环糊精对水中酚类化合物紫外光降解影响的动力学与机制研究
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摘要
酚类化合物是芳烃的含羟基衍生物。含酚废水是当今世界上危害大、污染范围广的工业废水之一,是环境中水污染的重要来源。近年来,由于双酚类环境内分泌干扰物可能给人类和动物造成潜在的不利影响,引起了人们的高度关注,有关这一类物质的处理研究成为目前环境污染控制领域研究的热点。众所周知,环境系统中的光化学转化是影响有机污染物行为与归属的重要因素之一。而水中污染物的直接光解是有机污染物转化的一个重要途径。环糊精外缘亲水而内腔疏水,能包络如有机分子、无机离子以及气体分子等各种客体。环糊精已被广泛证实可以作为一种介质用于控制化学和光化学反应。
因此本论文以酚类化合物,主要是双酚类化合物为研究对象,研究环糊精对这类物质紫外光降解影响的动力学与机制。作为包络作用主体的环糊精选取了β-环糊精(β-CD)、α-环糊精(a-CD)、γ-环糊精(γ-CD),采用15W紫外灯(λ=254 nm)为光源,在自制的恒温光反应装置中进行光化学反应实验,开展了以下几个方面的工作。
1.研究了β-CD对17种酚类化合物紫外光降解的影响。结果表明当酚类化合物和β-CD初始浓度为4.OE-5mol·L-1时,β-CD抑制1,3,5-benzenetriol、o-Nitrophenol、4,4'-thiodiphenol (TDP)、4,4'-dihydroxy-benzophenone (DHBP)、2-phenylphenol的紫外光解,促进bis(4-hydroxyphenyl) sulfone (BPS)、4,4-bis(4-hydroxyphenyl)pentanoic acid (DPA)、Bisphenol A (BPA)、bis(4-hydroxyphenyl)methane (BPF)、4,4'-ethylidene-bisphenol (BPE)的紫外光解,对p-chlorophenol、phenol、p-dihydroxybenzene、4-acetamidophenol、2,2'-dihydroxybipheny、4,4'-dihydroxy-biphenyl、2-isopropyl-5-methyl phenol的紫外光解没有影响。在此基础上研究了无CD以及α-CD、β-CD、γ-CD存在下TDP、BPS、DPA、BPA、BPF、BPE、DHBP的紫外光降解动力学。研究表明在无CD以及CD存在下,这七类双酚化合物的紫外光解反应均符合假一级反应动力学,在实验条件下,TDP、BPS、DPA、BPA、BPF、BPE、DHBP在无CD存在下的紫外光解速率常数分别为：0.429 min-1、0.102min-1、0.0164min-1、0.00848min-1、0.00451min-1、0.00406min-1、0.00343min-1；而在β-CD存在下TDP、BPS、DPA、BPA、BPF、BPE、DHBP的紫外光解速率常数分别为0.276min-1、0.126min-1、0.156min-1、0.0658min-1、0.0184min-1、0.0261min-1、0.00273min-1。β-CD对BPS、DPA、BPA、BPF、BPE光解速率常数的促进倍数分别是1.2倍、9.5倍、7.8倍、4.1倍、6.4倍。而β-CD对TDP、DHBP的紫外光解速率常数抑制倍数是1.6、1.3倍。
2.考察了β-CD浓度、底物初始浓度、pH值对TDP、BPS、DPA、BPA、BPF、BPE、DHBP紫外光降解的影响。结果表明当底物和β-CD浓度的比值由2：1增加到1：10时,β-CD浓度的增加会导致β-CD对双酚化合物紫外光解作用效果的增强；无环糊精存在以及α-CD、γ-CD存在下七种双酚化合物的紫外光解效率基本随着初始浓度的增加而降低。而在p-CD存在下,DPA、BPF、BPE的紫外光降解效率与初始浓度的改变没有明显关系；在碱性条件下,无环糊精存在时pH值对七种双酚化合物紫外光解作用的影响大于p-CD存在下。在酸性和中性条件下,p-CD对七种双酚化合物的紫外光解影响的规律基本一致；通过测定无CD存在时以及β-CD存在下七种双酚化合物光解过程溶液TOC值的变化情况,发现β-CD对七种双酚化合物在本研究体系的矿化不能起促进作用,反而会对BPS、TDP、DHBP的矿化起抑制作用。
3.运用紫外光谱、荧光光谱研究了双酚化合物／环糊精包络物。研究表明,加入环糊精后,BPS、TDP的紫外吸收峰强度会减弱,而DPA、BPA、BPF, BPE、DHBP的荧光强度增加,并随着CD浓度的增加而减弱或加强。除了DHBP之外,其他六类双酚化合物在β-CD存在下,光谱发生改变的程度都远远大于α-CD与γ-CD存在下双酚化合物光谱的改变,与测得的双酚化合物／环糊精包络物包络常数的数值大小相统一；根据改进的Hildebrand-Benesi方程,计算得出β-CD可分别与TDP、BPS、DPA、BPA、BPF、BPE、DHBP形成1：1稳定的包络物,其包络常数分别为：8.21×103L·mol--、1.48×104L·mol-1、3.80×104 L·mol-1、5.27×104 L·mol-1、1.18×104 L·mol-1、3.89×104L·mol-1、187L·mol-1;当pH由3.5提高到10.0时,七种双酚化合物／β-CD包络物在不同pH值条件下的包络常数值都基本相同；β-CD存在下,BPS、TDP、DPA、BPA、BPF, BPE, DHBP浓度与β-CD浓度比为1：2时这七类双酚化合物的紫外吸收峰强度都有一定程度的减弱。TDP、BPS、DPA, BPA、BPF、BPE、DHBP和这七种双酚化合物／β-CD包络物的紫外光谱在酸性和中性条件下基本一致。而在碱性条件下,这七种双酚化合物和双酚化合物／β-CD包络物的紫外光谱都发生了一定程度的改变。碱性条件下,TDP, DPA, BPA、BPF, BPE, DHBP和它们的β-CD包络物在254nm波长下的紫外吸收强度明显增强。
4.以BPE和BPE/p-CD包络物为代表对象,通过激光闪光光解和时间相关单光子计数法对p-CD对双酚化合物紫外光解促进作用机制进行了研究。研究表明BPE/UV和BPE/β-CD/UV两个体系中主要的光化学过程是光致电离,并产生水合电子、酚氧自由基。BPE光电离的量子产率φ(266 nm)=3.7×10-3,BPE/β-CD包络物光电离的量子产率φ(266nm)=1.9×10-2,提高了5倍。BPE在环糊精腔体内的包络反应使得BPE单重激发态的衰减速度下降,从而导致BPE光致电离、荧光量子产率以及荧光寿命的显著提高。由此可以解释稳态光解实验下p-CD促进双酚化合物的紫外光解。
5.利用GAUSS98软件对酚类化合物进行结构优化,结合结构优化后得到的量子化学参数以及查阅文献所得的17种酚类化合物的相关结构能量和物理化学参数构建酚类化合物紫外光解反应的QSPR方程。由方程可知酚类化合物的logP, pka,分子最高占据轨道和最低空轨道能量差(△E)与其紫外光解初始速率(r。)存在相关性,r。与物质的logP成正相关,与pka,△E成反相关。
Phenol compounds are aromatic compounds containing hydroxyl group. Today, Phenolic wastewater is one of the most serious water pollution in the world which endangers the environment widely and dramatically, and it is the main origin of the water pollution. As bisphenols may cause potential adverse effects on humans and animals, it concerns the public seriously. Consequently, the study of disposal of this type of material has arisen an issue of environmental pollution control which involves a large number of professional researches. It is accepted that photochemical transformations in environmental systems play a major role in determining the behavior and fate of organic pollutants. And direct photolysis of these pollutants is an important transformation route in the aquatic environment. However, the study of utilizing direct photolysis reaction as a way of organic wastewater treatment is not adequate, and it can only be applied in some limited fields. Cyclodextrins are cyclic oligosaccharides which have an external hydrophilic surface and an inner hydrophobic cavity; they are able to include a variety of objects such as organic molecules, inorganic ions, gas molecules and other compounds. Cyclodextrins have been widely proven as a medium for chemical control and photochemical reactions.
Therefore, the photodegradation behavior and corresponding mechanisms of phenol compounds mainly bisphenol comoounds in the present of cyclodextrins were studied, Used host compounds wereβ-cyclodextrin,α-cyclodextrin andγ-cyclodextrin. Irradiation experiments were carried out in a self-made cylindrical reactor, with a 15 W UV sterilization lamp (λ=254nm).
The experiments were carried out in the following areas of work.
1. The effect ofβ-CD on the degradation of 17 phenol compounds under UV light was studied with the initial concentration of phenol compounds andβ-CD being both 4.0E-5mol·L-1. The result showed thatβ-CD could inhibit the photodegradation of 1,3,5-benzenetriol、o-Nitrophenol、4,4'-thiodiphenol (TDP)、4,4'-dihydroxy-benzophenone (DHBP)、2-phenylphenol, but promote the photodegradation of bis(4-hydroxyphenyl) sulfone (BPS)、4,4-bis(4-hydroxyphenyl)pentanoic acid (DPA)、Bisphenol A (BPA)、bis(4-hydroxyphenyl)methane (BPF)、4,4'-ethylidene-bisphenol (BPE), and it has essentially no effect on the photodegradation of p-chlorophenol、phenol、p-dihydroxybenzene、4-acetamidophenol、2,2'-dihydroxybiphenyl、4,4'-dihydroxy-bipheny1、2-isopropyl-5-methyl phenol. Moreover, the kenetics of photodegradation of TDP、DHBP、BPS、DPA、BPA、BPF、BPE in the presence ofα-CD、β-CD、γ-CD and in the absence of CDs were studied. The photodegradation of these bisphenol compounds both in the presence and in the absence of CDs proceeds is in accord with the pseudo-first order reaction kinetics. The photodegradation rate constant of TDP、DHBP、BPS、DPA、BPA、BPF、BPE in the absence of CDs are 0.429 min-1、0.102min-1、0.0164min-1、0.00848min-1、0.00451min-1、0.00406min-1、0.00343min-1 respectively, while the photodegradation rate constant of TDP、DHBP、BPS、DPA、BPA、BPF、BPE in the absence ofβ-CD are 0.276min-1、0.126min-1、0. 156min-1、0. 0658min-1、0.0184min-1、0.0261min-1、0.00273min-1 respectively. The photodegradation rate constant of BPS, DPA, BPA, BPF, BPE after p-CD inclusion catalysis can reach 1.2、9.5、7.8、4.1、6.4 fold increase respectively, but the photodegradation rate constant of TDP、DHBP after p-CD inclusion catalysis will be 1.6、1.3 fold decrease respectively.
2. The effects of initial substrate concentration,β-CD concentration and pH value on the photodegradation of TDP, BPS, DPA, BPA, BPF, BPE and DHBP were studied. The results showed that when the amount ofβ-CD on the bisphenols photodegradation varied from 0.5 to 10 fold, the effect ofβ-CD on these bisphenols photodegradation increased with an increase in the amount ofβ-CD concentration. The pheotodegradation of these bisphenol compounds is essentially decrease with the increasing of initial concentration in the absence of CDs and in the presence ofα-CD,γ-CD, while in the presence of β-CD, there was no significant relationship between the DPA、BPF、BPE pheotodegradation efficiency and initial concentration. The effect of p-CD on the photodegradation of these bisphenol compounds in alkaline solution was less than in acidic and neutral solutions. And a similar trend of the effect ofβ-CD on the photodegradation of these bisphenol compounds was found in acidic and neutral solutions. The mineralization of these bisphenol compounds was followed by total organic carbon analysis (TOC) in the absence of CDs and in the presence of p-CD, the results showed thatβ-CD can not enhance the mineralization of these bisphenol compounds, but reduce the BPS, TDP, DHBP mineralization.
3. The inclusion complex of bisphenols with CDs was characterized by ultraviolet spectroscopy and fluorescence spectroscopy. Ultraviolet absorption and fluorescence spectra show that absorption peaks of BPS, TDP in inclusion withβ-CD significantly weaken, while fluorescence intensity of DPA、BPA、BPF、BPE、DHBP in inclusion withβ-CD significantly strengthen. The degree of weakening or strengthening of these bisphenol compounds spectrum except DHBP in the presence ofβ-CD is far greater than in the presence ofα-CD andγ-CD, which is in accordance with the results of the formation constants of inclusion complex measured by modified Benesi-Hildebrand method. According to a modified Bensi-Hildebrand equation, the formation constant of inclusion complex between TDP、BPS、DPA、BPA、BPF、BPE、DHBP andβ-CD is 8.21×103L·mol-1、1.48×104L·mol-1、3.80×104 L·mol-1、5.27×104 L·mol-1、1.18×104L·mol-1、3.89×104L·mol-1、187L·mol-1 respectively, the molar ratio is 1:1. The large constant values found suggest significant interaction between the guest and the host molecules. The formation constant of inclusion complex in the presence ofβ-CD does not show significant changes when the pH rose from 3.5 to 10.0. The bisphenols/β-CD complex shows a little smaller ultraviolet absorption than in the absence ofβ-CD when the concertation ritio of bisphenols/β-CD is 1:2. The Ultraviolet absorption spectra of these bisphenols compounds and bisphenols/β-CD complex are very similar at both acid and neutral pH. While at alkaline pH, the bisphenol compounds and bisphenols/β-CD complex change the shape of the ultraviolet spectrum. The UV absorption peaks of TDP, DPA, BPA, BPF, BPE, DHBP and these bisphenols/β-CD complex significantly increased at 254nm.
4. Photochemistry and photophysics of both BPE in the absence of CDs and inclusion complex of BPE withβ-CD was studied by nanosecond laser flash photolysis and time-correlated single photon counting techniques. For both systems the primary photochemical process was found to be photoionization with formation of hydrated electron and phenoxyl radical. The main difference between photochemistry of free BPE ((?)(266 nm)= 3.7x10-3) and BPE/β-CD complex ((?)(266 nm)= 1.9x10-2) is a 5-fold increase in photoionization quantum yield in the case of the complex. Inclusion of BPE in cyclodextrin cavity leads to great increase of photoionization and fluorescence quantum yield as well as fluorescence lifetime due to decreasing of relaxation processes in the singlet excited state of complexed BPE. This is in the good agreement with lower photochemical stability of BPE/p-CD complex observed in stationary photochemical experiments.
5. Quantitative structure-property relationship (QSPR) model was developed for photodegradation rates of phenol compounds. Molecule structure parameters were investigated with the help of the GAUSS98 software and related literatures. The photodegradation initial rates of these phenol compounds can be fitted by QSPR models. The photodegradation initial rates depend on the logP, pka, the gap of frontier molecular orbital energies (△E). Increasing logP of phenol compounds leads to an increase in photodegradation initial rate, increasing pka,△E leads to a decrease in photodegradation initial rate.
因此本论文以酚类化合物,主要是双酚类化合物为研究对象,研究环糊精对这类物质紫外光降解影响的动力学与机制。作为包络作用主体的环糊精选取了β-环糊精(β-CD)、α-环糊精(a-CD)、γ-环糊精(γ-CD),采用15W紫外灯(λ=254 nm)为光源,在自制的恒温光反应装置中进行光化学反应实验,开展了以下几个方面的工作。
1.研究了β-CD对17种酚类化合物紫外光降解的影响。结果表明当酚类化合物和β-CD初始浓度为4.OE-5mol·L-1时,β-CD抑制1,3,5-benzenetriol、o-Nitrophenol、4,4'-thiodiphenol (TDP)、4,4'-dihydroxy-benzophenone (DHBP)、2-phenylphenol的紫外光解,促进bis(4-hydroxyphenyl) sulfone (BPS)、4,4-bis(4-hydroxyphenyl)pentanoic acid (DPA)、Bisphenol A (BPA)、bis(4-hydroxyphenyl)methane (BPF)、4,4'-ethylidene-bisphenol (BPE)的紫外光解,对p-chlorophenol、phenol、p-dihydroxybenzene、4-acetamidophenol、2,2'-dihydroxybipheny、4,4'-dihydroxy-biphenyl、2-isopropyl-5-methyl phenol的紫外光解没有影响。在此基础上研究了无CD以及α-CD、β-CD、γ-CD存在下TDP、BPS、DPA、BPA、BPF、BPE、DHBP的紫外光降解动力学。研究表明在无CD以及CD存在下,这七类双酚化合物的紫外光解反应均符合假一级反应动力学,在实验条件下,TDP、BPS、DPA、BPA、BPF、BPE、DHBP在无CD存在下的紫外光解速率常数分别为：0.429 min-1、0.102min-1、0.0164min-1、0.00848min-1、0.00451min-1、0.00406min-1、0.00343min-1；而在β-CD存在下TDP、BPS、DPA、BPA、BPF、BPE、DHBP的紫外光解速率常数分别为0.276min-1、0.126min-1、0.156min-1、0.0658min-1、0.0184min-1、0.0261min-1、0.00273min-1。β-CD对BPS、DPA、BPA、BPF、BPE光解速率常数的促进倍数分别是1.2倍、9.5倍、7.8倍、4.1倍、6.4倍。而β-CD对TDP、DHBP的紫外光解速率常数抑制倍数是1.6、1.3倍。
2.考察了β-CD浓度、底物初始浓度、pH值对TDP、BPS、DPA、BPA、BPF、BPE、DHBP紫外光降解的影响。结果表明当底物和β-CD浓度的比值由2：1增加到1：10时,β-CD浓度的增加会导致β-CD对双酚化合物紫外光解作用效果的增强；无环糊精存在以及α-CD、γ-CD存在下七种双酚化合物的紫外光解效率基本随着初始浓度的增加而降低。而在p-CD存在下,DPA、BPF、BPE的紫外光降解效率与初始浓度的改变没有明显关系；在碱性条件下,无环糊精存在时pH值对七种双酚化合物紫外光解作用的影响大于p-CD存在下。在酸性和中性条件下,p-CD对七种双酚化合物的紫外光解影响的规律基本一致；通过测定无CD存在时以及β-CD存在下七种双酚化合物光解过程溶液TOC值的变化情况,发现β-CD对七种双酚化合物在本研究体系的矿化不能起促进作用,反而会对BPS、TDP、DHBP的矿化起抑制作用。
3.运用紫外光谱、荧光光谱研究了双酚化合物／环糊精包络物。研究表明,加入环糊精后,BPS、TDP的紫外吸收峰强度会减弱,而DPA、BPA、BPF, BPE、DHBP的荧光强度增加,并随着CD浓度的增加而减弱或加强。除了DHBP之外,其他六类双酚化合物在β-CD存在下,光谱发生改变的程度都远远大于α-CD与γ-CD存在下双酚化合物光谱的改变,与测得的双酚化合物／环糊精包络物包络常数的数值大小相统一；根据改进的Hildebrand-Benesi方程,计算得出β-CD可分别与TDP、BPS、DPA、BPA、BPF、BPE、DHBP形成1：1稳定的包络物,其包络常数分别为：8.21×103L·mol--、1.48×104L·mol-1、3.80×104 L·mol-1、5.27×104 L·mol-1、1.18×104 L·mol-1、3.89×104L·mol-1、187L·mol-1;当pH由3.5提高到10.0时,七种双酚化合物／β-CD包络物在不同pH值条件下的包络常数值都基本相同；β-CD存在下,BPS、TDP、DPA、BPA、BPF, BPE, DHBP浓度与β-CD浓度比为1：2时这七类双酚化合物的紫外吸收峰强度都有一定程度的减弱。TDP、BPS、DPA, BPA、BPF、BPE、DHBP和这七种双酚化合物／β-CD包络物的紫外光谱在酸性和中性条件下基本一致。而在碱性条件下,这七种双酚化合物和双酚化合物／β-CD包络物的紫外光谱都发生了一定程度的改变。碱性条件下,TDP, DPA, BPA、BPF, BPE, DHBP和它们的β-CD包络物在254nm波长下的紫外吸收强度明显增强。
4.以BPE和BPE/p-CD包络物为代表对象,通过激光闪光光解和时间相关单光子计数法对p-CD对双酚化合物紫外光解促进作用机制进行了研究。研究表明BPE/UV和BPE/β-CD/UV两个体系中主要的光化学过程是光致电离,并产生水合电子、酚氧自由基。BPE光电离的量子产率φ(266 nm)=3.7×10-3,BPE/β-CD包络物光电离的量子产率φ(266nm)=1.9×10-2,提高了5倍。BPE在环糊精腔体内的包络反应使得BPE单重激发态的衰减速度下降,从而导致BPE光致电离、荧光量子产率以及荧光寿命的显著提高。由此可以解释稳态光解实验下p-CD促进双酚化合物的紫外光解。
5.利用GAUSS98软件对酚类化合物进行结构优化,结合结构优化后得到的量子化学参数以及查阅文献所得的17种酚类化合物的相关结构能量和物理化学参数构建酚类化合物紫外光解反应的QSPR方程。由方程可知酚类化合物的logP, pka,分子最高占据轨道和最低空轨道能量差(△E)与其紫外光解初始速率(r。)存在相关性,r。与物质的logP成正相关,与pka,△E成反相关。
Phenol compounds are aromatic compounds containing hydroxyl group. Today, Phenolic wastewater is one of the most serious water pollution in the world which endangers the environment widely and dramatically, and it is the main origin of the water pollution. As bisphenols may cause potential adverse effects on humans and animals, it concerns the public seriously. Consequently, the study of disposal of this type of material has arisen an issue of environmental pollution control which involves a large number of professional researches. It is accepted that photochemical transformations in environmental systems play a major role in determining the behavior and fate of organic pollutants. And direct photolysis of these pollutants is an important transformation route in the aquatic environment. However, the study of utilizing direct photolysis reaction as a way of organic wastewater treatment is not adequate, and it can only be applied in some limited fields. Cyclodextrins are cyclic oligosaccharides which have an external hydrophilic surface and an inner hydrophobic cavity; they are able to include a variety of objects such as organic molecules, inorganic ions, gas molecules and other compounds. Cyclodextrins have been widely proven as a medium for chemical control and photochemical reactions.
Therefore, the photodegradation behavior and corresponding mechanisms of phenol compounds mainly bisphenol comoounds in the present of cyclodextrins were studied, Used host compounds wereβ-cyclodextrin,α-cyclodextrin andγ-cyclodextrin. Irradiation experiments were carried out in a self-made cylindrical reactor, with a 15 W UV sterilization lamp (λ=254nm).
The experiments were carried out in the following areas of work.
1. The effect ofβ-CD on the degradation of 17 phenol compounds under UV light was studied with the initial concentration of phenol compounds andβ-CD being both 4.0E-5mol·L-1. The result showed thatβ-CD could inhibit the photodegradation of 1,3,5-benzenetriol、o-Nitrophenol、4,4'-thiodiphenol (TDP)、4,4'-dihydroxy-benzophenone (DHBP)、2-phenylphenol, but promote the photodegradation of bis(4-hydroxyphenyl) sulfone (BPS)、4,4-bis(4-hydroxyphenyl)pentanoic acid (DPA)、Bisphenol A (BPA)、bis(4-hydroxyphenyl)methane (BPF)、4,4'-ethylidene-bisphenol (BPE), and it has essentially no effect on the photodegradation of p-chlorophenol、phenol、p-dihydroxybenzene、4-acetamidophenol、2,2'-dihydroxybiphenyl、4,4'-dihydroxy-bipheny1、2-isopropyl-5-methyl phenol. Moreover, the kenetics of photodegradation of TDP、DHBP、BPS、DPA、BPA、BPF、BPE in the presence ofα-CD、β-CD、γ-CD and in the absence of CDs were studied. The photodegradation of these bisphenol compounds both in the presence and in the absence of CDs proceeds is in accord with the pseudo-first order reaction kinetics. The photodegradation rate constant of TDP、DHBP、BPS、DPA、BPA、BPF、BPE in the absence of CDs are 0.429 min-1、0.102min-1、0.0164min-1、0.00848min-1、0.00451min-1、0.00406min-1、0.00343min-1 respectively, while the photodegradation rate constant of TDP、DHBP、BPS、DPA、BPA、BPF、BPE in the absence ofβ-CD are 0.276min-1、0.126min-1、0. 156min-1、0. 0658min-1、0.0184min-1、0.0261min-1、0.00273min-1 respectively. The photodegradation rate constant of BPS, DPA, BPA, BPF, BPE after p-CD inclusion catalysis can reach 1.2、9.5、7.8、4.1、6.4 fold increase respectively, but the photodegradation rate constant of TDP、DHBP after p-CD inclusion catalysis will be 1.6、1.3 fold decrease respectively.
2. The effects of initial substrate concentration,β-CD concentration and pH value on the photodegradation of TDP, BPS, DPA, BPA, BPF, BPE and DHBP were studied. The results showed that when the amount ofβ-CD on the bisphenols photodegradation varied from 0.5 to 10 fold, the effect ofβ-CD on these bisphenols photodegradation increased with an increase in the amount ofβ-CD concentration. The pheotodegradation of these bisphenol compounds is essentially decrease with the increasing of initial concentration in the absence of CDs and in the presence ofα-CD,γ-CD, while in the presence of β-CD, there was no significant relationship between the DPA、BPF、BPE pheotodegradation efficiency and initial concentration. The effect of p-CD on the photodegradation of these bisphenol compounds in alkaline solution was less than in acidic and neutral solutions. And a similar trend of the effect ofβ-CD on the photodegradation of these bisphenol compounds was found in acidic and neutral solutions. The mineralization of these bisphenol compounds was followed by total organic carbon analysis (TOC) in the absence of CDs and in the presence of p-CD, the results showed thatβ-CD can not enhance the mineralization of these bisphenol compounds, but reduce the BPS, TDP, DHBP mineralization.
3. The inclusion complex of bisphenols with CDs was characterized by ultraviolet spectroscopy and fluorescence spectroscopy. Ultraviolet absorption and fluorescence spectra show that absorption peaks of BPS, TDP in inclusion withβ-CD significantly weaken, while fluorescence intensity of DPA、BPA、BPF、BPE、DHBP in inclusion withβ-CD significantly strengthen. The degree of weakening or strengthening of these bisphenol compounds spectrum except DHBP in the presence ofβ-CD is far greater than in the presence ofα-CD andγ-CD, which is in accordance with the results of the formation constants of inclusion complex measured by modified Benesi-Hildebrand method. According to a modified Bensi-Hildebrand equation, the formation constant of inclusion complex between TDP、BPS、DPA、BPA、BPF、BPE、DHBP andβ-CD is 8.21×103L·mol-1、1.48×104L·mol-1、3.80×104 L·mol-1、5.27×104 L·mol-1、1.18×104L·mol-1、3.89×104L·mol-1、187L·mol-1 respectively, the molar ratio is 1:1. The large constant values found suggest significant interaction between the guest and the host molecules. The formation constant of inclusion complex in the presence ofβ-CD does not show significant changes when the pH rose from 3.5 to 10.0. The bisphenols/β-CD complex shows a little smaller ultraviolet absorption than in the absence ofβ-CD when the concertation ritio of bisphenols/β-CD is 1:2. The Ultraviolet absorption spectra of these bisphenols compounds and bisphenols/β-CD complex are very similar at both acid and neutral pH. While at alkaline pH, the bisphenol compounds and bisphenols/β-CD complex change the shape of the ultraviolet spectrum. The UV absorption peaks of TDP, DPA, BPA, BPF, BPE, DHBP and these bisphenols/β-CD complex significantly increased at 254nm.
4. Photochemistry and photophysics of both BPE in the absence of CDs and inclusion complex of BPE withβ-CD was studied by nanosecond laser flash photolysis and time-correlated single photon counting techniques. For both systems the primary photochemical process was found to be photoionization with formation of hydrated electron and phenoxyl radical. The main difference between photochemistry of free BPE ((?)(266 nm)= 3.7x10-3) and BPE/β-CD complex ((?)(266 nm)= 1.9x10-2) is a 5-fold increase in photoionization quantum yield in the case of the complex. Inclusion of BPE in cyclodextrin cavity leads to great increase of photoionization and fluorescence quantum yield as well as fluorescence lifetime due to decreasing of relaxation processes in the singlet excited state of complexed BPE. This is in the good agreement with lower photochemical stability of BPE/p-CD complex observed in stationary photochemical experiments.
5. Quantitative structure-property relationship (QSPR) model was developed for photodegradation rates of phenol compounds. Molecule structure parameters were investigated with the help of the GAUSS98 software and related literatures. The photodegradation initial rates of these phenol compounds can be fitted by QSPR models. The photodegradation initial rates depend on the logP, pka, the gap of frontier molecular orbital energies (△E). Increasing logP of phenol compounds leads to an increase in photodegradation initial rate, increasing pka,△E leads to a decrease in photodegradation initial rate.
引文
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