废水中有机污染物降解机理的研究方法

我国废水排放总量较大,且废水中含有的多种有机污染物一直是人类生命健康的潜在威胁,因此对废水处理的研究必不可少,而理解废水中有机污染物的降解机理是处理各种废水的基础.本综述概述了国内外针对各种有机污染物降解机理的研究方法,主要包括实验手段和计算模拟两大类.实验手段中主要采用光谱分析技术检测有机污染物降解过程中生成的中间产物,进而推测有机污染物的降解路径.但是由于实验条件和实验方法的不同,对于同种物质的降解机理研究,不同的实验结果存在着争议.基于量子化学计算、定量构效关系模型（QSAR）、定量结构-生物降解性能关系模型（QSBR）、统计分子碎化模型（SMF）等计算模拟方法为有机污染物降解机理的研究提供了新的方法.将实验手段和计算模拟有机结合起来,可为有机污染物的降解机理研究提供参考和指导.     

新型的乙烯聚合催化剂

简要介绍了新型的烯烃聚合催化剂－Ｎｉ（Ⅱ）、Ｐｄ（Ⅱ）、Ｆｅ（Ⅱ）、Ｃｏ（Ⅱ）类后过渡金属催化剂的发展,特点及催化乙烯聚合机理,并就它们的组成结构、聚合条件和配体体积对聚合产物结构,分子量等的影响根据配体不同分类进行了讨论。     

用于有机物降解的电化学阳极材料

电化学氧化法可将难降解的有机物转化为可生化降解物质或直接矿化,具有操作简便,清洁能源,无二次污染等优点。本文介绍了电催化氧化机理最新进展,包括近年来所报道的各种电极材料直接或间接电氧化降解有机物的机制;回顾了近年来阳极材料的研究现状,以碳电极、金属电极和钛基形稳电极为主,包括各种新型电极的组成、降解性能及其钝化原因等,并对今后电氧化阳极材料及相关工艺的研究方向提出建议。     

卤代有机污染物的光化学降解

包括全氟或部分氟代化合物（PFCs）、氯代有机物（COCs）以及溴代有机物（BOCs）等的卤代有机污染物（halogenated organic contaminants,HOCs）排放到环境中会表现出持久性有机污染物的特征,因此涉及HOCs性质、光吸收与量子效应、材料与界面特性、环境条件等方面优化的光化学清除方法成为一个重要的研究方向。基于此,本文归纳分析了光激发催化剂产生活性物种如h_VB⁺、e_CB^-、 ·OH、e_aq^-等氧化或还原全氟辛酸、多氯联苯、多溴联苯醚的反应机理及直接光解机理,指出HOCs的光化学降解主要是通过其与活性物种之间电子转移或其激发态光致还原脱卤来实现,认为光催化材料和反应过程优化设计是影响光催化降解HOCs的重要因素。基于目前已经取得的研究发现与成果,从界面电子转移、材料能带信息、反应与分离集成化等方面提出本领域未来学术与技术层面值得深入探索的关键问题。     

三亚甲基环碳酸酯及2,2-二甲基三亚甲基环碳酸酯开环均聚合*

生物降解聚合物聚三亚甲基环碳酸酯（PTMC）及聚2,2-二甲基三亚甲基环碳酸酯（PDTC）在药物控释载体及其它生物医学技术领域有着良好的应用前景。与脂肪族聚酯不同,PTMC、PDTC降解时,不会产生有害的酸性化合物。PTMC、PDTC主要由三亚甲基环碳酸酯（TMC）及2,2-二甲基三亚甲基环碳酸酯（DTC）开环均聚合制备。本文总结了催化TMC、DTC开环均聚合的不同催化剂及其聚合机理,综述了近年来国内外在TMC、DTC均聚合催化剂开发上的研究进展,并对生物相容性催化剂如稀土催化剂、Ca、Mg、Zn、Fe催化剂以及酶催化剂催化TMC、DTC开环聚合的优缺点进行了比较。     

凝胶渗透色谱法研究壳聚糖生物材料酶降解过程的均匀性

壳聚糖是一种重要的生物医用材料,脱乙酰度是影响其生物降解性能的重要因素。运用凝胶渗透色谱研究了脱乙酰 度及相对分子质量分布相似、而聚合单元N-乙酰氨基-D-葡萄糖和D-氨基葡萄糖分布不同的两种壳聚糖材料在溶菌酶作用 下的降解过程,分析检测了壳聚糖材料在降解过程中的重均相对分子质量、相对分子质量多分散性和相对分子质量分布 的变化。发现聚合单元为随机分布的壳聚糖样品,其降解是均匀的;而聚合单元为段状分布的壳聚糖样品,其降解是非 均匀的;表明其聚合单元的分布方式决定壳聚糖材料酶降解过程的均匀性。     

天然膨润土负载纳米铁的制备及其对阿莫西林的降解性能

采用液相还原法制备膨润土负载纳米铁（B-nZVI）用于降解水体中的阿莫西林（AMX）.通过SEM、XRD、FT-IR、BET等表征手段,对其微观结构和B-nZVI与阿莫西林反应前后进行了表征,还进行了其对阿莫西林的降解实验.研究表明,制成的B-nZVI材料中的纳米铁多数以30～90nm球形颗粒为主,均匀地分散在膨润土中,从而提高了纳米铁的反应活性,对阿莫西林的去除率要比单独使用纳米铁（nZVI）高,其降解过程符合表观一级反应动力学.基于表征和降解动力学的依据,B-nZVI对阿莫西林的可能降解机理是内酰胺键被零价铁还原作用而打开.     

ZnO/BiOI微球的合成及其光催化性能

通过一步溶剂热法合成ZnO/BiOI纳米复合材料,在Bi（NO₃）₃·6H₂O、KI、ZnO和乙二醇（EG）溶剂中,制备出的样品尺寸和形貌采用X射线粉末衍射（XRD）、场发射扫描电镜（FESEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（DRS）、X射线光电子能谱（XPS）、N₂吸附-脱附等,对实验所得产物的组成、结构及光学性质等进行表征。以染料罗丹明B（RhB）水溶液和气态乙醛作为降解对象,采用BiOI、ZnO/BiOI和ZnO微纳材料作为光催化剂,通过对BiOI、ZnO/BiOI和ZnO微纳材料在可见光下光催化降解染料罗丹明B（RhB）水溶液和气态乙醛,结果表明多孔微纳材料的ZnO/BiOI具有更高的降解效率,实验表明多孔微纳材料的ZnO/BiOI具有更高的氧空位浓度,因此使其催化活性增强,讨论了其可能的催化活性机理。     

ZnO/BiOI微球的合成及其光催化性能

通过一步溶剂热法合成ZnO/BiOI纳米复合材料,在Bi（NO₃）₃·6H₂O、KI、ZnO和乙二醇（EG）溶剂中,制备出的样品尺寸和形貌采用X射线粉末衍射（XRD）、场发射扫描电镜（FESEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（DRS）、X射线光电子能谱（XPS）、N₂吸附-脱附等,对实验所得产物的组成、结构及光学性质等进行表征。以染料罗丹明B（RhB）水溶液和气态乙醛作为降解对象,采用BiOI、ZnO/BiOI和ZnO微纳材料作为光催化剂,通过对BiOI、ZnO/BiOI和ZnO微纳材料在可见光下光催化降解染料罗丹明B（RhB）水溶液和气态乙醛,结果表明多孔微纳材料的ZnO/BiOI具有更高的降解效率,实验表明多孔微纳材料的ZnO/BiOI具有更高的氧空位浓度,因此使其催化活性增强,讨论了其可能的催化活性机理。     

开环聚合诱导自组装的挑战与展望

聚合诱导自组装（PISA）是一种新兴的纳米粒子制备技术,它集聚合与组装过程于一体,可在高固含量条件下进行,因此备受青睐.此外,通过改变嵌段聚合度以及固含量等参数,可以精确地控制纳米粒子的形貌,实现从球形胶束到空心囊泡的形貌转变.然而,受限于适用于PISA体系的聚合方法和单体种类,其发展也受到了一定的限制.目前,PISA主要基于可逆加成-断裂链转移聚合（RAFT）,其在聚合诱导自组装机理、形貌控制、结构表征等方面的研究成果,对于高分子化学其他领域具有重要的参考价值.然而,由于RAFT聚合诱导自组装（RAFT-PISA）体系中适用的单体往往局限于（甲基）丙烯酸酯类和苯乙烯类,导致RAFT-PISA制备的纳米粒子限于其碳-碳主链的基本结构难以生物降解,因此生物医用前景并不乐观.为了克服以上缺陷,开环聚合诱导自组装（ROPISA）应运而生,主要包括开环易位聚合诱导自组装（ROMPISA）、氨基酸-N-羧基-环内酸酐开环聚合诱导自组装（NCA-PISA）及自由基开环聚合诱导自组装（rROPISA）.由于ROMPISA体系对诸多功能性基团表现出化学惰性,从而为多功能纳米粒子的原位制备提供了新的方法;而rROPISA和NCA-PISA则使得生物可降解纳米粒子的原位制备成为可能.作为PISA领域崭新的研究方向,ROPISA不仅将新聚合方法引入了PISA体系,而且突破了以往PISA难以制备可降解纳米粒子的瓶颈,为PISA技术在生物医药领域的应用架起了桥梁.作者简要总结了ROPISA的发展现状,着重分析并提出了该领域面临的挑战,最后从机理研究、单体设计及转化应用等方面对ROPISA的发展前景进行了展望.     

Accelerated plasma degradation of organic pollutants in milliseconds and examinations by mass spectrometry

The rapid degradation of organic pollutants, process monitoring and online controlling to obtain advanced products and decreased by-products are great and challenging tasks in environmental treatments. Herein, an accelerated plasma degradation in milliseconds was achieved by combining electrospray-based acceleration and plasma-based degradation. Taking the degradation of chloroaniline as an example, 97% of the degradation can be achieved in milliseconds. The velocity distribution of droplets was determined to be 40–50 m/s after being degraded for 0.30 ms, which exhibited different degradation behaviors in different milliseconds. Simultaneously, by virtue of the real-time and on-line detection ability of ambient mass spectrometry, intermediates, by-products and advanced products were monitored. Therefore, degradation mechanisms for different degradation times were proposed, which would provide theoretical guidance on obtaining efficient and green degradation. The fabrication, examining and understanding of accelerated plasma degradation not only enlarged application of accelerated reactions, but also promoted green and efficient degradation for environmental treatments.     

Thermal degradation of polystyrene in the presence of hydrogen by catalyst in solution

For the first time, low temperature degradation (170-240 °C) of polystyrene in benzene is carried out in the presence of hydrogen using iron(III) oxide catalyst. The effect of temperature, catalyst loading and polymer loading on degradation are studied in hydrogen atmosphere. Degradation is also carried out at different initial hydrogen partial pressure. The time dependent molecular weight is calculated using viscosity average method. It is found that the degradation is enhanced considerably in the presence of hydrogen and followed random degradation chain scission. A random degradation kinetic model of Kelen [Kelen T. Polymer degradation. New York: Van Nostrand Reinhold Company; 1983.] is used to estimate the degradation rate constants. Empirical correlations are proposed to account for the effect of catalyst loading and initial hydrogen partial pressure on degradation. The true thermal degradation rate constants are calculated using these proposed correlations at given catalyst loading and initial hydrogen partial pressure with varying temperature. The frequency factor and activation energy are also determined using Arrhenius equation considering the true thermal degradation rate constants.     

Effect of degradation on electronic properties of polymer solar cells

We present here the effect of degradation on electronic properties of polymer solar cells. Investigations were performed on two types of solar cells based on the bulk‐heterojunction network of poly(3‐hexylthiophene) and phenyl [6,6] C₆₁ butyric acid methyl ester, one with slow degradation whereas other with faster degradation. Samples were prepared in identical conditions with controlled atmosphere, but for faster degradation, one of the samples was exposed to ambient air (rich in O₂ and H₂O molecules) before deposition of top metal electrode. The sample with slow degradation showed linear degradation in short circuit current density (J_sc), whereas the sample with faster degradation exhibited exponential degradation in J_sc. Linear degradation happens due to degradation in the active layer only whereas the exponential degradation is because of through degradation of the solar cell. The effect of degradation is investigated on different diode parameters. Because of different degradation processes in the two samples, the variations in diode parameters with time are different. Copyright © 2013 John Wiley & Sons, Ltd.     

几种典型有毒有机污染物的光催化降解研究

本文研究了氯代苯酚和苯胺类化合物的光催化降解,探讨了这些有机污染物分子的氯取代和化合物毒性与光催化降解之间的关系.研究表明,氯代苯酚和苯胺类化合物的光催化降解均符合表观一级反应动力学模型.有机物分子中氯取代基的引入加快了化合物的光催化降解,且反应速率随氯取代基个数的增多而增大.光催化降解的表观速率常数与正辛醇-水分配系数之间存在有较好的线性关系:logk=alogKow+b,该模型可以用于有机污染物的光催化降解性预测.     

Thermo-oxidative degradation of ultrahigh molecular weight poly(ethylene oxide) in volatile organic solvents

The degradation of ultrahigh molecular weight poly(ethylene oxide) (UHMWPEO) was investigated in three volatile organic solvents, methanol, chloroform, and tetrahydrofuran. Particularly, degradation rate was determined by means of Ubbelohde viscometry and degradation products were characterized by using electron spin resonance spectroscopy (ESR) and Fourier transform infrared spectroscopy (FTIR). The highest degradation rate was observed for UHMWPEO in tetrahydrofuran, with the lowest one in methanol. The ESR results showed that PEO-C• and •OH radicals were produced during the degradation process. Among these selected solvents, tetrahydrofuran was found to generate free radicals through an autoxidation mechanism. This would accelerate the degradation of UHMWPEO, resulting in the observed highest degradation rate in the UHMWPEO/tetrahydrofuran solution. Esters were also detected in the degradation products of these UHMWPEO solutions, while formates and formate ions were generated in the solutions of UHMWPEO/tetrahydrofuran and UHMWPEO/cloroform except for PEO/methanol. Furthermore, the degradation mechanism of UHMWPEO was deduced. This work enabled an in-depth understanding on the thermo-oxidative degradation mechanism of UHMWPEO in representative organic solvents, which would be instructive for developing optimal solution-based processing technique of UHMWPEO.     

Oxidative and photooxidative degradation of poly(acrylic acid)

The oxidative degradation of poly(acrylic acid) (PAA), a water soluble polymer, was studied at various temperatures with different concentrations of persulfates, potassium persulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS). The photodegradation of PAA was also examined with APS as oxidizer. The degraded samples were analyzed for the time evolution of molecular weight distribution by gel permeation chromatography. A theoretical model based on the continuous distribution kinetics was developed that accounted for the polymer degradation and the dissociation of persulfate. The rate coefficients for the oxidative and photooxidative degradation of PAA were determined from the parametric fit of the model with experimental data. The rate of degradation increased with increasing amount of persulfate in both oxidative and photooxidative degradation. The rate of degradation also increased with increasing temperature in the case of oxidative degradation.     

部分水解聚丙烯酰胺降解研究进展

高分子量的水溶性聚丙烯酰胺 (PAM)在不同领域均有广泛的应用 ,但其分子量的降解行为直接影响到从生产、使用到最终处置的各个环节。本文将主要对各环节中涉及的降解作用研究进展进行综述 ,包括化学降解、生物降解、热降解和机械降解等。     

氯化天然橡胶的等速升温热降解动力学

天然胶乳;氯化天然橡胶的等速升温热降解动力学     

Radiolysis of alkyl benzene sulfonat (ABS) in aqueous solution

Degradation of alkyl benzene sulfonate (ABS) in aerated aqueous solution irradiated with gamma radiation with doses up to 1.8 kGy were studied. The degree of degradation, pH change, the effect of pH on the degradation, COD values and the degradation products were determined. The degradation of ABS increases with the increase of doses and decreases with the increase of ABS concentration. The degradation was somewhat more efficient in slightly acidic and neutral solutions than at basic pH oxalic acid was detected by HPLC as degradation product.     

Performance of pyrophyllite and halloysite clays in the catalytic degradation of polystyrene

Summary The performance of pyrophyllite and halloysite clays in the degradation of polystyrene (PS) was investigated. The degradation was carried out in a semi-batch reactor with a mixture of polystyrene and catalysts at 400-450^oC. The catalysts showed good catalytic activity for the degradation of PS with high selectivity to aromatics liquids. Styrene is the major product, and ethylbenzene is the second most abundant one in the liquid product. The catalytic degradation showed much less production of styrene dimers and higher selectivity to ethylbenzene than the thermal degradation did. High degradation temperature favored the production of styrene monomer, but it decreased the ethylbenzene production.