Fenton反应及其参与的光催化体系的机理研究进展

综述了光催化降解有机污染物和杀菌的机理,其中降解有机物机理的主要内容为空穴和羟基自由基(·OH)氧化分解有机污染物,杀菌机理与降解有机物类似,即电子和空穴或含氧自由基攻击细菌的细胞壁、细胞膜和胞内成分,使细菌失活。分别从Fe~(2+)和Cu~(2+)两种离子介导的Fenton反应总结了Fenton反应的机理,得出两种离子介导的Fenton反应具有类似机理的结论。最后阐述了目前在光催化体系中引入Fenton反应的研究现状及作用机理,发现将Fenton反应引入光催化体系是促进光催化活性的有效途径。     

Quantitation of Hydroxyl Radicals from Photolysis of Fe(III)-Citrate Complexes in Aerobic Water (5 pp)

Background For their high photoreactivity, Fe(III)-carboxylate complexes are important sources of H2O2 for some atmospheric and surface waters. Citrate is one kind of carboxylate, which can form complexes with Fe(III). In our previous study, we have applied Fe(III)-citrate complexes to degrade and decolorize dyes in aqueous solutions both under UV light and sunlight. Results have shown that carboxylic acids can promote the photodegradation efficiency. It is indicated that the photolysis of Fe(III)-citrate complexes may cause the formation of some reactive species (e. g. H2O2 and ·OH). This work is attempted to quantify hydroxyl radicals generated in the aqueous solution containing Fe(III)-citrate complexes and to interpret the photoreactivity of Fe(III)-citrate complexes for degrading organic compounds. Methods By using benzene as the scavenger to produce phenol, the photogeneration of ·OH in the aqueous solution containing Fe (III)-citrate complexes was determined by HPLC. Results and Discussion In the aqueous solution containing 60.0/30.0 mM Fe(III)/citrate and 7.0 mM benzene at pH 3.0, 96.66 mM ·OH was produced after irradiation by a 250W metal halide light (l ≥ 313 nm) for 160 minutes. Effects of initial pH value and concentrations of Fe(III) and citrate on ·OH radical generation were all examined. The results show that the greatest photoproduction of ·OH in the aqueous solution (pH ranged from 3.0 to 7.0) was at pH 3.0. The photoproduction of ·OH increased with increasing Fe(III) or citrate concentrations. Conclusion In the aqueous solutions containing Fe(III)-citrate complexes, ·OH radicals were produced after irradiation by a 250W metal halide light. It can be concluded that Fe(III)-citrate complexes are important sources of ·OH radicals for some atmospheric and surface waters. Recommendations and Outlook It is believed that the photolysis of Fe(III)-citrate complexes in the presence of oxygen play an important role in producing ·OH both in atmospheric waters and surface water where high concentrations of ferric ions and citrate ions exist. The photoproduction of ·OH has a high oxidizing potential for the degradation of a wide variety of natural and anthropogenic organic and inorganic substances. We can use this method for toxic organic pollutants such as organic dyes and pesticides.     

Decontamination of Cr(VI) facilitated formation of persistent free radicals on rice husk derived biochar

PFRs were produced on biochar during Cr(VI) decontamination. PFRs formation on biochar was owing to the oxidization of phenolic-OH by Cr(VI). Appearance of excessive oxidant led to the consumption of PFRs on biochar. Biochar charred at high temperature possessed great performance to Cr(VI) removal. This study investigated the facilitation of Cr(VI) decontamination to the formation of persistent free radicals (PFRs) on rice husk derived biochar. It was found that Cr(VI) remediation by biochar facilitated the production of PFRs, which increased with the concentration of treated Cr(VI). However, excessive Cr(VI) would induce their decay. Biochar with high pyrolysis temperature possessed great performance to Cr(VI) removal, which was mainly originated from its reduction by biochar from Inductively Coupled Plasma Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy. And the corresponding generation of PFRs on biochar was primarily ascribed to the oxidization of phenolic hydroxyl groups by Cr(VI) from Fourier Transform Infrared Spectroscopy analysis, which was further verified by the H₂O₂ treatment experiments. The findings of this study will help to illustrate the transformation of reactive functional groups on biochar and provide a new insight into the role of biochar in environmental remediation.     

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

羟基自由基杀灭压载水赤潮入侵生物试验研究

采用羟基自由基对斯式根管藻、日本星杆藻、裸甲藻和细菌进行杀灭实验，确定杀灭入侵赤潮生物的所需OH^-比值浓度为0.68mg／L。当OH^-比值浓度达到0．68mg／L时，致死多甲藻(Peri.Spp)等10种赤潮生物效率达到99.8％，致死膝沟孢子、多甲藻孢子效率达到100％。试验数据表明，强电离先进氧化OH^-是治理赤潮有效、可行的绿色新方法。     

有机污染物的光催化降解过程中的分析技术进展

本文对有机物的光催化降解动力学研究 ,降解产物的鉴定、定量检测等过程中所使用的一些分析技术和手段 ,尤其是在有机物的光降解机理研究中羟自由基的检测技术和方法进行了综述     

羟基自由基氧化降解水中土臭素的效率与机制

土臭素(Geosmin,GSM)是一种由蓝绿藻及放线菌产生,具有令人讨厌土霉味的化合物.地表水中存在土臭素,尽管量少,但因传统水处理工艺难以去除,大大降低了饮用水的感官质量.本文采用大气压强电场电离放电结合水力射流空化方式制备的羟基自由基(Hydroxyl radicals,·OH)对水中GSM进行氧化降解,研究了氧化剂投加剂量、接触时间因素的影响,并根据气相色谱-质谱(GC-MS)全扫描获取的中间产物探讨了·OH氧化降解GSM的机制.实验结果表明:当氧化剂投加剂量为0.8 mg·L~(-1),管路中接触反应6 s,可把初始浓度100 ng·L~(-1)的GSM降解到10 ng·L~(-1)以下;提高氧化剂投加量至2.6 mg·L~(-1),接触反应180 s,可氧化降解500 ng·L~(-1)的GSM至10 ng·L~(-1)以下,达到我国《生活饮用水卫生标准》(GB5749—2006).在GSM水样中加入叔丁醇(Tertiary butyl alcohol,TBA)·OH淬灭剂,GSM氧化降解效果明显降低,间接证明了降解GSM的主要物质为·OH.对氧化降解GSM的中间产物分析表明·OH可以破坏GSM双环结构并最终将其矿化成CO_2和H_2O.     

丰枯水期鄱阳湖表层水中羟基自由基浓度及其抗生素净化作用研究

鄱阳湖位于我国农业大省江西省,表层湖水中羟基自由基(HO·)引发的水体光化学反应,可能对流域内的农业污染物—抗生素具有潜在的净化作用.因此,本研究以氙灯模拟太阳光测得鄱阳湖及周边河流羟基自由基表观光量子产率(ΦHO·),在丰水期为(0.57~10.33)×10~(-5),枯水期为(0.45~3.52)×10~(-5).丰水期溶解态有机物(DOM)对HO·形成的贡献率为85.8%~98.7%,枯水期为58.5%~97.6%,表明DOM是HO·形成的主导物质.可能由于水体混合均匀,丰水期除抚河水体可能有其特殊的化学组成外,其它湖泊与河流的水化学组成接近,表现出随溶解态有机碳含量升高,ΦHO·呈先增大后减小的现象.枯水期水体各化学组成含量显著高于丰水期,光屏蔽与淬灭可能起主要作用,只有当NO_2~-含量较高时才显示出对HO·形成的贡献.依据太阳光强可得鄱阳湖丰水期及枯水期表层水HO·的稳态浓度分别为9.51×10~(-16)与4.92×10~(-17)mol·L~(-1),湖水中5种抗生素在HO·作用下的半衰期分别为2.3~13.9 d与44.5~268.7 d,丰水期鄱阳湖表现出更高的光化学净化能力.