Fenton反应及其参与的光催化体系的机理研究进展

综述了光催化降解有机污染物和杀菌的机理,其中降解有机物机理的主要内容为空穴和羟基自由基(·OH)氧化分解有机污染物,杀菌机理与降解有机物类似,即电子和空穴或含氧自由基攻击细菌的细胞壁、细胞膜和胞内成分,使细菌失活。分别从Fe~(2+)和Cu~(2+)两种离子介导的Fenton反应总结了Fenton反应的机理,得出两种离子介导的Fenton反应具有类似机理的结论。最后阐述了目前在光催化体系中引入Fenton反应的研究现状及作用机理,发现将Fenton反应引入光催化体系是促进光催化活性的有效途径。     

二氧化钛光催化消毒技术在水处理中的研究

二氧化钛光催化消毒是一种新型的水处理技术,可以有效地去除水中常规的和新出现的致病微生物,杀菌效果好且相对常规消毒手段消毒副产物较少,处理工艺自身不会对处理水造成二次污染。通过总结光催化技术的研究历史,阐述了光催化氧化机理和杀灭微生物的具体过程,综述了二氧化钛光催化技术在水处理领域中杀灭细菌、真菌、藻类、原生动物和病毒的研究成果,论述了二氧化钛光催化消毒的必要性,并对二氧化钛光催化消毒的应用前景作了展望。     

Advances in photocatalytic disinfection of bacteria: Development of photocatalysts and mechanisms

Photocatalysis has attracted worldwide attention due to its potential in solar energy conversion. As a “green” advanced oxidation technology, it has been extensively used for water disinfection and wastewater treatment. This article provides a review of the recent progress in solar energy-induced photocatalytic disinfection of bacteria, focusing on the development of highly efficient photocatalysts and their underlying mechanisms in bacterial inactivation. The photocatalysts are classified into TiO₂-based and non-TiO₂-based systems, as TiO₂ is the most investigated photocatalyst. The synthesis methods, modification strategies, bacterial disinfection activities and mechanisms of different types of photocatalysts are reviewed in detail. Emphasis is given to the modified TiO₂, including noble metal deposition, non-metal doping, dye sensitization and composite TiO₂, along with typical non-TiO₂-based photocatalysts for bacterial disinfection, including metal oxides, sulfides, bismuth metallates, graphene-based photocatalysts, carbon nitride-based photocatalysts and natural photocatalysts. A simple and versatile methodology by using a partition system combined with scavenging study is introduced to study the photocatalytic disinfection mechanisms in different photocatalytic systems. This review summarizes the current state of the work on photocatalytic disinfection of bacteria, and is expected to offer useful insights for the future development in the field.     

悬浮型光催化纳滤膜反应器对染料中间体H酸溶液的降解

在多组分条件下通过采用悬浮型光催化纳滤膜反应器进行目标污染底物H酸的光催化降解效率及反应动力学研究,控制干扰污染物吐氏酸和变色酸浓度分别为5,10,20,25,40mg/L,控制H酸浓度100mg/L恒定不变.实验结果表明,在单组分光催化纳滤膜反应器中,在Ct/C030.7条件下,降解过程遵循L-H 零级(0~12min)与L-H一级(12~20min)的混合动力学模型;在多组分光催化纳滤膜反应器中,随着干扰物浓度的增加,在Ct/C030.7条件下(约0~20min反应时间段)其降解过程均对应地遵循L-H一级反应动力学模型.通过实验进一步证实,H酸光催化降解动力学的改变主要由耦合光催化反应器内底物和光催化剂表面H酸的浓度差异性引起.     

高铁酸盐对微生物的灭活特性及影响因素

高铁酸盐是一种集氧化、消毒和絮凝等多功能于一体的水处理剂,具有广阔的应用前景。综述了高铁酸盐在消毒方面的研究进展,包括高铁酸盐对细菌和病毒的灭活特性及影响消毒效果的主要因素,并将高铁酸盐与氯、臭氧等常规消毒技术在消毒效果、消毒机理、消毒副产物生成量等方面进行了详细比较。高铁酸盐在较宽的pH范围内对不同水体中的细菌和病毒均呈现较好的灭活效果,pH、温度和有机物是影响高铁酸盐消毒效果的重要因素,高铁酸盐和其他消毒技术联用将是未来研究的关注点。     

连续流光催化消毒器灭活E.coli及病毒的性能

紫外消毒是污水处理常用技术.紫外线仅能破坏微生物的遗传物质,阻断其繁殖,并不能彻底杀死微生物,一旦停止紫外光照射,微生物可在修复酶的作用下恢复活性.光催化过程能产生强氧化性·OH,破坏细胞壁和细胞膜,彻底杀死微生物.为考察光催化技术消毒效率、抑制复活性能及应用潜力,在市售紫外消毒器中安装了光催化组件,搭建了连续流动式光催化消毒器.以大肠杆菌(E.coli)和噬菌体为目标物评价其消毒能力.紫外剂量50 m J·cm-2条件下,初始浓度3.40×106CFU·m L-1的E.coli原水流经紫外消毒器后被去除4.12 log10的E.coli,而流经光催化消毒器后去除4.79 log10.同时光催化处理后E.coli的光复活率仅为紫外消毒后的17%.连续运行40 h的灭菌能力稳定.光催化设备对噬菌体F2和噬菌体MS2的去除率分别为6.37 log10和6.00 log10,表明该设备也具有病毒去除能力.     

太阳能固定膜光催化灭菌的特性

以实用型太阳能固定膜光催化中试装置对水中大肠杆菌的灭活特性进行了研究.结果表明,太阳能固定膜光催化灭菌包含光催化灭菌和阳光直接灭菌的协同作用,光催化杀菌效果优于阳光的直接杀菌效果.环境扫描电镜分析(ESEM)表明,光催化处理对菌体产生了致命性破坏.光催化灭菌还具有良好的持久性,灭菌处理8 h后,没有出现明显复活再生现象.光催化灭菌速率随循环流速、光强的增大而增大.太阳能固定膜光催化灭菌技术具有良好的应用前景.     

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。     

红球菌跨膜运输荧蒽的差异膜蛋白分析

提取不同时间荧蒽诱导下红球菌BAP-1分泌的膜蛋白,利用同位素标记相对和绝对定量技术（iTRAQ技术）结合液相二级质谱对差异膜蛋白进行聚类以及生物信息学分析.旨在从蛋白质层面上研究红球菌BAP-1跨膜运输荧蒽过程中起关键作用的膜蛋白种类及其作用机制.结果共鉴定到172个差异膜蛋白.通过差异膜蛋白的COG和GO功能分析,发现荧蒽的加入主要影响了红球菌BAP-1细胞膜上与能量、转运相关的膜蛋白.ABC转运蛋白和TonB依赖转运蛋白作为微生物主要的载体蛋白对BAP-1跨膜运输荧蒽起到了重要作用.过氧化氢酶和超氧化物歧化酶在第6d有一个显著上调,作为抗氧化防御机制来保护微生物.各种膜蛋白在不同阶段发挥着各自作用,这些蛋白共同组成蛋白互作网络调控红球菌BAP-1的跨膜运输过程.     

采油污水的电催化杀菌工艺及其作用机理

利用形稳阳极借助于电催化方法对油田污水中的硫酸盐还原菌(SRB)、铁细菌(FB)、腐生菌(TGB)进行杀菌实验研究,确定了最佳操作条件,并对杀菌机理作了初步探讨。结果表明,在电流密度30mA/cm2、极板间距2cm、pH值5.0下处理30min时三种细菌的杀菌率均达100%。通过对杀菌机理的初步探讨表明,在电催化过程中产生的活性氯对杀菌效果起主要作用。     

ClO2消毒工艺对污水处理厂出水超级耐药基因的影响

为了研究二氧化氯（chlorine dioxide,ClO₂）消毒工艺对污水处理厂出水中超级耐药基因（super antibiotic resistance genes,SARGs）的去除效果,对污水处理厂出水消毒前后的水样进行了全年采集,并采用微孔滤膜正压过滤法及核酸吸附柱-洗脱法分别富集水中细菌和胞外核酸后,利用荧光定量PCR技术对其中的9种SARGs进行定量检测.结果表明,无论是胞内还是胞外核酸,均有NDM-1、MCR-1 和MEC-A被检测出;同时,ClO₂消毒后上述3种SARGs的胞内相对总浓度明显上升（P<0.05）,且ClO₂消毒对胞内SARGs相对浓度的影响与季节有关,其中春季、夏季和秋季均发生上升,且春季升高最为明显,达2倍,而冬季出水在消毒前后均未测出胞内SARGs;胞外SARGs则在ClO₂消毒前后没有明显浓度变化.因此,ClO₂消毒不能有效去除污水处理厂出水中胞内和胞外SARGs污染.     

屋面雨能驱动微滤膜池耦合电氧化消毒处理雨水

为屋面雨水的再生研发合适的处理技术,提出了 一种利用屋面雨能驱动微滤膜池耦合电氧化消毒处理屋面雨水的系统,研究了重力驱动膜生物反应器处理模拟屋面雨水的效果.在运行280 h的设定水头(△H = 0.6 m)下,膜通量稳定在7 L/(m2.h),膜出水浊度控制在0.34 NTU以下,其对有机物的去除率很低,但对氨氮的去除...     

污水厂二级出水中抗生素抗性细菌的紫外灭活与复活特性

抗生素抗性细菌(ARB)作为新兴污染物受到了广泛关注,但紫外线(UV)消毒对ARB去除效果的研究尚不够充分。以某城市污水处理厂过滤后的二级出水为研究对象,通过分析UV消毒前后水中四环素、氨苄西林、氯霉素及链霉素抗性细菌丰度的变化,探究了UV消毒对ARB的去除作用及ARB的光复活与暗修复潜能。结果表明:UV对过滤后二级出水中的4种ARB具有一定灭活能力,4种ARB对UV消毒的耐受能力由高到低分别为:氨苄西林抗性细菌>四环素抗性细菌>链霉素抗性细菌≈氯霉素抗性细菌。当UV消毒剂量为20 mJ/cm2时,氯霉素与链霉素抗性细菌可被完全灭活,消毒后24 h内,这2种ARB未出现光复活或暗修复现象,这一剂量的UV不能完全灭活氨苄西林与四环素抗性细菌,且被灭活后的ARB可实现部分光复活及暗修复。当UV消毒剂量达到80 mJ/cm2时,这4种ARB均被全部灭活,消毒后6 h内,氨苄西林抗性细菌出现了复活现象。不论是在光照还是避光的条件下,UV消毒24 h后水中的总异养菌群中有超过70.32%的细菌对氨苄西林具有抗性,因此,单独UV消毒并不能有效地控制ARB从污水处理厂向环境中的传播。     

Assessment and management of the performance risk of a pilot reclaimed water disinfection process

Chlorination disinfection has been widely used in reclaimed water treatment plants to ensure water quality. In order to assess the downstream quality risk of a running reclaimed water disinfection process, a set of dynamic equations was developed to simulate reactions in the disinfection process concerning variables of bacteria, chemical oxygen demand （COD）, ammonia and monochloramine. The model was calibrated by the observations obtained from a pilot disinfection process which was designed to simulate the actual process in a reclaimed water treatment plant. A Monte Carlo algorithm was applied to calculate the predictive effluent quality distributions that were used in the established hierarchical assessment system for the downstream quality risk, and the key factors affecting the downstream quality risk were defined using the Regional Sensitivity Analysis method. The results showed that the seasonal upstream quality variation caused considerable downstream quality risk; the effluent ammonia was significantly influenced by its upstream concentration; the upstream COD was a key factor determining the process effluent risk of bacterial, COD and residual disinfectant indexes; and lower COD and ammonia concentrations in the infiuent would mean better downstream quality.     

光催化氧化法的影响因素和发展趋势

概述了光催化氧化有机物的机理，讨论了影响其反应速率的诸多因素和如催化剂，光强，有机物浓度，ＰＨ值，温度，外加氧化剂和盐等，探讨了提高反应效率的途径，并指出了今后光催化氧化法在水处理中的应用与研究方向。     

Photocatalytic removal of NO and NO2 using titania nanotubes synthesized by hydrothermal method

In this study, the photocatalysts of titania nanotubes(TNTs) were synthesized at different calcination temperatures using commercial Degussa TiO2(P25) as a precursor. The materials were then characterized by BET, SEM, TEM, and XRD analyses. The photocatalytic reactions with NO and NO2 under UV-A irradiation were both performed. The results showed that the photocatalytic reaction rate of NO was much faster than that of NO2, and the conversion of NO2 to nitrate was the rate-limiting step for photocatalytic removal of NOx if the nitrate produced cannot be removed continuously from the photocatalyst surface. For TNTs calcined at different temperatures, a significant enhancement was observed on the total NOx removal efficiency by TNT calcined at 500°C for both NO and NO2 photocatalytic reaction, which could be attributed to its high anatase crystallinity as well as high surface area. These two factors affect primarily on the NO2conversion step in which the high anatase crystallinity could be responsible for the high efficiency at the beginning, while the high surface area could be accounted for retaining this high efficiency from nitric acid poisoning during the test period.     

Visible-light-driven photocatalytic inactivation of bacteriophage f2 by Cu-TiO2 nanofibers in the presence of humic acid

Pathogenic viruses in drinking water are great threats to public health. Visible-light-driven photocatalysis is a promising technology for virus inactivation. However, the existing photocatalytic antiviral research studies have mostly been carried out in single-component systems, neglecting the effect of natural organic matter, which exists widely in actual water bodies. In this paper, electrospun Cu-TiO₂ nanofibers were prepared as photocatalysts, and their photocatalytic antiviral performance in the presence of humic acid (HA) was comprehensively studied for the first time. The properties of the reaction mixture were measured during the reaction. In addition, the safety, reliability and stability of photocatalytic disinfection in the mixed system were evaluated. The results showed that the virus removal efficiency decreased with the increase of the HA concentration. The type of reaction solution, such as PBS buffer solution or water, did not affect the removal efficiency noticeably. Under acidic conditions, the electrostatic forces between photocatalysts and viruses were strengthened, leading to higher virus removal efficiency. As the reaction time went on, the pH value in the solution increased first and then tended to be stable, the conductivity remained stable, and the dissolved oxygen increased first and then decreased. The safety test showed that the concentration of Cu ions released into the solution was lower than specified by the international standards. No photoreactivation was observed, and the addition of HA significantly reduced the reutilization efficiency of the photocatalysts.     

Photocatalytic degradation of bisphenol A using an integrated system of a new gas-liquid-solid circulating fluidized bed reactor and micrometer Gd-doped TiO2 particles

A new gas-liquid-solid circulating fluidized bed photocatalytic reactor (GLSCFBPR) with internally placed multi-layered UV lamps was developed. Micrometer Gd-TiO₂ particles and commercial nanometer P25-TiO₂ were chosen as the photocatalysts, and the hazardous substance bisphenol A (BPA) was chosen as the model pollutant to investigate the performance of this new photocatalytic system. The results showed that the photocatalytic degradation efficiency of the micrometer Gd-TiO₂ particles was similar to that of the nanometer P-25 particles at their respective optimum dosage but the former could be easily separated out by gravity. After investigating the effects of process parameters on the photocatalytic BPA degradation, the response surface method (RSM) was further used for process optimization. The interactions among process parameters, i.e., TiO₂ concentration, superficial gas velocity and superficial liquid velocity were discovered and a related analysis was carried out to explore the underlying mechanism. A quadratic mathematic model was established and performed satisfactorily when used for prediction. The optimum conditions for this new process were as follows: TiO₂ concentration 4.5 g/L, superficial gas velocity 7.83 × 10^-3 m/sec and superficial liquid velocity 8.65 × 10^-3 m/sec.     

模拟配水管网中悬浮颗粒物对生物膜形成的影响

分别采用2 μm、8 μm醋酸纤维滤膜过滤活性炭柱出水,滤出水分别通入BAR反应器,以活性炭出水做对照试验通入BAR反应器,加氯（次氯酸钠）量均为0.5 mg·L^－１（总氯）,对比3种水质情况下生物膜的形成过程,采用颗粒计数仪测定BAR进水的颗粒物分布.结果表明,悬浮颗粒物能携带大量细菌避开消毒剂的作用,且对生物膜上的细菌量有直接影响.生物膜上的细菌量为：活性炭出水>8 μm滤出水>2 μm滤出水.颗粒物的存在使生物膜结构不稳定,推迟了达到最大生物量的时间,且颗粒物数量越多,粒径越大,生物膜稳定性越差,达最大生物量的时间越长,试验中2号BAR生物膜达最大生物量的时间比1号BAR中生物膜迟4 d,3号BAR生物膜达最大生物量的时间比2号BAR生物膜迟8 d;进水颗粒物数量对出水的细菌量影响很大,颗粒物数量越多,出水细菌量越多.     

紫外线消毒中的光复活作用

近年来,紫外线消毒技术在水处理中得到了越来越广泛的应用,它主要是利用短波紫外对微生物的伤害作用,通过在DNA中形成环丁烷嘧啶二聚体,阻碍基因的正常复制,从而导致细菌失活.但是细菌体内的光裂解酶在远紫外光和可见光作用下能够使失活的细菌重新获得活性,这就是光复活作用.低压消毒设备处理后大肠杆菌表现出了一定的光复活能力,但中压消毒设备能够有效的抑制其光复活作用;而噬肺军团菌在低压和中压设备处理后都表现出了很强的光复活能力.在应用紫外线消毒技术时光复活作用的影响不容忽视.