有机锡化合物降解机制的激光闪光光解研究

利用激光闪光光解技术进行了三苯基锡(TPT)与HNO2水溶液体系的355 nm紫外光光解研究,考察了其瞬态物种的生长和衰减等行为.瞬态吸收光谱分析结果表明,pH为1.5条件下,HNO2在355 nm紫外光照射下可产生羟基自由基(·OH),·OH与TPT的苯反应生成C6H6-OH加合物,其加合反应速率常数为3.3×109 L/(mol·s).     

Thermal degradation of 2-chlorophenol promoted by CuCl2 or CuCl: formation and destruction of PCDD/Fs

The oxidative degradation of 2-chlorophenol in air (equivalence ratio phi=0.8) was investigated at 350 degrees C by using the sealed tube technique under different conditions: in the gas phase and in the presence of copper chlorides (CuCl2 and CuCl in different proportions). Not only PCDD/Fs but carbon oxides and other organic products such as chlorophenols, chlorobenzenes, tetrachloroethylene and tetrachlorocyclopentenedione were quantified in order to evaluate the relative importance of reaction pathways. Additional experiments were performed to analyse the degradation products of octachlorodibenzodioxin and 2-monochlorodibenzodioxin. Although it was stated that chlorobenzenes could be formation precursors for PCDD/Fs, experimental data obtained in this work show that chlorobenzenes can also be degradation products of PCDD/Fs.     

XPS investigation of air pollution ejected by a coal-fired power plant

A method for sampling and investigating the aerosol participates and gaseous pollutants of the air is described. The pollutants were collected on silver (Ag), copper (Cu) and graphite surfaces placed in the neighbourhood of a coal-fired power plant. The study of the composition of the aerosol and gaseous pollutants was carried out by means of XPS (X-ray photoelectron spectroscopic) method, as a function of the distance from the power plant.     

Facile synthesis of CoOOH@MXene to activate peroxymonosulfate for efficient degradation of sulfamethoxazole: performance and mechanism investigation

Environmental Science and Pollution Research - Using MXene as substrate, CoOOH@MXene with different mass content of CoOOH were prepared and used to active peroxymonosulfate (PMS) for the...     

US-UV-Fenton降解硝基苯

采用超声波(US)、紫外光(UV)和Fenton联合降解硝基苯,初步探讨了其作用规律。研究结果表明, UV可以促进双氧水转化自由基的效率,而US同时具有强化传质作用和超声氧化作用,两者均能够强化Fenton氧化硝基苯的降解过程。正交实验结果表明,H2O2初始浓度是硝基苯降解和矿化的最显著影响因素,反应时间和超声功率是矿化的显著影响因素。最佳反应条件为:H2O2 500 mg/L、Fe2+10 mg/L、反应时间60 min、超声波功率100 W,此时,硝基苯完全降解,TOC去除率达到73.0%。Fenton、UV/Fenton和US/UV/Fenton降解硝基苯过程均符合伪一级反应动力学模式,反应速率常数分别为3.37×10-2、3.81×10-2和5.10×10-2min-1。     

Oxidative degradation of 2,4-xylidine by photosensitization with 2,4,6-triphenylpyrylium: homogeneous and heterogeneous catalysis

The possibility of using zeolites containing the 2,4,6-triphenylpyrylium cation as photocatalysts for the degradation of pollutants has been tested on aqueous xylidine (2,4-dimethylaniline) solutions as models for contaminated wastewaters. The influence of the photocatalyst and substrate concentrations on xylidine oxidation has been investigated in homogeneous solution, by performing a series of experiments chosen according to the experimental design methodology (Doehlert uniform array). The empirical models and the corresponding response surfaces obtained from data analysis have been used for simulating and predicting degradation efficiency. The results have shown that conversion increases with increasing amounts of photocatalyst and decreasing concentration of the model pollutant. The fluorescence of 2,4,6-triphenylpyrylium was quenched by xylidine with a rate constant k(q) of 3.1x10(9)M(-1)s(-1). This result suggests a direct electron transfer between the excited pyrylium salt and xylidine. Because of the limited stability of the photocatalyst in homogeneous media, a pyrylium containing Y-zeolite has been tested for the photocatalytic oxidation of xylidine under heterogeneous conditions. The results suggest that the supported catalyst has a much improved stability and that xylidine oxidation rates remain nearly constant during the whole reaction time. An additional advantage of the pyrylium containing zeolite photocatalyst is that it can be recycled and used for further experiments.     

Electrocatalytic oxidation of PCP-Na by a novel nano-PbO2 anode: degradation mechanism and toxicity assessment

Environmental Science and Pollution Research - This study aims at investigating the electrocatalytic oxidation of sodium pentachlorophenate (PCP-Na) using a novel nano-PbO2 powder anode. The...     

超声波/纳米铁协同降解氯代苯酚的试验

通过间歇试验对超声波/纳米铁协同降解氯代苯酚(CPs)废水进行了研究,结果表明,超声波/纳米铁协同对CPs的降解率明显高于单纯超声波和单纯纳米铁的降解率;协同体系、单纯超声波和单纯纳米铁降解CPs均符合准一级反应动力学,协同体系的降解速率较单纯超声波提高了5.1~5.6倍,较单纯纳米铁提高了17.7~21倍,并且比它们的几何迭加值高4倍以上;氯代苯酚降解的准一级速率常数和降解率满足以下规律:PCP>2,4,5-TCP>2,4-DCP>3-CP;探讨了混合废水的降解:在混合废水体系中,结构易裂解的优先降解,然后为浓度高的优先降解。     

超声波／纳米铁协同降解氯代苯酚的试验

通过间歇试验对超声波／纳米铁协同降解氯代苯酚（CPs）废水进行了研究，结果表明，超声波／纳米铁协同对CPs的降解率明显高于单纯超声波和单纯纳米铁的降解率；协同体系、单纯超声波和单纯纳米铁降解CPs均符合准一级反应动力学，协同体系的降解速率较单纯超声波提高了5．1-5．6倍，较单纯纳米铁提高了17．7～21倍，并且比它们的几何迭加值高4倍以上；氯代苯酚降解的准一级速率常数和降解率满足以下规律：PEP〉2，4，5-TCP〉2，4-DCP〉3-CP；探讨了混合废水的降解：在混合废水体系中，结构易裂解的优先降解，然后为浓度高的优先降解。     

辉光放电等离子体氧化降解水中邻苯二甲酸二丁酯

研究了辉光放电等离子体降解水中典型的环境内分泌干扰物邻苯二甲酸二丁酯(DBP)及降解过程中过氧化氢(H2O2)的生成规律。考察了电解质种类、共存污染物(甲醇、叔丁醇)及催化剂等条件对DBP降解及H2O2生成的影响。结果表明,在硫酸钠溶液中DBP降解效率和H2O2生成速率最高;甲醇、叔丁醇等共存污染物对DBP降解和H2O2生成有抑制作用;Fe2+,Fe3+和Cu2+对DBP的降解有催化作用,其催化效果为Fe2+>Fe3+>Cu2+。用高效液相色谱、离子色谱及气质联用仪等仪器分析了降解中间产物,提出了可能的降解机理。     

Oxidative ring cleavage of low chlorinated biphenyl derivatives by fungi leads to the formation of chlorinated lactone derivatives

The yeast Trichosporon mucoides and the filamentous fungus Paecilomyces lilacinus as biphenyl oxidizing organisms are able to oxidize chlorinated biphenyl derivatives. Initial oxidation of derivatives chlorinated at C4 position started at the non-halogenated ring and went on up to ring cleavage. The products formed were mono- and dihydroxylated 4-chlorobiphenyls, muconic acid derivatives 2-hydroxy-4-(4-chlorophenyl)-muconic acid and 2-hydroxy-5-(4-chlorophenyl)-muconic acid as well as the corresponding lactones 4-(4-chlorophenyl)-2-pyrone-6-carboxylic acid and 3-(4-chlorophenyl)-2-pyrone-6-carboxylic acid. Altogether T. mucoides formed 12 products and P. lilacinus accumulated five products. Whereas the rate of the first oxidation step at 4-chlorobiphenyl seems to be diminished by the decreased bioavailability of the compound, no considerable differences were observed between the degradation of 4-chloro-4'-hydroxybiphenyl and 4-hydroxybiphenyl. Twofold chlorinated biphenyl derivatives did not serve as substrates for oxidation by either organism with the exception of 2,2'-dichlorobiphenyl, transformed by the yeast Trichosporon mucoides to two monohydroxylated derivatives. The results show, that soil fungi may contribute to the aerobic degradation of low chlorinated biphenyls accumulating from anaerobic dehalogenation of PCB by bacteria.     

纳米铁协同超声降解氯苯的研究

报道了纳米铁协同超声波降解一氯代苯 (CB)的研究。探讨了有效声强、pH、CB初始浓度对降解效果的影响。比较了纳米铁协同超声波和单纯超声波对CB的降解效果和降解速率 ,反应 2 0min时 ,纳米铁协同超声波的降解率达到95 % ,而单纯超声波的降解率仅为 1 0 8%。上述两者都符合准一级反应动力学 ,超声波降解CB的准一级速率动力学常数k=6× 1 0 -3 min-1 ,而协同作用降解CB的准一级动力学常数k =1 6 3× 1 0 -1 min-1 ,提高了 2 7倍。     

高铁酸钾降解苯胺废水的机制研究

研究了高铁酸钾投加量、初始pH及苯胺初始浓度对苯胺降解效果的影响.结果表明.苯胺废水的COD去除事随高铁酸钾投加量和苯胺初始浓度的增大而升高,而初始pH对COD去除率影响不明显.对高铁酸钾降解苯胺废水后的产物进行了气相色谱/质谱(GCIMS)分析.在此基础上详细探讨了高铁酸钾降解苯胺的机制.     

Oxidative degradation of dimethylsulfoxide by locally concentrated hydroxyl radicals in streamer corona discharge process

This study systematically investigates the characteristic degradation behaviors of dimethylsulfoxide (DMSO) by the streamer corona discharge process (SCDP) in water. The analysis of the oxidized intermediates of DMSO shows that hydroxyl radical (*OH) is the main oxidant responsible for the degradation of DMSO in the SCDP. The various experiments on the degradation and mineralization of DMSO, and the effect of the *OH scavenger suggest that the SCDP produces locally concentrated *OHs in and around the plasma channel. This explanation was also supported by the formation of H(2)O(2) and the effect of the *OH scavenger on the H(2)O(2) production rate in the SCDP. Based on the kinetic data for the degradation of DMSO and the production of H(2)O(2) in the SCDP, the volume of the active region in which the *OHs are concentrated, and the effective concentration of *OH in that region were estimated to be 0.21 microl and 5.0 x 10(-3)M, respectively. This level of *OH concentration in the SCDP is approximately 10(7)-10(9) times higher than that generated in ordinary advanced oxidation processes using *OH. The ramifications of the results obtained in this study on successful water treatment using the SCDP are also discussed.     

Fenton试剂和活化过硫酸钠氧化降解土壤中的二氯酚和三氯酚

氯酚类物质（chlorophenols, CPs）在环境介质中广泛存在且具有很强环境毒性。为探究化学氧化修复场地氯酚类污染的可行性,通过室内实验、模拟搅拌实验、现场中试,开展应用Fenton试剂和活化过硫酸钠氧化降解土壤CPs的研究。结果表明,化学氧化可有效降解土壤中的CPs,在氧化剂用量和CPs总量摩尔比为15:1时,CaO活化Na2S2O8能高效降解土壤中的二氯酚（2,4-DCP）和三氯酚（2,4,6-TCP）,室内实验和现场中试的去除率均达90%以上,处理后的2,4-DCP和2,4,6-TCP浓度均低于《展览会用地土壤环境质量评价标准》（HJ 350-2007）A类标准限值。Fenton试剂在室内实验中降解率达90%以上,但现场中试对2,4-DCP和2,4,6-TCP的降解率仅为66.1%、23.8%,处理后2,4-DCP浓度仍超过A类标准限值1倍以上。此外,在修复过程中,约70%的2,4-DCP、2,4,6-TCP会向液相转移,因此,需要关注修复系统引入水后污染物向液相中的转移可能造成的二次污染。研究结果可为氯酚类污染土壤的修复提供新思路,并为实际工程应用提供理论依据。     

钨酸铋光催化降解萘普生效果及其机理

以萘普生(NPX)为目标污染物,钨酸铋(Bi₂WO₆)为光催化剂,考察NPX浓度、Bi₂WO₆投加量、阴离子种类、溶液pH对Bi₂WO₆光催化降解NPX效果的影响并确定最佳反应条件。通过原位捕获实验、中间产物识别及反应体系化学需氧量(COD)去除效果,解析光催化过程产生的活性自由基种类及其作用、NPX降解路径及反应体系矿化度,揭示NPX降解机理。结果表明：经水热法制备的Bi₂WO₆为纯正交晶系,具有由2D纳米方片构成的3D花朵状结构,平均孔径为10.79 nm,比表面积为32.54 m²·g⁻¹,带隙能为2.54 eV;在500 W长弧氙灯照射下,当NPX浓度为10 mg·L⁻¹、Bi₂WO₆投加量0.4 g·L⁻¹、溶液pH值为4.6时,NPX降解率可达99.83%,光照180 min时矿化度为67.91%,光照反应时间延长至360 min时矿化度为82.14%;Bi₂WO₆价带电势(3.01 eV)高于OH⁻/·OH和H₂O/·OH的电势,因此,空穴(h⁺)能氧化OH⁻和H₂O生成羟基自由基(·OH);而Bi₂WO₆导带电势(0.47 eV)同样高于O₂/$ \cdot {\rm{O}}_2^ - $的电势,单电子(e⁻)还原O₂过程很难发生,只能经多e⁻还原O₂,生成超氧自由基($ \cdot {\rm{O}}_2^ - $)。同时还发现,h⁺和·OH在NPX降解过程中起主要氧化作用,$ \cdot {\rm{O}}_2^ - $起辅助作用。综合上述结果,NPX的降解机理是在活性自由基协同氧化下,NPX分子中的C—C、C—O、C=C键断裂发生脱羧反应和羟基化反应,生成结构简单的中间产物,中间产物继续氧化分解为小分子化合物并部分矿化成CO₂和H₂O。     

高频超声辐照降解水中4-氯酚的研究

本文着重探讨了高频超声波 (1.7MHz)降解 4 氯酚的反应过程和反应机理 ,研究了高频超声波降解 4 氯酚的效果 ,并讨论了 4 氯酚初始浓度等因素对降解效果的影响。高频超声波降解 4 氯酚为一级反应 ,超声波空化效应在降解过程中起主导作用     

超声吹脱去除氨氮的机理和动力学研究

采用超声吹脱技术对某印染厂印染废水中的氨氮进行了处理实验,探索了其反应机理并进行了动力学研究。研究表明,叔丁醇的存在没有降低废水中氨氮的去除率,证明.OH不是超声吹脱去除氨氮反应中的主导氧化物种。通过对反应产物的分析发现,超声吹脱去除氨氮的机理主要是氨氮以游离态的方式在空化效应下高温高压热解成氮气和氢气排出,同时氨气在空化效应产生的超临界状态下传质速度加快,在吹脱条件下更易于从废水中散失。动力学分析表明,印染废水中氨氮的超声去除反应属于一级反应,符合一级反应动力学。     

超声波光催化协同降解对甲基苯磺酸水溶液的机理研究

采用超声波与光催化联合法对模拟废水中难生物降解的对甲基苯磺酸(4-TSA)进行降解实验研究,借助紫外光谱、红外光谱、质谱、气相色谱、高效液相色谱、化学需氧量和总有机碳的检测结果对反应机理进行了初步探讨.实验结果表明:超声波和光催化之间存在着协同效应;当溶液初始质量浓度30 mg/L,光催化剂TiO2投加量为100 mg...     

催化臭氧氧化降解PCB有机废液及其机理

为了高效、快速治理高浓度难降解PCB(printed circuit board)有机废液,研究了氧化钙非均相催化臭氧氧化降解PCB废液的催化机理和催化性能。采用叔丁醇淬灭自由基实验和水杨酸羟基化实验探究催化机理;通过GC/MS研究了PCB废液中有机物可能降解途径;通过单纯形优化法对实验因素进行优化,并通过XRD和BET探究催化剂的循环稳定性。结果表明：氧化钙非均相催化臭氧氧化过程遵循羟基自由基机理;在pH为12.97、CaO质量为1.0 g、废液深度为11 cm、降解时间为150 min、臭氧用量为120 mg·min⁻¹时,COD去除率可达到90.045%;氧化钙经过5次循环后,废液的COD去除率没有显著降低,从92.78%降低至84.04%。CaO应用于催化臭氧氧化过程处理高浓度且难降解的PCB废液,能维持良好的催化性能和循环稳定性,具有良好的应用前景。