TiO2可见光降解水中污染物的研究进展

介绍了TiO2光催化降解水中污染物的作用机理,综述了实现TiO2可见光进行光催化降解水中污染物的方法,包括金属掺杂、非金属元素掺杂、半导体复合、表面光敏化等TiO2光催化剂的改性方法及光催化反应器的研制等,指出TiO2光催化是一种可以充分利用太阳能,具有很大发展潜力的水处理方法。     

Preparation and characterization of visible-light-active nitrogen-doped TiO2 photocatalyst

A visible-light photocatalyst was prepared by calcination of the hydrolysis product of Ti(SO4)2 with ammonia as precipitator. The color of this photocatalyst was vivid yellow. It could absorb light under 550 nm wavelength. The crystal structure of anatase was characterized by XRD. The structure analysis result of X-ray fluorescence(XRF) shows that doped-nitrogen was presented in the sample. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants. The photocatalytic activities of samples were increasing gradually with calcination temperature from 400℃ to 700℃ under UV irradiation. It can be seen that the degradation of methyl orange follows zero-order kinetics. However, the calcination temperatures have no significant influence on the degradation of phenol under sunlight. The N-doped catalyst shows higher activity than the bare one under solar irradiation.     

TiO2/粉煤灰光催化降解双氯芬酸钠研究

以燃煤电厂外排的废弃物粉煤灰(CFA)为载体,采用混合泥浆法将TiO2负载在CFA的表面,得到一种新型的复合光催化剂TiO2/CFA.对TiO2/CFA进行了扫描电镜分析、X射线衍射分析和氮吸附测试,并以双氯芬酸钠的光催化降解为评价手段,研究了TiO2负载量对TiO2/CFA光催化性能及重复使用性能的影响.结果表明,TiO2负载量的增加有助于提高TiO2/CFA的光催化性能,但当TiO2负载量过高时,CFA上的TiO2在水处理过程中容易脱落,对TiO2/CFA光催化剂的重复使用性能不利.本研究中,最佳的TiO2负载量约为50%,循环使用6次,其光催化降解效率没有明显降低,双氯芬酸钠的降解率均可达70%以上.     

Efficient degradation of organic pollutants by S-NaTaO3/biochar under visible light and the photocatalytic performance of a permonosulfate-based dual-effect catalytic system

Removing large concentrations of organic pollutants from water efficiently and quickly under visible light is essential to developing photocatalytic technology and improving solar energy efficiency. This study used a simple hydrothermal method to prepare a non-metallic, S-doped NaTaO₃ (S-NTO) photocatalyst, which was then loaded onto biochar (BC) to form a S-NTO/BC composite photocatalyst. After uniform loading onto BC, the S-NTO particles transformed from cubic to spherical. The photogenerated electron-hole pair recombination probability of the composite photocatalyst was significantly lower than those of the NTO particles. The light absorption range of the catalyst was effectively widened from 310 nm UV region to visible region. In addition, a dual-effect catalytic system was constructed by introducing peroxymonosulfate (PMS) into the environment of the pollution to be degraded. The Rhodamine B, Methyl Orange, Acid Orange 7, tetracycline, and ciprofloxacin degradation efficiency at 40 mg/L reached 99.6%, 99.2%, 84.5%, 67.1%, and 70.7%, respectively, after irradiation by a 40 W lamps for 90 min. The high-efficiency visible-light catalytic activity of the dual-effect catalytic system was attributed to doping with non-metallic sulfur and loading of catalysts onto BC. The development of this dual-effect catalytic system provides new ideas for quickly and efficiently solving the problem of high-concentration organic pollution in aqueous environments, rationally and fully utilizing solar energy, and expanding the application of photocatalytic technology to practice.     

Variation of cyanobacteria with different environmental conditions in Nansi Lake, China

Nansi Lake is located on the east line of the South-to-North Water Diversion Project in China. A comprehensive study was carried out to investigate the spatial and temporal distribution of cyanobacteria in the lake from June 2008 to May 2011 based on monthly sample monitoring from five stations. The effect of environmental factors on cyanobacterial abundance was also evaluated. The cyanobacterial community contained 15 genera and 23 species. The cyanobacterial abundance of each monitoring station ranged from 0 to 1.53× 10⁷ cells/L with an average of 1.45×10⁶ cells/L, which accounted for 11.66% of the total phytoplankton abundance. The dominant species of cyanobacteria were Pseudanabaena (32.94%) and Merismopedia (19.85%), not the bloom-forming algae such as Microcystis and Anabaena. In addition, the cyanobacterial community structure and water quality variables changed substantially over the survey period. Redundancy analysis (RDA) suggested that temperature and phosphorus were important environmental factors that affected cyanobacteria. Temperature was the most important factor affecting cyanobacterial abundance. The effect of phosphorus on cyanobacterial abundance was more notable in warm periods than in periods with low temperature.     

Synthesis, characterization, and photocatalytic activity of porous La–N–co-doped TiO2 nanotubes for gaseous chlorobenzene oxidation

The photocatalytic oxidation of gaseous chlorobenzene(CB) by the 365 nm-induced photocatalyst La/N–Ti O2, synthesized via a sol–gel and hydrothermal method, was evaluated. Response surface methodology(RSM) was used to model and optimize the conditions for synthesis of the photocatalyst. The optimal photocatalyst was 1.2La/0.5N–Ti O2(0.5) and the effects of La/N on crystalline structure, particle morphology, surface element content, and other structural characteristics were investigated by XRD(X-ray diffraction), TEM(Transmission Electron Microscopy), FTIR(Fourier transform infrared spectroscopy), UV–vis(Ultraviolet–visible spectroscopy), and BET(Brunauer Emmett Teller). Greater surface area and smaller particle size were produced with the co-doped Ti O2 nanotubes than with reference Ti O2. The removal of CB was effective when performed using the synthesized photocatalyst,though it was less efficient at higher initial CB concentrations. Various modified Langmuir-Hinshelwood kinetic models involving the adsorption of chlorobenzene and water on different active sites were evaluated. Fitting results suggested that competitive adsorption caused by water molecules could not be neglected, especially for environments with high relative humidity. The reaction intermediates found after GC–MS(Gas chromatography–mass spectrometry) analysis indicated that most were soluble, low-toxicity, or both. The results demonstrated that the prepared photocatalyst had high activity for VOC(volatile organic compounds) conversion and may be used as a pretreatment prior to biopurification.     

AgCl/ZnO/GO光催化降解甲基橙的性能研究

为了提高ZnO对偶氮染料污染物的光催化降解效率,以AgCl和GO（氧化石墨烯）作为改性剂,通过水热法和化学沉积法制备了AgCl/ZnO/GO光催化材料,采用XRD、SEM、XPS、UV-Vis方法对材料的物相组成、微观形貌及光学特性进行表征;以MO（甲基橙）为目标污染物,探究其在可见光下的催化降解性能,考察AgCl含量、催化剂投加量、pH对其可见光催化活性的影响.结果表明:①AgCl的沉积和GO的负载增强了ZnO对可见光的响应能力,提高了光生电子-空穴产生、分离效率,同时增加了材料的分散性及其对MO的吸附率,因此AgCl/ZnO/GO光催化材料对MO有良好的可见光催化降解效率.②AgCl/ZnO/GO对MO的催化降解效率随着AgCl含量的增加而增加,随着催化剂投加量的增加呈先增后降的趋势,溶液pH对其降解效果有一定影响,但不显著.③当AgCl/ZnO（二者物质的量的比）为2:1、AgCl/ZnO/GO投加量为70 mg、pH为7、室温下经过可见光照射50 min后,AgCl/ZnO/GO对质量浓度为10 mg/L的MO的降解率可达98.93%;此外,该催化剂重复使用4次对MO仍具有88%的去除率,显示出良好的稳定性.因此,AgCl/ZnO/GO是一种高效、稳定的可见光光催化剂,在废水净化方面具有良好的应用前景.      

片状Bi2O3的制备及其光催化性能

利用化学沉淀法,分别以Bi（NO₃）₃·5H₂O为铋源、稀HNO₃为溶剂和HTMA为沉淀剂,制备出片状Bi₂O₃光催化剂.利用SEM、XRD和BET分别对制备的Bi₂O₃形貌、厚度、晶型和比表面积进行表征,并借助紫外可见漫反射和光化学反应仪对材料的光催化性能进行测试.结果表明：制备的片状Bi₂O₃光催化剂形貌较好,厚度均一,a-Bi₂O₃晶型,对可见光的吸收较强,表现出较好的光催化性能.在模拟可见光300W下,3.0h后Bi₂O₃光催化剂对四环素溶液的降解率可以达到82.6%,远远高于市售纳米Bi₂O₃颗粒.     

H_3PW_(12)O_(40)/TiO_2可见光下光催化降解孔雀石绿的研究

以钛酸四丁酯为原料,采用溶胶-凝胶法制备TiO2光催化剂,然后浸渍法制备出H3PW12O40/TiO2复合型光催化剂,并运用XRD、SEM、FT-IR和DRS对催化剂进行表征和分析.研究了可见光光照下H3PW12O40/TiO2对孔雀石绿降解的光催化活性,考察了浸渍量、催化剂用量、底物浓度、pH值对光催化降解率的影响.实验表明,在pH=5条件下,H3PW12O40/TiO2催化剂用量为0.3g.L-1,浓度为10mg·mL-1的孔雀石绿溶液在2L·min-1曝气、300W可见光下光照4h后光催化降解率为78%,比TiO2光催化活性提高了24%.     

硼掺杂CeO2/TiO2光催化剂的制备及其活性研究

在三氯化钛和钛酸丁酯水解过程中引入硼酸、硝酸铈,制备了具有可见光活性的硼(B)掺杂CeO₂/TiO₂复合氧化物光催化剂,采用XRD、DRS、XPS等手段进行表征,以偶氮染料酸性红B为模型污染物评估了催化活性.结果表明,硝酸铈加入量影响催化剂的吸收带边,随用量增加,吸收带边红移至481nm(Ce/Ti=1.0,摩尔比),继续增加用量,吸收带边轻微蓝移.催化剂晶相组成与焙烧温度有关,500℃时焙烧样品主要由立方晶型CeO₂和锐钛矿TiO₂组成,焙烧温度高于700℃时,TiO₂转化为金红石型,CeO₂则无显著变化.随焙烧温度升高,催化剂吸收带边明显蓝移,综合考虑催化剂稳定性和太阳能利用,认为500℃焙烧较为合适.B1s XPS显示仅有少量B原子进入复合氧化物晶格取代了氧原子,主要以B₂O₃形式存在.酸性红B降解试验显示B掺杂CeO₂/TiO₂可以提高TiO₂的催化活性,紫外光辐射10min最高可使96.0%的酸性红B分解,且反应彻底,表现出较强的氧化能力,但Ce/Ti>0.5(摩尔比)时催化活性显著下降.     

稀土掺杂TiO2膨润土光催化降解中性红的研究

文章主要以膨润土为载体,钛酸正四丁酯和硫酸高铈为原料,采用溶胶-凝胶法制备稀土掺杂TiO2膨润土复合光催化剂,用XRD和SEM对稀土掺杂TiO2膨润土的结构和形貌进行表征,表征结果表明其具有很高的比表面积,并且存在明显的锐钛矿型TiO2晶型特征峰.研究催化剂的用量、染料的初始浓度、光照时间、pH值等因素对中性红染料脱色...     

Response surface methodology analysis of the photocatalytic removal of Methylene Blue using bismuth vanadate prepared via polyol route

Visible-light driven photocatalyst bismuth vanadate (BiVO₄) photocatalyst was synthesized by the polyol route using ethylene glycol. The precipitate was washed, dried and calcined at 450℃ for 3 hr. The sample was characterized by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), zeta potential, surface area (BET method) and band gap energy via diffuse reflectance spectroscopy (DRS). The synthesized BiVO₄ has a monoclinic phase with a surface area of 4.3 m²/g and a band gap energy of 2.46 eV. A majority of the particles were in the range of 90-130 nm as obtained from the particle size distribution histrogram. The efficiency of the sample as a visible-light driven photocatalyst was examined by photodegrading Methylene Blue (MB). The effects of some operational photodegradation parameters such as mass loading, initial dye concentration and pH were also examined. Experimental design methodology was applied by response surface modeling and optimization of the removal of MB. The multivariate experimental design was employed to develop a quadratic model as a functional relationship between the percentage removal of MB and three experimental factors (BiVO₄ loading, MB initial concentration and pH). The percentage removal of MB approached 67.21% under optimized conditions. In addition, a satisfactory goodness-of-fit was achieved between the predictive and the experimental results.     

黄浦江原水中土臭素冬季超标机制研究

基于黄浦江原水中土臭素浓度出现的季节性超标现象,采用高通量测序技术对比分析了夏、冬季微生物群落结构差异,发现夏、冬季水样中微生物群落结构差异显著.土臭素浓度较低的夏季水样中相对丰度较高的微生物为Microcystis、Synechococcus等蓝藻类微生物,其与嗅味物质的合成相关且易于汇集到沉积物内,导致夏季水样与冬季沉积物微生物种群相关;冬季水样中丰度较高的微生物主要为Flavobacterium、Candidatus Pelagibacter、Limnohabitans等水华蓝藻分解微生物,由此推测夏季增殖并汇集于沉积物的水华蓝藻分解是导致原水冬季土臭素超标的主要原因.本研究基于微生物种群结构分析提出了冬季原水中嗅味物质超标的可能机制,为饮用水原水嗅味污染控制提供了理论参考.     

超声对蓝藻细胞生理影响的研究

蓝藻水华会使水体水质恶化,破坏水生生态系统,同时会增加水处理成本,产生臭味并释放藻毒素。蓝藻水华问题成为社会各界的关注热点。超声由于具有反应速度快,操作简便,在处理过程中不引入其他化学物质等优点,已被广泛应用于水处理领域,包括用于蓝藻水华的控制。总结了超声作用参数对蓝藻生长效果的影响,从藻细胞的光合活性、酯酶活性和抗氧化酶系统等方面探讨了超声对蓝藻生理方面产生的影响,分析了超声对藻细胞的作用机理,并对后续的研究进行了展望,以期为超声控制蓝藻水华的相关研究提供参考。     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

光催化剂Bi3.84W0.16O6.24在模拟太阳光下对双酚A的降解

采用水热合成法在pH12的条件下合成圆片状Bi3.84W0.16O6.24催化剂.通过XRD、FESEM、TEM、UV-vis漫反射等表征分析Bi3.84W0.16O6.24的物相、形貌和吸光性能.以双酚A(BPA)为目标污染物,研究了Bi3.84W0.16O6.24在模拟太阳光辐射下的光催化反应活性.设计L18(37)正交试验研究了BPA初始浓度、催化剂投入量、反应溶液pH值以及光催化反应时间对Bi3.84W0.16O6.24光催化降解BPA的影响.正交试验的极差和方差分析结果表明,BPA初始浓度和反应时间影响非常显著,催化剂用量影响显著,反应溶液pH值影响不显著,初始浓度和催化剂量的交互作用很小.在BPA初始浓度为20mg/L、催化剂量2g/L、反应溶液pH7、反应时间为90min的条件下Bi3.84W0.16O6.24对BPA去除率达99.5%,TOC去除率为86.0%,BPA的降解符合一级反应动力学.     

花状软锰矿的超声合成及其对亚甲基蓝的脱色性能

首次通过操作简便成本低廉的超声方法合成花状软锰矿(MWs).采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)以及能量散布分析仪(EDS)等测试手段对其结构和形貌进行表征.研究了MWs对偶氮染料亚甲基蓝(MB)的脱色性能,考察pH值、反应时间、MWs投加量以及MB初始浓度等影响因子对脱色效果影响.结果表明,MWs对MB具有优良的脱色性能,90min达到近100%的脱色率,无需使用H2O2或者UV灯和超声等其它辅助设备,这明显优于其他催化剂,如Mn3O4/H2O2需3h达到99.7%最大脱色率、ZnS/CdS在光照下需6h最大脱色率仅为73%、硫改性的TiO2光照下需4h才能达到近100%的脱色率.     

稻香湖景酒店景观再生水生产中的细菌群落结构变化

为了解生活污水处理系统对水体细菌群落结构及多样性的影响,以北京稻香湖景酒店生活污水处理系统为例,利用16SrDNA文库技术研究了不同处理阶段水体细菌的群落结构及多样性.结果表明,酒店排放的生活污水中细菌类型较多,Shannon-Weaver多样性指数为3.12,其中ε-变形杆菌纲在克隆文库中所占比例最高,达32%;另外还有9%～15%的克隆分别与CFB类群、γ-变形杆菌纲、梭杆菌门和厚壁菌门的细菌高度同源;经中水站处理后,水体细菌多样性指数下降到2.41,β-变形杆菌纲的细菌占据绝对优势,比例高达73%;进一步经小型人工湿地处理后,细菌的多样性指数提高到3.38,其中放线菌门的细菌比例最高达33%,成为最优势的类群,蓝细菌的比例次之,达26%;而对照样品中蓝细菌为最主要的优势类群,比例高达38%,主要涉及的种属为蓝菌属、聚球藻属和微囊藻属,比例分别为47.1%、17.6%和8.8%,且检测到少量铜绿微囊藻,水体有轻度蓝藻水华暴发.因此,该酒店的生活污水经过逐级处理改造成景观再生水的过程中改变了细菌的优势群落结构和多样性;经过处理的水体未有蓝藻水华出现,水体状况优于对照.该研究对了解景观再生水生产过程中细菌微生态的变化、将来从生态学的角度加强蓝藻水华的控制提供有用的资料.     

TiO2/PS/Fe3O4 光催化剂的低温制备及其光催化和磁回收性能

以聚苯乙烯(PS)包覆油酸修饰过的纳米Fe3O4为磁核,在低温(90℃)、中性(pH=7左右)条件下,制备了以PS为惰性隔离层的磁载TiO2光催化剂.用X射线衍射仪(XRD)、透射电子显微镜(TEM)、傅里叶红外分光光度计(FT-IR)、振动样品磁强计(VSM)对催化剂的物相组成、形貌、表面性质、磁学性质进行了表征.以苯酚为模拟污染物,考察了其光催化活性,以自制的磁回收装置,考察其回收特性.结果表明,低温制备的TiO2为锐钛矿结构,平均粒径为2～5 nm,催化剂TiO2/PS/Fe3O4[其中物质的量比为n(TiO2)∶n(St)∶n(Fe3O4)=60∶2.5∶1]具有结构完整的壳/壳/核结构,TiO2在PS/Fe3O4表面负载牢固;光催化降解苯酚遵循一级反应动力学方程,TiO2/PS/Fe3O4[n(TiO2)∶n(St)∶n(Fe3O4)=60∶2.5∶1]的反应速率常数K=0.025 8,与纯TiO2的活性接近(K=0.026 2);循环使用5次后,反应速率常数仅降低0.003 4.所制催化剂具有较强的磁感应强度,平均回收率可达到92%以上.该低温水解法制备的磁载TiO2光催化剂具有良好的应用前景.     

Synthesis and enhanced visible-light responsive of C,N,S-tridoped TiO2 hollow spheres

C,N,S-tridoped TiO2 hollow spheres （labeled as C,N,S-THs） were synthesized using carbon spheres as template and C,N,S-tridoped TiO2 nanoparticles as building blocks. The structure and physicochemical properties of the catalysts were characterized by X- ray diffraction （XRD）, scanning electron microscopy （SEM）, UV-Vis diffuse reflectance spectrum （DRS）, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy （XPS） and Photoluminescence emission spectroscopy （PL）. The results showed that the hollow spheres had average diameter of about 200 nm and the shell thickness was about 20 nm. The tridoped TiO2 hollow spheres exhibited strong absorption in the visible-light region. C,N,S-tridoped could narrow the band gap of the THs by mixing the orbit O 2p with C 2p, N 2p and S 3p orbits and shift its optical response from ultraviolet （UV） to the visible-light region. PL analysis indicated that the electron-hole recombination rate of TiO2 hollow spheres had been effectively inhibited when doped with C, N and S elements. The photocatalytic activities of the samples were evaluated for the degradation of X-3B （Reactive Brilliant Red dye, C.I. Reactive Red 2） aqueous solution under visible-light （λ 〉 420 nm） irradiation. It was found that the C,N,S-tridoped TiO2 hollow spheres indicated higher photocatalytic activity than commercial P25 and the undoped counterpart photocatalyst.