超声波/零价铁体系降解五氯酚的机理

在超声波/零价铁体系中,以五氯酚为目标污染物,分别对各种形态铁离子浓度和羟基自由基表观生成率进行了定量测定,探讨了超声波与零价铁的协同作用机理.结果表明,在超声波/零价铁体系降解五氯酚过程中,同时存在超声波的羟基自由基氧化作用和零价铁的还原作用,其中超声波的羟基自由基氧化作用占主导,零价铁大大地促进了该体系羟基自由基的生成.同时,采用气相色谱.质谱联用仪测定中间产物,并结合相关研究推测,超声波/零价铁降解五氯酚主要是通过羟基自由基的氧化脱氯、五氯酚氧自由基的自身耦合,以及零价铁的还原脱氯3种降解途径完成的.     

超声波/零价铁协同降解苯酚的研究

研究了超声波/零价铁协同降解苯酚的过程,并对其降解机理进行了研究,分别考察了零价铁投加量,溶液初始浓度,初始pH值,超声功率等因素对苯酚降解的影响规律。结果表明,超声波/零价铁工艺能有效的降解水中的苯酚,零价铁的最佳投加量为0.8 g/L,苯酚浓度越低处理效果越好,苯酚在酸性条件的降解率高于碱性条件,在0~400 W超声作用下,功率越大,降解率越大;超声波与零价铁粉对苯酚的降解具有协同作用,其降解过程符合一级动力学规律。在体系中加入自由基捕获剂正丁醇抑制了苯酚的降解,说明苯酚的降解过程主要依靠羟基自由基(.OH)的氧化作用。     

超声波/零价铁体系降解苯胺废水的影响因素及机理研究

以苯胺为研究对象,通过试验对超声波/零价铁体系降解苯胺的过程与机理进行了研究,分别考察了零价铁投加量、废水初始pH值、废水初始浓度对苯胺污染物降解的影响规律,结果表明:超声波/零价铁体系适宜处理苯胺浓度较低的废水,零价铁的最佳投加量为2.8g/L,废水初始pH值的适宜范围为7～8;超声波/零价铁体系降解苯胺具有协同作用,对苯胺的降解以.OH自由基的氧化作用为主,其降解过程符合一级反应动力学规律;紫外可见光谱显示,苯胺在超声波/零价铁体系中发生了开环反应。     

零价铁表面积对泥浆反应体系中硝基苯降解行为的影响

硝基苯能够被零价铁还原成为苯胺. 利用气相色谱分析方法,研究了泥浆体系中零价铁表面积对硝基苯污染底质降解行为的影响. 结果表明,在沉积物中初始w(硝基苯)为8.87 μg/g,按照3.27 g/L最佳比例投加还原铁粉,经2 h反应约有97%的硝基苯被降解;其还原机理为表面接触反应,铁粉总表面积是影响硝基苯降解的主要参数;沉积物中硝基苯降解速率常数(K)和残留量(y)与单位体积泥浆中零价铁总表面积(ρ_a)之间表现为线性和负指数相关性,其关系式分别为:K0.006　5+5.165　87×10－4ρ_a和y8.57exp(-ρ_a/7.66)+0.25;零价铁还原硝基苯的降解过程,其降解动力学符合准一级方程,并且通过SEM扫描电镜发现零价铁在反应过程中表面被严重腐蚀,颗粒组成发生明显改变.      

三种零价铁对土壤中六氯联苯PCB138降解研究

采用纳米级零价铁、镍铁双金属和微米级零价铁在常温常压条件下还原降解土壤中的六氯联苯PCB138,GC-MS分析降解产物。结果表明,3种零价铁对土壤中的PCB138均有明显的降解效果。在实验条件下,随着3种零价铁投加量的增大,土壤PCB138的降解率也随之升高。反应体系初始p H值越低,3种零价铁对土壤中PCB138的降解效果越好。在20~60℃实验条件下升高温度对土壤中PCB138含量影响不大。动力学分析显示,纳米级零价铁、镍铁双金属和微米级零价铁对土壤中PCB138降解过程均符合一级反应动力学,反应速率常数分别为0.015 46/h、0.019 37/h和0.009 89/h。3种零价铁粉比表面积和扫描电镜分析结果显示,纳米级零价铁和镍铁双金属的比表面积比微米级零价铁粉大600~800倍,其表面形态更利于污染物质发生还原降解反应。     

超声波-零价铁粉还原降解含氯有机物的研究

文章研究了零价铁粉的投加量、超声波的协同作用以及水浴摇床时间对甲醇溶液中氯苯的还原性脱氯作用的影响,并将其脱氯的最佳条件应用到二氯苯和四氯化碳。结果表明:在实验范围内,零价铁粉投加量为0.2g/mL时,氯苯的去除效果最好;在实验范围内,超声波反应时间为30min,水浴摇床反应时间为1h时,氯苯的去除效率好;零价铁降解氯苯的最佳条件为:零价铁粉投加量0.2g/mL,超声波时间30min,水浴摇床时间1h,降解率可达89.11%;在氯苯的最佳处理条件下,二氯苯和四氯化碳也有稳定的处理效果,分别为49.98%和50.69%。     

ANAMMOX菌铁自养反硝化工艺的稳定性

在非严格厌氧的连续流反应器中,通过调节进水pH、外加一定浓度的Fe~(2+)以及定期更换新鲜铁粉这3种运行方式探讨维持厌氧氨氧化(ANAMMOX)菌利用零价铁去除硝酸盐反应体系长期稳定运行的适宜条件.结果表明,随着反应进行、受零价铁表面钝化的影响,该体系硝酸盐去除率逐渐下降,反应器难以持续运行.在一定范围内降低进水pH(5～7),或者额外投加一定量的Fe~(2+)对改善该反应体系的稳定性效果不显著.通过定期更换新鲜铁粉的方式,可以有效提高硝酸盐去除率、增强反应器稳定性.相比对照组可稳定运行7 d,实验组可至少稳定运行60 d,硝酸盐平均去除率提高22. 23%.因此,采取适宜措施保证体系内有足够具有活性的零价铁、消除零价铁钝化的不利影响,是ANAMMOX菌利用零价铁去除硝酸盐反应体系高效、稳定运行的关键.     

超声波强化零价铁/过硫酸钾体系处理柠檬酸镍络合废水

以柠檬酸镍络合废水为目标废水,考察了超声波(US)强化零价铁(Fe~0)/过硫酸钾(PS)体系的初始pH、过硫酸钾用量(C_(PS))、超声波功率、零价铁与过硫酸钾质量比(m)、零价铁粒径(d_(Fe~0))对镍去除的影响.结果表明,在超声波功率为600 W,pH为3,过硫酸钾用量为0.45g·L~(-1),Fe~0∶PS(质量比)为0.8,零价铁粒径为75μm的条件下反应60 min时,镍的去除率可以达到100%.不同体系的对照实验和反应前后零价铁SEM、EDS分析结果表明,US/Fe~0/PS体系效果明显优于US/Fe~0、US/PS和Fe~0/PS体系,超声波对Fe~0/PS体系具有强化作用,能促进零价铁持续释放具有催化作用的Fe~(2+).最后,通过红外光谱和紫外光谱分析了柠檬酸镍破络机理.TOC变化规律表明,体系矿化速率低于体系中柠檬酸的降解速率,说明柠檬酸镍降解首先是一个快速破络过程,随后是破络后的中间产物进一步降解矿化.     

Fe3+或Fe2+均相催化H2O2生成羟基自由基的规律

利用电子自旋共振-自旋捕集技术(ESR)研究了不同条件下Fenton和类Fenton反应中羟基自由基的变化规律.结果表明,Fenton和类Fenton在起始反应阶段羟基自由基的生成速率都随着H₂O₂和Fe³⁺或Fe²⁺浓度的增大而增大,但Fenton反应在起始阶段羟基自由基生成速率显著高于类Fenton反应.Fenton反应pH在2.5～3.5,而类Fenton反应pH在2.8～3.0范围内有较高的自由基生成速率.起始反应完成后,反应过程中Fenton与类Fenton反应自由基的生成速率也存在显著差异.结果表明,两体系在反应起始和反应过程中都存在着机制的差异.     

柠檬酸配体促进Cu/Fe0电子转移增强氧化性能的研究

该研究通过掺杂过渡金属Cu和Ni方式制备了2种改性纳米零价铁材料,在有无柠檬酸(CA)2种体系下,探究了材料对诺氟沙星的降解效果并分析其作用机理。结果表明,1% Cu/Fe⁰-CA对诺氟沙星有最佳降解效果,1 h降解效率约为73%;而没有柠檬酸的Cu/Fe⁰体系,也有70%左右的降解效率。结合DFT理论计算分析,对体系中·O₂^-、H₂O₂、·OH等自由基形成过程探究表明,无柠檬酸配体时主要是还原降解过程,在Fe⁰转化Fe²⁺时,电子直接传递至铁表面吸附的诺氟沙星,且还原氢(H*)起到还原作用。在有柠檬酸配体存在时则源于活化分子氧过程,在电子传递过程中产生H₂O₂,继而与柠檬酸亚铁产生类Fenton反应,体现出强氧化效应。     

无机助催化(类)芬顿反应降解有机污染物的研究进展

芬顿技术常用于去除水中的有机污染物,通过向溶液中加入Fe2+和H₂O₂便可以产生自由基并进一步氧化有机物,但传统的芬顿技术总是伴随着诸如铁泥、较窄的pH适用范围等缺点. 近年来,以MoS₂为代表的一类无机助催化剂可以有效地促进(类)芬顿反应中Fe2+/Fe3+的循环以及反应中自由基的生成,MoS₂因其表面存在的还原态金属活性中心可以有效地还原Fe3+或Co3+等金属离子并减少元素的流失. 为了进一步明确无机助催化剂的性能和微观机制,本文综述了以MoS₂为代表的助催化剂在均相和非均相芬顿反应中对于H₂O₂及PMS的活化效果. 结果表明:无论是在均相还是非均相(类)芬顿反应中,MoS₂、CoS₂等表面存在的还原态金属活性中心均能显著促进(类)芬顿反应中金属离子的循环,并提高反应中强氧化性活性氧物种的浓度,而一些助催化剂在助催化芬顿反应的同时,甚至可以自产活性氧物种或是自主活化PMS. 但目前的研究仍存在一些不足,如无机助催化剂极有可能会给反应体系带来重金属离子的二次污染,一般的非均相催化剂及助催化剂的使用时限较短,并不能满足实际工业化的应用. 因此在未来的研究中,提高催化剂和助催化剂的反应稳定性和进一步提高反应活性应作为研究的重点. 其中,将纳米技术与催化剂和助催化剂的制备相结合,或进一步改善助催化剂的效能均可能有效推进无机催化剂及助催化剂在工业应用上的进程.      

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。     

TiO2及负载Fe(Ⅲ)可见光催化H2O2降解扑草净的协同效应

以TiO2P25(TIO-P25)及Fe(NO3)3为前驱物制备TiO2负载Fe3+多相催化剂Fe/TIO-P25,研究Fe/TIO-P25可见光催化H2O2降解扑草净的协同效应.XRD、XPS、EDS及SEM结果表明,Fe元素以Fe2O3形式高度分散于TiO2表面,负载量约1.5%(wt%),未对TIO-P25的粒径及形貌产生明显影响,Fe/TIO-P25的粒径约20~40nm;光催化结果表明,Fe/TIO-P25能可见光催化H2O2降解扑草净,反应30min降解率达100%,远大于TIO-P25的催化活性,负载Fe与TIO-P25之间存在明显的协同效应;通过对反应体系的荧光光谱分析显示,扑草净的降解涉及较单纯羟基自由基(·OH)过程更为复杂的反应机理.     

Effect of phosphate on heterogeneous Fenton oxidation of catechol by nano-Fe3O4: Inhibitor or stabilizer?

The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene, in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy (ATR-FTIR) was used to monitor the surface speciation at the nano-Fe₃O₄ catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H₂O₂. This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H₂O₂. In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H₂O₂ and formation of hydroxyl radicals, and inhibit the catalytic ability of Fe₃O₄ catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H₂O₂ stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.     

Application of percarbonate and peroxymonocarbonate in decontamination technologies

Sodium percarbonate (SPC) and peroxymonocarbonate (PMC) have been widely used in modified Fenton reactions because of their multiple superior features, such as a wide pH range and environmental friendliness. This broad review is intended to provide the fundamental information, status and progress of SPC and PMC based decontamination technologies according to the peer-reviewed papers in the last two decades. Both SPC and PMC can directly decompose various pollutants. The degradation efficiency will be enhanced and the target contaminants will be expanded after the activation of SPC and PMC. The most commonly used catalysts for SPC activation are iron compounds while cobalt compositions are applied to activate PMC in homogenous and heterogeneous catalytical systems. The generation and participation of hydroxyl, superoxide and/or carbonate radicals are involved in the activated SPC and PMC system. The reductive radicals, such as carbon dioxide and hydroxyethyl radicals, can be generated when formic acid or methanol is added in the Fe(II)/SPC system, which can reduce target contaminants. SPC can also be activated by energy, tetraacetylethylenediamine, ozone and buffered alkaline to generate different reactive radicals for pollutant decomposition. The SPC and activated SPC have been assessed for application in-situ chemical oxidation and sludge dewatering treatment. The challenges and prospects of SPC and PMC based decontamination technologies are also addressed in the last section.     

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals(·OH)from reactions between recyclable solid catalysts and H_2O_2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions(HO_2./O_2~-.)and high-valent iron are the three main types of reactive oxygen species(ROS),with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.     

铁刨花-Fenton-絮凝工艺对染料生产废水中AOX、色度和TOC的去除效果研究

采用铁刨花-Fenton-絮凝工艺处理染料生产废水,考察了不同Fe~(2+)与H_2O_2摩尔比(1∶3~1∶15)、铁刨花反应时间(2~5h)、Fenton氧化反应时间(20~80 min)下可吸附性有机卤代物(AOX)、色度和总有机碳(TOC)的去除效果.结果表明,AOX、色度和TOC去除率随Fe~(2+)与H_2O_2摩尔比的降低先升高后减少,随铁刨花和Fenton反应时间的增加而持续升高.最优化条件为Fe~(2+)与H_2O_2摩尔比1∶8、铁刨花反应时间4 h和Fenton反应时间60 min,该条件下AOX、色度和TOC的去除率分别为94.2%、93.7%和27.2%.比较实验结果表明,铁刨花-Fenton-絮凝组合工艺对废水AOX、色度和TOC的去除效果远优于铁刨花处理、Fenton氧化、絮凝沉淀的单个技术或两两技术组合效果.GC-MS分析表明,废水中的有机卤代物和苯胺类污染物得到高效去除,此外硝基苯类、苯酚类、苯甲醛类、醚类、腈类和杂环化合物等有毒有害物质也均得到高效去除.叔丁醇捕获·OH实验表明·OH在Fenton反应中的主导作用.     

New insights into FeS/persulfate system for tetracycline elimination: Iron valence, homogeneous-heterogeneous reactions and degradation pathways

In this study, complete tetracycline（TTC） and above 50% of total organic carbon（TOC） were removed by Fe S/PS after 30 min under optimized conditions. Although free radicals and high-valent iron ions were identified to generate in the process, the apparent similarity between intermediate products of Fe S/PS, Fe/PS, and UV/PS systems demonstrated that the degradation of TTC was due to sulfate radicals(SO₄^·-) and hydroxyl radicals（ ·OH）. Based on the reaction between free radi...