the unilateral irradiation of the membrane, where only one side of the membrane is exploited. To overcome this issue, we developed a reactor where the membrane can be irradiated on both sides. Polyacrylonitrile membranes containing different amounts of TiO₂ nanoparticles up to 60% were first prepared by electrospinning. These membranes were used in a 3D-printed crossflow photocatalytic membrane reactor for the degradation of methylene blue under different combinations of lights. The use of both sides of the photocatalytic membrane significantly enhanced the photocatalytic activity for the decolorization of methylene blue in water. The prepared membranes showed the best decolorization rate for a loading of 60% of TiO₂ and the use of dual ultraviolet lights, where the methylene blue solution was completely discolored after 90 min. This is the first report of a such system configuration, and this new irradiation concept is promising for photocatalytic membrane reactions and water cleaning.

     

Effect of molecular properties on the photocatalytic degradation rates of dichlorophenols and dichloroanilines in aqueous TiO2 suspensions

The kinetics of the photocatalytic degradation of 10 different dichlorophenols and dichloroanilines have been investigated experimentally and theoretically. With the intention of finding certain molecular indices in order to determine the degradation rates of aromatic pollutants, geometry optimizations of the compounds have been performed with the semiempirical PM3 method. The molecular orbital calculations have been carried out by an SCF method using the RHF formalism. The correlations between the apparent first-order rate constants and the calculated molecular properties of the compounds have been examined. Four different structure–activity relationships have been developed expressing the logarithms of the rate constants in terms of the Hammett constants, electron densities of the substituents, the coefficients and the energies of the highest occupied molecular orbitals HOMO, and 1-octanol/water partition coefficients log?K _OW.     

Preparation and characterization of a new TiO2/SiO2 composite catalyst for photocatalytic degradation of indigo carmin

The TiO₂/SiO₂ composite was prepared by means of the SiO₂-particle-entrapment method. The FTIR data showed the presence of Si–O–Ti stretching vibration band at 970 cm⁻¹ in the TiO₂/SiO₂ composite, suggesting a reaction between TiO₂ and silica on the TiO₂ particle surface during the silicagel formation around the TiO₂ particles. The photocatalytic efficiency of TiO₂ immobilized in silicagel was compared with that of the conventional TiO₂ Degussa P25 catalyst. For this purpose, the degradation of indigo carmin (IC) dye was used as model molecule in the tests. The effect of operational parameters such as catalyst loading and dye concentration on the photocatalytic degradation of the model dye was investigated. The rate of degradation increased with increasing catalyst loading, and when the concentration of the dye decreases.     

Effect of iron speciation on the photodegradation of Monuron in combined photocatalytic systems with immobilized or suspended TiO2

Photodegradation kinetics of Monuron (3-(4-chlorophenyl)-1,1-dimethylurea) in photoreactor with immobilized and suspended TiO₂ photocatalyst were studied. The effect of addition of ferric or ferrous perchlorate was investigated. Whatever the concentration of Fe(III/II) added there is no significant negative effect on the photodegradation rate of pollutants. On the contrary, depending on speciation and concentration of iron salts, slight or marked acceleration of the photodegradation kinetics was observed. This positive influence was more pronounced in the case of TiO₂ suspensions than for TiO₂ layers. Fe(III) was generally more effective than Fe(II).