Fe~(3+)诱导全氟羧酸的光化学降解:pH值及链长的影响

以全氟辛酸(PFOA)为代表的全氟化合物是环境水体中新出现的一类持久性有机污染物,Fe3+的存在促进了其在254 nm紫外光下的有效降解.在此基础上,主要考察了溶液初始pH值对Fe3+诱导PFOA光化学降解的影响,并以全氟丁酸(PFBA)、全氟戊酸(PFPeA)、全氟己酸(PFHxA)和全氟庚酸(PFHpA)为对象,研究了Fe3+诱导短链全氟羧酸(PFCAs)的降解,通过对降解中间产物的分析,进而推断了其降解机理.结果表明,强酸性条件有利于PFOA的降解,弱酸性或中性反应条件下,PFOA的降解和脱氟均受到明显地抑制,进一步证实PFOA的降解主要是溶解性铁作用的结果,此时Fe(OH)2+则是铁(III)-羟基配合物的主要分配形态.Fe3+诱导PFCAs的降解表明:当碳原子数大于5,长链的PFCAs更易于降解,但对于碳原子数小于6的PFCAs,其降解没有明显的规律.降解中间产物主要是链更短的PFCAs,由此推断,PFCAs的降解遵循逐级降解的规律.     

无机阴离子、异丙醇及TiO_2对Fe~(3+)诱导全氟辛酸光化学降解影响的研究

254nm紫外光辐照下,溶解性Fe3+的存在有效促进了全氟辛酸(PFOA)的光化学降解.Fe3+浓度为30μmol·L-1时,Fe2(SO4)3,FeCl3和Fe(NO3)3三种溶解性铁盐对PFOA的降解和脱氟没有显著的差别.过量的SO24-与Fe3+具有较强的形成配合物的能力,由软件Visual MINTEQ2.52计算得出,Fe3+与过量的SO42-形成Fe(SO4)+和Fe(SO4)-2两种形态的配合物,其分配比的总和占16.32%,从而减少了PFOA与铁离子形成配合物的机会,进而抑制了其有效的光化学降解;过量的Cl-与Fe3+形成一配位的FeCl2+,其生成量仅占所有铁物种形态总和的0.12%,对PFOA的降解没有明显的影响,理论计算与实验结果相一致.羟基自由基捕获剂-异丙醇的加入未抑制PFOA的降解,二氧化钛的存在亦未促进其降解,进一步表明Fe3+诱导PFOA的光化学降解不是羟基自由基直接作用的结果.     

全氟辛酸的环境行为及其在多环境介质中的分布

全氟辛酸(PFOA)具有优良的疏水疏油性能及热稳定性,是我国重要的化工产品.但近年来,相关研究已经逐步证实PFOA具有持久性有机污染物的诸多特性,如环境持久性、难降解性及生物蓄积性.动物实验表明低剂量条件下,PFOA就能引发生殖、免疫、心血管和遗传发育等毒性.PFOA等现已成为继二恶英、有机氯农药等有机化合物之后的一种新型持久性有机污染物,是目前全氟化合物中最受关注的种类之一.本文作者针对全氟辛酸的环境行为及其在不同环境介质中的分布及特征做了综述,为将来进一步的研究工作的开展提供借鉴.     

紫外光致氯生水合电子对全氟辛酸的降解

研究了185 nm紫外光激发氯离子生成的水合电子还原降解全氟辛酸(PFOA)的效果. 结果表明, 该体系中氯离子、 紫外光和绝氧环境是保证PFOA高效降解的必要条件; 当PFOA的浓度为0.03 mmol/L时, 最佳反应条件为氯离子与PFOA摩尔浓度比(\begin{array}{c}{c}_{C{l}^{{}^{-}}}\end{array}/c_PFOA)为10.0, 溶液初始pH值为10.0, 体系温度为25 ℃. 该条件下反应23 h后PFOA的降解率和脱氟率分别达到99.6%和65.0%. PFOA在该体系中0~8 h的降解符合一级反应动力学, 反应速率常数为6.3×10^-3 min^-1. PFOA在该体系中降解的主要产物有氟离子、 短链全氟羧酸、 甲酸和乙酸. PFOA的降解有2种途径: (1) 氯离子在紫外光照射下产生水合电子, 水合电子进攻PFOA, 造成C—F键及C—C键的断裂; (2) 具有较高能量的185 nm紫外光光解PFOA, 发生脱羧反应, 并通过水解作用逐步脱氟.     

全氟辛酸和全氟辛烷磺酸人体暴露途径解析及其污染控制技术*

全氟辛酸（PFOA）和全氟辛烷磺酸（PFOS）是人工合成全氟化合物的典型代表。近年来,大量的环境调查数据表明它们普遍存在于多种环境介质、生物体甚至人体中,呈现出全球分布的态势,具有环境持久性和生物富集性,对人体健康存在潜在的危害,已成为一类新的环境持久性有机污染物而引起人们广泛的关注。本文介绍了PFOA和PFOS的环境来源和传输途径,解析了人体暴露的三种主要途径以及在食物、饮用水和空气/灰尘中的污染现状,并就围绕着它们所开展的污染控制技术方面的研究进行了评述。在此基础上,通过分析目前研究中所存在的问题,对今后的发展方向和研究重点进行了展望。     

无 氧 条 件 下ＴｉＯ２ 薄 膜 界 面 光 催 化 反 应 的ＸＰＳ 研 究

设计利用X射线光电子能谱仪的高真空系统作为无氧条件下光催化反应和分析的场所,研究真空无氧环境和大气有氧环境中紫外光激发TiO2薄膜表面的光催化反应,并对无氧条件下TiO2薄膜降解亚甲基蓝进行初步探索.结果表明,在大气有氧和真空无氧条件下TiO2薄膜经紫外光照后,表面的化学组成和化学状态均发生了变化;在有氧环境中TiO2薄膜表面氧含量增加,而在无氧环境中TiO2薄膜表面氧含量减少.TiO2薄膜表面的吸附氧是维持无氧条件下光催化反应的重要原因,增加薄膜表面吸附氧的含量能提高TiO2薄膜在无氧环境中的催化活性.此外,无氧条件下TiO2薄膜降解亚甲基蓝光催化反应过程中,亚甲基蓝分子只是脱去了某个含氮的基团,生成了中间产物,而并没有完全降解.     

二氧化碳/环氧丙烷/γ-丁丙酯三元共聚物微球降解性的研究

动物体内的体液和肠胃等器官的环境各不相同[1],这就要求各种不同用途的载药体的降解性能必须满足特定环境的要求.同时,可降解材料在不同的降解介质中通常有着不同的降解表现,这也决定着可降解材料的运用环境[2].因此,有必要对降解性材料在不同降解介质中的降解性进行专门的研究.由CO2和环氧化物合成的脂肪族聚碳酸酯具有良好的生物降解性能.但CO2与环氧丙烷的共聚物聚碳酸亚丙酯(PPC)的玻璃化转变温度较低[3],影响其加工性能,且降解速度较慢.在之前的研究中,我们通过引入第三单体来改善PPC的降解性并提高其玻璃化转变温度,获得一种由CO2/环氧丙烷/γ-丁内酯共聚的可降解三元脂肪族聚碳酸酯(PPCG)[4].本文在此基础上,通过复相乳液法制得PPCG载药微球,并对PPCG微球的降解性进行研究;考察了PPCG在不同降解液中的降解特性以及PPCG载葡萄糖微球在各种环境中的释药行为.     

高分子材料生物降解性能的分析研究进展

本文介绍了近年来生物降解材料降解方法的研究现状,主要从不同的降解环境,包括在堆肥环境、水性环境、惰性固体介质环境等进行的材料生物降解性能研究进行了比较、评述与展望。     

纳米针状氧化镓光催化降解纯水和废水中全氟辛酸

采用聚乙烯醇调控的水热法合成了对全氟辛酸(PFOA)有高光催化活性的纳米针状Ga₂O₃.其颗粒长3-6μm,宽100-200nm,具有较大的比表面积(25.95m²/g)和纳米孔结构(4-25nm).在普通紫外光照射下(λ=254nm),纳米针状Ga₂O₃光催化降解纯水中PFOA的反应半衰期为18.2min,PFOA的一级反应降解动力学常数为2.28h^-1,分别为商品Ga₂O₃和TiO₂作为催化剂时的7.5和16.8倍.此外,当纳米针状Ga₂O₃与真空紫外光(λ=185nm)结合时,不仅可以更高效地降解纯水中的PFOA(反应速率常数4.03h^-1),而且能有效消除废水中共存有机物的影响,从而高效分解废水中的PFOA(反应速率常数3.51h^-1),且此方法的能耗远远低于文献报道的其他方法的能耗值.     

多环麝香(PCMs)的环境行为及毒性效应

多环麝香(PCMs)作为重要的人工合成麝香广泛应用于日用品中,目前在各种环境介质中都能检测到PCMs的存在。由于其持续不断地进入环境并能够在生物体内积累,其效应类似于持久性污染物。作为一类新型污染物,PCMs所引起的环境问题受到了广泛重视。本文介绍了PCMs的物理化学性质、来源以及在不同环境介质中的分析方法和污染现状,概述了其在环境中的降解转化、生物富集行为,并总结了其能产生的急性毒性效应、亚慢性毒性效应、内分泌干扰效应和其他潜在的毒性效应,最后讨论了目前研究中存在的问题,并对未来研究进行了展望。今后,应该建立有效的、可比对的标准分析方法,更加系统地进行环境污染现状、迁移转化规律和生物降解代谢途径的研究;重视暴露途径和生物有效性的研究,并与风险评价结合;结合环境中PCMs的污染现状,探讨低剂量长期暴露和复合暴露对生物的影响。     

Photochemical degradation of environmentally persistent perfluorooctanoic acid (PFOA) in the presence of Fe(III)

Environmentally persistent and bioaccumulative perfluorooctanic acid (PFOA) was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol /L Fe(III), 80% of PFOA with initial concentration of 48μmol/L (20 mg/L) was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe(III) initiated degradation of PFOA irradiated with 254 nm UV light.     

Photochemical degradation of environmentally persistent perfluorooctanoic acid （PFOA） in the presence of Fe（Ⅲ）

Environmentally persistent and bioaccumulative perfluorooctanic acid （PFOA） was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol/L Fe（Ⅲ）, 80% of PFOA with initial concentration of 48μmol/L （20 mg/L） was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe（Ⅲ） initiated degradation of PFOA irradiated with 254 nm UV light.     

A comparative study of bismuth-based photocatalysts with titanium dioxide for perfluorooctanoic acid degradation

Bismuth-based material has been broadly studied due to their potential applications in various areas, especially used as promising photocatalysts for the removal of persistent organic pollutants (POPs) and several approaches have been adopted to tailor their features. Herein, the bismuth-based photocatalysts (BiOCl, BiPO₄, BiOPO₄/BiOCl) were synthesized by hydrothermal method and advanced characterization techniques (XRD, SEM, EDS elemental mapping, Raman and UV–vis DRS) were employed to analyze their morphology, crystal structure, and purity of the prepared photocatalysts. These synthesized photocatalysts offered a praiseworthy activity as compared to commercial TiO₂ (P25) for the degradation of model pollutant perfluorooctanoic acid (PFOA) under 254 nm UV light. It was interesting to observe that all synthesized photocatalysts show significant degradation of PFOA and their photocatalytic activity follows the order: bismuth-based catalysts > TiO₂ (P25) > without catalyst. Bismuth-based catalysts degraded the PFOA by almost 99.99% within 45 min while this degradation efficiency was 66.05% with TiO₂ under the same reaction condition. Our work shows that the bismuth-based photocatalysts are promising in PFOA treatment.     

FTIR-ATR技术研究聚氨酯类文物保护材料的光降解

Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory （FTIR-ATR）. It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate （urethane） groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color.     

Studies of photochemical transformations in polystyrene and styrene-maleic anhydride copolymer

Thin films of polystyrene (PS) and styrene-maleic anhydride copolymer (St-MAn) were exposed to monochromatic UV radiation (254 nm) for varied time intervals. The course of photochemical transformations was monitored by absorption spectroscopy (FT-IR, UV-vis) and thermogravimetry, which were also applied for the estimation of the thermal stability of samples studied. The changes of surface properties were monitored by contact angle measurements.Changes in chemical structure were found in irradiated films (inside and at the surface). The efficiency of photooxidative degradation in St-MAn copolymer was slightly lower than that in PS homopolymer but photo-crosslinking and chromophore formation were enhanced. An increase of hydrophilicity and oxidation degree in UV-irradiated samples was accompanied by destruction processes. The thermal stability of St-MAn was lower in comparison to polystyrene alone.The mechanism of photochemical reactions in the copolymer is proposed.     

A comparative study of bismuth-based photocatalysts with titanium dioxide for perfluorooctanoic acid degradation

The fabricated bismuth-based photocatalysts presented an outstanding performance as compared to commercial TiO₂ (P25) for PFOA degradation under 254 nm UV light irradiation.     

Mechanistic Aspects of the Effects of Stress on the Rates of Photochemical Degradation Reactions in Polymers

Abstract

This review examines the mechanistic origins of the effects of stress on the photochemical degradation rates of polymers. Recent studies have shown that tensile and shear stresses accelerate the rate of the photochemical degradation of polymers. Conversely, compressive stress generally retards the rate of photochemical degradation. After an initial discussion of the photochemical auto‐oxidation mechanism, the three primary hypotheses that purport to explain how stress affects photochemical degradation are examined. The first hypothesis is attributed to Plotnikov, who proposed that stress changes the quantum yields of the reactions that lead to bond photolysis. The second hypothesis, attributed to a number of researchers, says that stress affects the ability of the geminate radical pairs, formed in the photochemical bond cleavage reactions, to recombine. The third hypothesis proposes that stress changes the rates of radical reactions subsequent to radical formation. A further attempt to account for the effects of stress on degradation rates is a modification of the so‐called Zhurkov equation that has been used rather successfully to predict the effects of stress on degradation rates in thermal reactions. This empirical equation relates the quantum yield of degradation to a composite activation barrier for the overall photochemical reaction. Following the discussion of these hypotheses, experimental mechanistic studies of stress effects are summarized, and what little data there is is shown to be consistent with the hypothesis that proposes that stress primarily affects the ability of photochemically generated radical pairs to recombine. By decreasing the efficiency of radical–radical recombination, the effect is to increase the relative efficiencies of the radicals' other reactions and hence the rate of degradation. In addition to stress, other factors can affect the rates of polymer photodegradation. These factors include the absorbed light intensity, the polymer morphology, the rate of oxygen diffusion in the polymer, and the chromophore concentration. Each of these parameters must be carefully controlled in mechanistic studies that probe the effects of stress on degradation rates.     

ß‐Ga2O3 Nanorod Synthesis with a One‐step Microwave Irradiation Hydrothermal Method and its Efficient Photocatalytic Degradation for Perfluorooctanoic Acid

ß‐Ga₂O₃ nanorod was first directly prepared by the microwave irradiation hydrothermal way without any subsequent heat treatments, and its characterizations were analyzed by X‐ray diffraction (XRD), scanning electron microscope (SEM), high‐resolution transmission electron microscope (HRTEM), UV–Vis diffuse reflection spectroscopy techniques, and also its photocatalytic degradation for perfluorooctanoic acid (PFOA) was investigated. XRD patterns revealed that ß‐Ga₂O₃ crystallization increased with the enhancement of microwave power and the adding of active carbon (AC). PFOA, as an environmental and persistent pollutant, is hard decomposed by hydroxyl radicals (HO·); however, it is facilely destroyed by ß‐Ga₂O₃ photocatalytic reaction in an anaerobic atmosphere. The important factors such as pH, ß‐Ga₂O₃ dosage and bubbling atmosphere were researched, and the degradation and defluorination was 98.8% and 56.2%, respectively. Reductive atmosphere reveals that photoinduced electron may be the major reactant for PFOA. Furthermore, the degradation kinetics for PFOA was simulated and constant and half‐life was calculated, respectively.