单线态氧与氯代酚作用机理的理论研究
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摘要
氯代酚作为常见的环境污染物,对其降解的研究已成为热点。本实验室在前期的研究中发现氯代酚敏化光降解的初级产物(中间体)遇氧化剂NBS,会有发光现象产生,且发光信号强度与氯代酚浓度密切相关,并由此建立了测定氯代酚的流动注射化学发光分析方法。同时实验研究已证实单线态氧与氯代酚反应直接导致了氯代酚的敏化光降解,但是目前我们无法通过实验手段来确定氯代酚敏化光降解后产生的中间体的结构,进而也无法深入探讨单线态氧参与下的氯代酚的敏化光降解机理。计算化学利用有效的数学近似以及电脑程序来计算分子性质进而研究化学问题。利用计算化学方法预测某些反应已取得很好的效果。为此,本文先后选择氯代酚中的代表物质2,4-二氯苯酚和邻氯苯酚作为模型分子,借助计算化学的方法从理论上来模拟单线态氧与氯代酚的反应,以期来推测出该类中间体的结构。依据Bobrowski等人提出的“单线态氧与芳香性和不饱和化合物加成时所涵盖的四大反应类型”,总结归纳出单线态氧与2,4-二氯苯酚(邻氯苯酚)反应的十二条具体的反应路径。通过密度泛函理论B3LYP方法在6-31+G(d, p)基组水平优化得到了反应路径上的反应物(反应复合物)、中间体、过渡态和产物的几何构型、零点能和谐振频率,同时在B3LYP/6-311+(2df, p)水平上进行了单点能计算。最后得出单线态氧与2,4-二氯苯酚(邻氯苯酚)的含有含氢基团的双键进行1,3加成反应,生成一个烯丙基氢过氧化物以及单线态氧与2,4-二氯苯酚(邻氯苯酚)进行1,4加成生成一个氢过氧化物酮类物质的反应,在热力学上发生的可能性较大;进而再通过对它们二者反应活化能垒的分析,发现单线态氧与2,4-二氯苯酚(邻氯苯酚)的含有含氢基团的双键进行1,3加成反应,生成一个烯丙基氢过氧化物的反应在动力学更可行。其间还通过反应过程中所涉及到的各驻点,对它们中的相关原子间的距离以及相关原子的NBO电荷的分析来揭示单线态氧与2,4-二氯苯酚(邻氯苯酚)反应的机理。
Chlorophenols are frequently encountered organic pollutants in the environment. The study of its degradation has become a hot issue. In previous study, it was found in our laboratory that luminescence phenomenon can be produced when the photosensitized degradation products (light emitting precursors) of chlorophenols are treated with NBS. And there is a close correlation between chemiluminescence intensities and the concentrations of chlorophenols. Based on this principle, a series of flow injection chemiluminescence (FIA-CL) analytical methods for the determination of chlorophenols were established. It was generally recognized that the reaction between singlet oxygen and chlophenols is responsible to cause the photosensitized degradation of chlorophenols directly. But due to the complexity of the reaction matrix, the determination of the structures of the light emitting precursors by experimental means is often difficult. Hence it is also difficult to explain the reaction mechanism between singlet oxygen and chlorophenols. Computational chemistry methods are increasingly used for resolving chemistry problems by calculating the molecular properties with computer program. To better understand the chemical structures of the intermediate products formed in the photodegradation process, the reaction between singlet oxygen and chlorophenols is investigated with computational methods in this paper. 2, 4-dichlorophenol and o-chlorophenol were chosen as the model molecules for chlorophenols. Twelve reaction routes for the reaction between singlet oxygen and 2,4-dichlorophenol (o-chlorophenol) were induced by the four principal types of oxygen-addition reactions to aromatic and unsaturated compounds proposed by Bobrowski. The geometries of reactants (reactant complexes), intermediates, transition states and products were optimized at B3LYP/6-31+G (d, p) level. The corresponding vibration frequencies and zero-point energies were calculated at the same level. The single-point energies for all the stationary points were obtained at B3LYP/6-311+ (2df, p) level. We find that the reaction types of“1,3-addition to a double bond connected to a hydrogen-carrying group, resulting in the formation of allylic hydroperoxides”and“1,4-addition to chlorophenols with the formation of hydroperoxide ketones”have much probability than the other two reaction types. But the type of“1,3-addition to a double bond connected to a hydrogen-carrying group, resulting in the formation of allylic hydroperoxides”has the lowest reaction barriers, therefore is predicted to be the preferred route. We also analysis the distances between the correlation atoms and their NBO charges in order to study the reaction mechanism between 2, 4-dichlorophenol (o-chlorophenol) and singlet oxygen.
Chlorophenols are frequently encountered organic pollutants in the environment. The study of its degradation has become a hot issue. In previous study, it was found in our laboratory that luminescence phenomenon can be produced when the photosensitized degradation products (light emitting precursors) of chlorophenols are treated with NBS. And there is a close correlation between chemiluminescence intensities and the concentrations of chlorophenols. Based on this principle, a series of flow injection chemiluminescence (FIA-CL) analytical methods for the determination of chlorophenols were established. It was generally recognized that the reaction between singlet oxygen and chlophenols is responsible to cause the photosensitized degradation of chlorophenols directly. But due to the complexity of the reaction matrix, the determination of the structures of the light emitting precursors by experimental means is often difficult. Hence it is also difficult to explain the reaction mechanism between singlet oxygen and chlorophenols. Computational chemistry methods are increasingly used for resolving chemistry problems by calculating the molecular properties with computer program. To better understand the chemical structures of the intermediate products formed in the photodegradation process, the reaction between singlet oxygen and chlorophenols is investigated with computational methods in this paper. 2, 4-dichlorophenol and o-chlorophenol were chosen as the model molecules for chlorophenols. Twelve reaction routes for the reaction between singlet oxygen and 2,4-dichlorophenol (o-chlorophenol) were induced by the four principal types of oxygen-addition reactions to aromatic and unsaturated compounds proposed by Bobrowski. The geometries of reactants (reactant complexes), intermediates, transition states and products were optimized at B3LYP/6-31+G (d, p) level. The corresponding vibration frequencies and zero-point energies were calculated at the same level. The single-point energies for all the stationary points were obtained at B3LYP/6-311+ (2df, p) level. We find that the reaction types of“1,3-addition to a double bond connected to a hydrogen-carrying group, resulting in the formation of allylic hydroperoxides”and“1,4-addition to chlorophenols with the formation of hydroperoxide ketones”have much probability than the other two reaction types. But the type of“1,3-addition to a double bond connected to a hydrogen-carrying group, resulting in the formation of allylic hydroperoxides”has the lowest reaction barriers, therefore is predicted to be the preferred route. We also analysis the distances between the correlation atoms and their NBO charges in order to study the reaction mechanism between 2, 4-dichlorophenol (o-chlorophenol) and singlet oxygen.
引文
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3.葛利云,张喆,吴峰,等.水溶液中2,4-二氯苯酚的光降解研究[J].环境科学与技术, 2004,27(1):27-29
4.范经华,范彬,张忠国,等.多孔钛板负载Pd阴极电催化加氢还原水中五氯酚[J].环境科学,2006,27(8):1586-90
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6. Pera-Titus M, Garcia-Molina V, Banos M, etc. Degradation of chlorophenols by means of advanced oxidation processes: a general review. Applied Catalysis B:Environmental, 2004, 47:219-256
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9.李景印,郭玉凤,张亚通,等.邻氯酚在TiO2膜上光催化降解及反应动力学特征[J].环境科学与技术,2003,26(1):3-5
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11.张大仁.酚取代衍生物的QSAR研究[J]环境科学,1995,16(2):4
12.安淼,周琪.氯代酚类化合物的生物降解与污染控制技术研究[J].给水排水,2004, 10:114-115
13. Sheikheldin S Y, Cardwell T J, Cattrall R W, etc. Determination of Henry’s law cons- tants of phenols by pervaporation - flow injection analysis. Environmental Science & Techno- logy,2001,35(1): 178-181
14. Miller J S. Rose bengal sensitized photo-oxidation of 2-chlorophenol in water using solar simulated light. Water research,2005,39: 412-422
15. Marianna C. Photo-degradation of chlorophenols in the aqueous solution. Journal of Hazardous materials,2006,B134: 45-59
16. Da Silva J P, Ferreira L F, Da Siva A M. Aqueous photochemistry of pesticides triadimenol. Journal of Photochemistry and Photobiology,2003,154: 293–298
17. Benitez F J, Acero J L, Real F J, etc. Kinetics of photodegradation of pentachlorophenol.Chemosphere,2003,51: 651–662
18. Boule P, Guyon C, Lemaire J. Photochemistry and environment IV-photochemical behavior of monochlorophenols in dilute aqueous solution. Chemosphere,1982,11: 1179–1188
19. Czaplicka M, Czaplicki A. Photodegradation of 2,3,4,5-tetrachlorophenol in water/ methanol mixture. Journal of Photochemistry and Photobiology A: Chemistry, 2006,178: 90–97
20. Gryglik D, Miller J S, Ledakowicz S. Singlet molecular oxygen application for 2- chlorophenol removal. Journal of Hazardous Materials, 2007,146: 502–507
21. Svetlichnyi V A, Chaikovskaya O N, Bazyl O K, etc. Photolysis of phenol and para- chlorophenol by UV laser excitation. High Energy Chemistry,2001,35: 288–294
22. Gsponer H E, Previtali C M, Garcia N A. Kinetics of the photosensitized oxidation of polychlorophenols in alkaline aqueous. Toxicological & Environmental Chemistry,1987,16: 23–37
23. Crosby D G, Tutoss H G. Photodecomposition of 2,4-dichlorophenoxyacetic acid. Journal of Agriculture and Food Chemistry, 1966,14: 596–599
24. Boule P, Guyon C, Lemaire J. Photochimie et environnemeny VIII. Comporte-ment photochimique de dichlorophenols en solution aqueuse diluee. Chemosphere,1984,13(5-6):
603–612
25. Pandiyan T, Martinez R O, Orozco M J, etc, Martinez-Carrillo M A, Comparison of methods for the photochemical degradation of chlorophenols. Journal of Photochemistry and Photobiology, 2002,146: 149–155
26. Barakat M A, Schaeffera H, Hayesa G., etc. Photocatalytic degradation of 2-chloro- phenol by Co-doped TiO2 nanoparticles. Applied Catalysis B: Environmental 2005,57 : 23–30
27. Bum G K, Dong S L, Namgoo K. Characteristics of p-chlorophenol oxidation by fenton's reagent. Water Research,1999,33(9): 2110-2118
28. Ozoemena K, Kuznetsova N. Comparative photosensitized transformation of poly- chlorophenols with different sulphonated metallophthalocyanine complexes in aqueous medium. Journal of Molecular Catalysis A Chemical,2001,176: 29–40
29. Tratnyek P G, Holigne V G, Oxidation of substituted phenols in theenvironment: a QSAR analysis of rate constants for reaction with singlet oxygen. Environmental Science & Technology,1991,25: 1596–1607
30. Jeffrey R. Singlet Oxygen Production From The Reaction Of Superoxide Ion with Halocarbons in Acetonitrile. Journal of the American Chemical Society,1988,110: 3698- 3699
31.王能辉.竹红菌甲素半醌自由基的变化特点[J].化学学报,1992,50(7): 702- 707
32.夏璐.光催化光敏化氧化含酚含氯废水的实验研究[J].科学研究,化学与生物工程,2004,5:16-18
33.马建明,龚文杰,邬晨阳.高效液相色谱法测定尿液中的2,3,4,6-四氯酚[J].中华预防医学杂志,2006,40(2):118-119.
34.王逸虹,候定远.水和废水中2,4-滴、2,4-二氯酚、2,4,6-三氯酚的测定[J].环境监测管理与技术,1995,7(3):26-28
35.张岚,李淑敏,岳银玲,等.顶空固相微萃取气相色谱法测定饮水中氯酚[J].卫生研究, 2006,35(1):92-94.
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