308 nm光作用下α-Fe2O3表面HNO3的光解

采用紫外可见光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)及离子色谱(IC)技术对HNO3在α-Fe2O3表面暗反应和308nm下光解反应进行了研究.考察了时间、HNO3浓度、相对湿度(RH)等条件对反应的影响.结果表明,随着HNO3浓度、光照时间的增加,HNO3在气相与α-Fe2O3表面光解产物浓度均呈指数增加;HNO3在α-Fe2O3表面光解产生的NO2、NO分别为气相产生的3.27及3.87倍,而无论气相还是表面光解的NO2浓度均约为NO的2倍.随着RH的增加,HNO3光解产生的HONO的浓度随之呈指数增大,其产率从RH 20%时的0.023增加到90%时的0.087.α-Fe2O3的表面效应在HNO3的表面光解反应中起主导作用.     

β-In2S3的制备及其太阳光下降解土霉素

利用水热反应法制备β-In2S3纳米颗粒光催化剂,并利用SEM、TEM和XRD等对其进行分析表征;采用土霉素溶液模拟四环素类抗生素废水,探讨In2S3对土霉素的降解效果.结果表明,β-In2S3为立方相纳米颗粒结构,该纳米颗粒由纳米片组成,直径约15~30 nm.以太阳光为辐射光源,In2S3对土霉素具有良好的光催化降解效果,在4 h内对初始浓度为30 mg·L-1的土霉素降解率可达98%以上.降解土霉素后的催化剂在无水乙醇中清洗并烘干,经4次循环利用后,β-In2S3的降解能力仍能达到85%以上,表明β-In2S3光催化剂具有良好的稳定性以及光催化活性.     

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.     

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.     

纳米Fe_3O_4/膨润土的制备、表征及光催化降解焦化废水

以铝柱撑膨润土负载纳米Fe_3O_4制备出性能良好的复合型催化剂。结合X射线粉末衍射(XRD)、扫描电镜(SEM)和比表面孔隙分析(BET)对催化剂的晶相、比表面积和粒度进行表征。负载的纳米Fe_3O_4粒径约为20～30nm,均匀分散到膨润土表面,未发生明显的团聚。在紫外光作用下用该催化剂对焦化厂二沉池出水进行深度处理。结果表明,在催化剂投加量为0.7 g/L,pH为2.5,温度40℃,H_2O_2初始浓度为17.6mmol/L的反应条件下,二沉池出水(化学需氧量COD=140mg/L,色度=400度)经催化氧化降解后,COD和色度可分别降低到54.44 mg/L和10度,达到国家工业再生用水水质标准GB/T 19923-2005(COD≤60 mg/L,色度≤30度)。催化剂重复使用4次时,废水COD和色度去除率保持稳定。     

光氧化反应脱汞技术发展综述

燃煤电厂烟气中汞污染的控制技术研究是目前重要的环保课题之一。气相元素汞成为大气中汞污染的主要来源。文章分析了光氧化反应脱汞技术(包括光化学氧化反应和光催化氧化反应)的反应机理,认为光化学氧化反应技术脱汞均是在紫外光作用下,产生具有强氧化性的基态原子或自由基,将难以脱除的Hg0氧化为高价汞,再通过配套的电除尘器等设备将高价汞捕集,进而达到汞污染控制的目的。不同的是,在光化学氧化反应中,汞的氧化需要借助于电厂烟气中的O2、H2O等成分,而在光催化氧化反应中,反应需要在光催化剂(TiO2或TiO2负载复合物等)的催化作用下进行。阐述了光氧化反应汞脱除技术研究进展。光氧化反应脱汞技术的汞脱除率均可达到60%~70%,具备设备简单、无二次污染等优点。     

V_2O_5-TiO_2离子存储电极薄膜的溶胶-凝胶法制备与性能研究

利用无机溶胶-凝胶技术制备了V2O5-（TiO2）x离子存储电极薄膜。采用X射线衍射（XRD）、原子力显微镜（AFM）、Raman光谱、循环伏安法（CV）和紫外-可见光透射光谱分别研究了复合薄膜的微观结构、化学计量、锂离子注入性能以及光学性能。结果表明复合薄膜具有V2O5的层状结构,其c轴方向的结构取向性有所降低;颗粒尺寸和表面粗糙度显著减小;同时TiO2的复合导致薄膜中V2O5的化学计量发生偏移,氧空位数量增多。当x=0.2时,薄膜具有相对较高的离子存储容量及循环稳定性,并且在离子注入/脱出状态均获得相当高的可见光透过性。     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

ZnO-PMMA复合材料光催化去除水中低浓度氨氮

通过水热法制备纳米ZnO,采用热粘固法成功地将其负载于聚甲基丙烯酸甲酯(PMMA)微球表面,并对ZnO-PMMA复合材料光催化去除水中低浓度氨氮的能力进行了考察.同时,探究了负载比例、初始氨氮浓度、催化剂浓度和pH对低浓度氨氮去除效率的影响.实验结果显示,PMMA改善了纳米ZnO的分散性和光催化能力,ZnO-PMMA能够有效地催化去除氨氮废水.在汞灯照射下,当pH=12、温度为30℃时,1 g·L~(-1)的催化剂(ZnO-PMMA)对50 mg·L~(-1)的氨氮废水去除率达到66%,且反应产物硝氮和亚硝氮含量较低,体现了该催化剂具有将氨氮转化为N2的良好的光催化降解能力.同时,纳米材料可以简单方便地回收,减轻了对环境的潜在影响,符合绿色化学的原则.     

Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

• Selective molecularly imprinted polymer (MIP) binding gel was prepared. • MIP-DGT showed excellent uptake performance for antibiotics. • In situ measurement of antibiotics in wastewaters via MIP-DGT was developed. • The MIP-DGT method was robust, reliable, and highly sensitive. Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.