双极液膜法可见光光催化降解染料废水

采用溶胶-凝胶法制备了Bi2O3-TiO2/Ti膜电极,X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射(DRS)和光电性能测试进行了表征,结果表明,Bi元素掺杂进入了TiO2催化剂,拓展了催化剂的光响应波长,使其在可见光下有较明显的光电响应.将Bi2O3-TiO2/Ti光阳极与Cu阴极组装成双极液膜反应器,在可见光下光催化处理活性艳红X-3B,得出当初始pH值为2.52,废水流量为80mL/min时,处理20mg/L活性艳红X-3B 150min,脱色率可达88%.双极液膜法可见光光催化的初步机理考察表明,光生电子自发由Bi2O3-TiO2表面转移到Cu电极表面,并在Cu电极表面直接还原染料,或与其表面液膜中的溶解氧反应生成H2O2,进而参与染料的氧化,由此可实现Bi2O3-TiO2/Ti的直接氧化和Cu阴极的直接还原和间接氧化的双极双效效果.     

Mesopolymer modified with palladium phthalocyaninesulfonate as a versatile photocatalyst for phenol and bisphenol A degradation under visible light irradiation

A novel versatile photocatalyst, FDU-PdPcS, was prepared by immobilizing palladium phthalocyaninesulfonate (PdPcS) onto the FDU-15 mesopolymer via multi-step chemical modification processes involving chloromethylation of the FDU-15 mesopolymer first with chloromethyl methyl ether, a subsequent amination reaction with ethylenediamine, and finally modification with palladium phthalocyaninesulfonate via ionic interaction. The obtained FDU-PdPcS photocatalyst was characterized by the X-ray diffraction (XRD), UV-Vis spectrosopy and inductively coupled plasma (ICP) techniques. This photocatalyst not only affords a high dispersion of monomeric PdPcS molecules, which may further be stabilized by the π-electron of benzene rings of FDU-15, but also provides a number of diamino groups inside the mesopores, which could be advantageous for the photodegradation of phenolic pollutants. In photodegradation studies of phenolic pollutants, the FDU-PdPcS catalyst exhibited excellent visible light photocatalytic activity and reusability. The photodegradation products of phenol and bisphenol A were investigated by the gas chromatoghraphy-mass spectrometry (GC-MS) technique. The results showed that the photodegradation products were composed of carboxylic acids and CO2. Isopropanol, sodium azide and benzoquinone were used as hydroxyl radical (OH.), singlet oxygen (1O2) and superoxide radical (O2.-) scavengers, respectively. The results suggested that 1O2 and O2. were the prominent active species during the photodegradation process. A possible mechanism for the photodegradation of phenol was also discussed.     

Mechanism of enhanced removal of quinonic intermediates during electrochemical oxidation of Orange Ⅱ under ultraviolet irradiation

The effect of ultraviolet irradiation on generation of radicals and formation of intermediates was investigated in electrochemical oxidation of the azo-dye Orange I1 using a TiO2-modified β- PbO2 electrode. It was found that a characteristic absorbance of quinonic compounds at 255 nm, which is responsible for the rate-determining step during aromatics degradation, was formed only in electrocatalytic oxidation. The dye can be oxidized by either HO radicals or direct electron transfer. Quinonic compounds were produced concurrently. The removal of TOC by photo-assisted electrocatalytic oxidation was 1.56 times that of the sum of the other two processes, indicating a significant synergetic effect. In addition, once the ultraviolet irradiation was introduced into the process of electrocatalytic oxidation, the degradation rate of quinonic compounds was enhanced by as much as a factor of two. The more efficient generation of HO radicals resulted from the introduction of ultraviolet irradiation in electrocatalytic oxidation led to the significant synergetic effect as well as the inhibiting effect on the accumulation of quinonic compounds.     

BiOCl/TiO_2复合材料的可见光活性及机理研究

采用水热法和溶胶凝胶法制备新型BiOCl/TiO2复合材料并明确了最优的掺杂比例(2%).随后利用X射线衍射(XRD)、紫外可见漫反射(DRS)、透射电镜(TEM)和X射线光电子能谱(XPS)对该材料进行表征.由于禁带宽度较大,纯BiOCl和TiO2的可见光催化性能极差,然而二者复合后,同条件下的苯降解率却大幅提升,可以达到40%以上.经证实,催化剂制备过程中,Bi的状态发生变化,在TiO2导、价带之间插入新的能级,使其禁带宽度变窄,电子可以实现可见光跃迁.     

Mesoporous WO3-graphene photocatalyst for photocatalytic degradation of Methylene Blue dye under visible light illumination

Advanced oxidation technologies are a friendly environmental approach for the remediation of industrial wastewaters. Here, one pot synthesis of mesoporous WO_3 and WO_3-graphene oxide(GO) nanocomposites has been performed through the sol–gel method. Then, platinum(Pt) nanoparticles were deposited onto the WO_3 and WO_3-GO nanocomposite through photochemical reduction to produce mesoporous Pt/WO_3 and Pt/WO_3-GO nanocomposites. X-ray diffraction(XRD) findings exhibit a formation of monoclinic and triclinic WO_3 phases. Transmission Electron Microscope(TEM) images of Pt/WO_3-GO nanocomposites exhibited that WO_3 nanoparticles are obviously agglomerated and the particle sizes of Pt and WO_3 are ~ 10 nm and 20–50 nm, respectively. The mesoporous Pt/WO_3 and Pt/WO_3-GO nanocomposites were assessed for photocatalytic degradation of Methylene Blue(MB) as a probe molecule under visible light illumination.The findings showed that mesoporous Pt/WO_3, WO_3-GO and Pt/WO_3-GO nanocomposites exhibited much higher photocatalytic efficiencies than the pure WO_3. The photodegradation rates by mesoporous Pt/WO_3-GO nanocomposites are 3, 2 and 1.15 times greater than those by mesoporous WO_3, WO_3-GO, and Pt/WO_3, respectively. The key factors of the enhanced photocatalytic performance of Pt/WO_3-GO nanocomposites could be explained by the highly freedom electron transfer through the synergetic effect between WO_3 and GO sheets, in addition to the Pt nanoparticles that act as active sites for O2 reduction, which suppresses the electron hole pair recombination in the Pt/WO_3-GO nanocomposites.     

水热合成温度对纳米TiO2特性及其可见光波段光催化性能的影响

以乙醇-丙酮-吡啶为溶剂，采用水热法制备了在可见光波段（≤450nm）具有良好光催化活性的纳米TiO2粉体,通过XRD、TEM、DTA、漫反射谱（DRS）与光电压谱等手段，研究了水热合成温度及250℃热处理对合成纳米TiO2粉体的材料特性，以及在可见光激发下纳米TiO2对甲基橙光催化降解的影响．结果显示，纳米TiO2晶型（锐钛矿）与粒径不随水热合成温度及热处理（250℃）条件的变化发生明显改变；各样品的表面吸附物状态以及可见光响应特性在未经热处理时随水热合成温度变化发生明显变化，而在经250℃热处理后则差异不明显；样品的表面吸附物状态、可见光响应以及可见光催化活性之间有显著关联，水热合成温度显著地影响了纳米TiO2粉体的表面吸附物状态及可见光催化活性。     

Fe-Ni-TiO2/AC粒子电极的制备及可见光光电催化协同降解RhB

制备Fe-Ni-TiO2/AC粒子电极,应用于可见光助三维电极/电Fenton(Vis-3D/EF)光电催化体系中,以RhB为目标污染物,研究了可见光光电催化对RhB的协同降解.实验优化了Fe-Ni-TiO2/AC粒子电极的制备条件,并与活性炭粒子电极、活性炭负载TiO2粒子电极在Vis-3D/EF体系中的光电催化性能进行对比,结果表明:TiO2浸渍液浓度为2g/L,Fe-Ni掺杂比为5:5,Fe:Ni:TiO2物质的量比为0.5:0.5:100的条件下制备的粒子电极在Vis-3D/EF体系中表现出最优的光电催化性能,60min对RhB的去除率达92.58%,优于活性炭粒子电极和活性炭负载TiO2粒子电极.自制粒子电极在Vis-3D/EF体系比在3D/EF体系对RhB的去除率提高29.46%,表现出明显的光催化和三维电极/电Fenton协同处理效果,协同指数为1.18,说明了自制粒子电极应用在Vis-3D/EF组合技术中,实现对RhB的可见光光电协同降解是可行的.     

TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应

以内分泌干扰物阿特拉津为模型污染物,研究了TiO2-Fe3+可见光催化H2O2降解阿特拉津的协同效应.结果表明,在H2O2存在条件下,金红石TiO2经可见光激发可持续稳定地产生.OH自由基,在Fe3+协同作用下,.OH自由基生成量急剧增加;TiO2能可见光催化H2O2降解阿特拉津,金红石TiO2显示出较锐钛矿TiO2及混晶TiO2(TiO2P25)更高的催化活性,反应60 min,阿特拉津的降解率可达40%;以Fe3+协同TiO2可见光催化H2O2降解阿特拉津时,反应效率显著加快,反应5 min即对阿特拉津的降解率达到100%,而金红石TiO2显示出更为明显的协同效应.     

Bi2WO6可见光催化降解染料废水实验研究

采用水热法合成了新型的可见光催化剂Bi2WO6,以活性蓝M-2GE染料废水为目标污染物,研究了催化剂的用量、污染物初始浓度、溶液pH、盐效应等因素对光催化降解效果的影响.结果表明,在优化实验条件下(催化剂的投加量为3g·L-1、pH值中性偏酸性、反应90min),对目标污染物的去除率可达到99%;溶液中盐浓度的增加对降解有抑制作用;催化剂对不同初始浓度活性蓝M-2GE染料的去除过程遵循一级动力学方程;催化剂重复使用后催化效果有所下降,但仍然可以保持在90%左右.因此,用水热法合成的催化剂Bi2WO6具有良好的可见光活性.     

Enhanced photocatalytic activity of rGO/TiO2 for the decomposition of formaldehyde under visible light irradiation

Due to the low concentration of indoor air contaminants,photocatalytic technology shows low efficiency for indoor air purification.The application of TiO_2 for photocatalytic removal of formaldehyde is limited,because TiO_2 can only absorb ultraviolet(UV) light.Immobilization of TiO_2 nanoparticles on the surface of graphene can improve the visible light photocatalytic activity and the adsorption capacity.In this study,rGO(reduced graphene oxide)/TiO_2 was synthesized through a hydrothermal method using titanium tetrabutoxide and graphene oxide as precursors,and was used for the degradation of low concentration formaldehyde in indoor air under visible light illumination.Characterization of the crystalline structure and morphology of rGO/TiO_2 revealed that most GO was reduced to rGO during the hydrothermal treatment,and anatase TiO_2 nanoparticles(with particle size of 15–30 nm) were dispersed well on the surface of the rGO sheets.rGO/TiO_2 exhibited excellent photocatalytic activity for degradation of formaldehyde in indoor air and this can be attributed to the role of rGO,which can act as the electron sink and transporter for separating photo-generated electron–hole pairs through interfacial charge transfer.Furthermore,rGO could adsorb formaldehyde molecules from air to produce a high concentration of formaldehyde on the surface of rGO/TiO_2.Under visible light irradiation for 240 min,the concentration of formaldehyde could be reduced to 58.5 ppbV.rGO/TiO_2 showed excellent moisture-resistance behavior,and after five cycles,r GO/TiO_2 maintained high photocatalytic activity for the removal of formaldehyde(84.6%).This work suggests that the synthesized rGO/TiO_2 is a promising photocatalyst for indoor formaldehyde removal.     

透明Cl-TiO2水分散液的制备及其可见光降解甲苯和灭菌的性能

开发具有高稳定性和高可见光活性的光催化剂透明分散液对光催化材料的实际应用至关重要.本文采用非水解溶胶凝胶法制备了透明Cl掺杂TiO₂分散液(Cl-TiO₂).该分散液经过60 d仍能保持稳定,没有颗粒沉降.与商用P25、PEG400-TiO₂相比,Cl-TiO₂具有最优的可见光降解甲苯的光催化活性,并且具有良好的循环稳定性.Cl-TiO₂在可见光下同时具有优异的灭菌效果,对大肠杆菌的灭菌率达到98.75%.其优异的可见光响应性归因于Cl掺杂增强了对可见光的吸收,提高了电子空穴的分离效率.Cl-TiO₂水分散液良好的稳定性得益于表面带有的电荷以及较小的水合粒径.这项工作为光催化剂用于改善室内环境提供了新策略.     

Bi2WO6可见光催化降解活性艳红X-3B的研究

采用水热合成法制备Bi2WO6催化剂,并通过XRD,UV-vis DRS等手段对其进行表征;以活性艳红X-3B为目标污染物,研究催化剂量、X-3B初始浓度、反应溶液pH值以及H2O2等因素在可见光辐射下对其光催化降解效果的影响.结果表明,所制备的Bi2WO6催化剂结晶度好,具有较强的可见光吸收能力;最佳催化反应条件为: X-3B初始浓度20mg/L,Bi2WO6用量2g/L, pH5.18(原始pH值).在此条件下,光照60min,对X-3B的去除率可达到86%;加入2mL/L 30%的H2O2,光照30min,降解率可达到96%以上,降解反应符合一级反应动力学.光催化反应可以有效地破坏X-3B的发色基团偶氮结构使其脱色,但在所设定的反应时间(80 min)内X-3B不能被完全矿化,反应过程中有中间产物生成.     

纳米TiO_2-CS微球光催化降解亚甲基兰的研究

将用化学方法改性后的纳米TiO2与壳聚糖(CS)共混,通过反相悬浮、交联制备了纳米TiO2-CS微球光催化剂,以亚甲基兰为对象,紫外灯为光源,研究了亚甲基兰的初始浓度、光照时间、不同pH值、纳米TiO2的含量、催化剂用量对亚甲基兰光降解率的影响。结果表明:纳米TiO2-CS微球能显著地降解亚甲基兰,且易于回收、能重复使用,为其实际应用提供了有价值的参数。     

锌铝水滑石负载羧酸基酞菁锌可见光降解水中氯苯酚

以锌铝类水滑石为载体,1.0%(质量分数)水溶性羧酸基酞菁锌为光敏剂,制备了不溶于水的负载型光敏剂,并对其结构进行表征.结果表明,在可见光和氧气作用下,该复合催化剂能够引发水中对氯苯酚、2,4-二氯苯酚和2,4,6-三氯苯酚的降解.但有机物降解的速率与载体的锌铝比和煅烧温度有关.研究表明,最佳的锌铝比和煅烧温度分别为2.0和300℃.在反应过程中,载体及其煅烧产物具有电子导体的功能,可加快光敏剂与氧气之间的电子转移过程,进而引发氯苯酚的降解.此外,该复合催化剂能被重复循环使用,但光敏活性逐渐降低.     

上转光剂掺杂新型纳米TiO2催化剂的制备及利用可见光降解反应艳蓝KN-R染料的研究

合成了一种新型含有稀土金属Er的上转光剂,40CdF2·60BaF2·0.8Er2O3,此上转光剂在488 nm可见光的激发下,产生了5个波长均小于387 nm的上转换紫外发射峰.采用超声波分散的方法制备出了上转光剂掺杂的纳米TiO2可见光光催化剂.采用X射线衍射(XRD)及透射电镜(TEM)对催化剂进行了表征.以反应艳蓝KN-R为研究对象,研究了在(三基色灯下发出的)可见光的照射下该可见光光催化剂的催化降解性能,并与未掺杂纳米TiO2粉末的催化剂性能进行了对比.实验结果表明,作为掺杂成分的上转光剂可有效地将可见光转化为紫外光并被纳米TiO2粉末吸收利用,在可见光照射50 h后反应艳蓝KN-R降解率达74.36%,大大高于未掺杂纳米TiO2的降解率(23.10%).     

Detection of intermediates in the TiO2-assisted photodegradation of Rhodamine B under visible light irradiation

The photocatalytic degradation of dye Rhodamine B （RhB） in the presence of TiO2 nanostdpe or P25 under visible light irradiation was investigated. The degradation intermediates were identified using Infrared spectra （IR spectra）, ^1H nuclear magnetic resonance （^1HNMR） spectra, and gas chromatography-mass spectroscopy （GC-MS）. The IR and the ^1HNMR results showed that the large conjugated chromophore structure of RhB was efficiently destroyed under visible light irradiation in both the photocatalytic systems （TiO2 nanostfipe or P25 and Rhodamine B systems）. GC-MS results showed that the main identified intermediates were ethanediotic acid, 1,2-benzenedicarboxylic acid, 4-hydroxy benzoic acid and benzoic acid, which were almost the same in the TiO2 nanostdpes and P25 systems. This work provides a good insight into the reaction pathway（s） for the TiO2-assisted photocatalytic degradation of dye pollutants under visible light irradiation.     

氮掺杂型纳米TiO2在可见光及太阳光下的光催化性能研究

采用钛酸四丁酯为原料,以氨水水解-沉淀法制备出了氮掺杂型纳米TiO2催化剂(N/TiO2),以XRD、XPS、UV-Vis等手段对其进行表征;并通过对偶氮染料橙黄G的降解反应,研究了N/TiO2在可见光及太阳光下的光催化性能,探讨了pH值、外加H2O2氧化剂对光催化降解率的影响,并与P25型纳米TiO2进行了对比.结果表明,在可见光下,N/TiO2对橙黄G具有较高的催化活性,反应150min后降解率可达96.29%,显著高于P25型TiO2(42.55%);在太阳光下,N/TiO2对橙黄G的光催化降解速率较快,反应60min降解率与P25型TiO2基本相同,分别为99.37%、99.94%;较低的pH值环境并适量添加H2O2可显著提高N/TiO2催化效率,在可见光及太阳光下的最佳pH值均为2～3,最佳H2O2加入量分别为0.5mL·L-1、1.5 mL·L-1.     

负载型纳米Bi2WO6/AC的制备及在可见光下降解邻硝基苯酚

采用水热法在160℃条件下以活性炭(AC)为载体合成了光催化剂Bi2WO6/AC,用X射线衍射仪(XRD)、电子扫描电镜(SEM)对催化剂进行了表征.同时,以邻硝基苯酚为目标污染物,在可见光照射下,讨论了催化剂用量、溶液的pH、污染物初始浓度等因素对催化剂光催化活性的影响.结果表明,当[Bi2WO6/AC]=5 g·L-1、pH=5[邻硝基苯酚]0=100 mg·L-1时,催化剂可见光降解活性最好,60 min后邻硝基苯酚的降解率可达到99.81%.     

原位红外光谱法研究CdS-TiO_2/MWCNTs可见光光催化降解气相甲苯

通过原位红外光谱技术研究了可见光下甲苯在CdS-TiO2/MWCNTs（多壁碳纳米管）和CdS-TiO2光催化剂表面的吸附、光催化降解过程,并考察了水汽对光催化反应的影响.结果表明,在吸附过程中甲苯在CdS-TiO2和CdS-TiO2/MWCNTs光催化剂表面就能被氧化成苯甲醛、苯甲酸等中间产物,水汽的存在有利于提高光...     

Acid-treated Fe-doped TiO2 as a high performance photocatalyst used for degradation of phenol under visible light irradiation

The photocatalytic activity of Fe-doped TiO2 nanoparticles is significantly increased by an acid-treatment process. The photocatalyst nanoparticles were prepared using sol–gel method with 0.5 mol% ratio of Fe:Ti in acidic pH of 3. The nanoparticles were structurally characterized by means of X-ray diffraction(XRD), high-resolution transmission electron microscope(HRTEM), energy-dispersive X-ray spectroscopy(EDX), X-ray photoelectron spectroscopy(XPS) and diffuse reflectance spectroscopy(DRS). It was observed that the photocatalytic activity suffered from an iron oxide contaminating layer deposited on the surface of the nanoparticles. This contamination layer was removed using an HCl acidtreatment process. The photocatalytic activity using 500 mg/L of Fe0.5-TiO2 in a 10 mg/L of phenol solution increased significantly from 33% to 57%(about 73% increase in the performance), within 90 min of reaction time under visible light irradiation. This significant improvement was achieved by removing the iron oxide contamination layer from the surface of the nanoparticles and adjusting p H to mild acidic and basic pHs.