文献类型：期刊文献

中文题名：硫酸根自由基氧化过程中硝基和溴代副产物协同/抑制生成机制

英文题名：Synergistic formation/inhibition of nitrated and brominated byproducts in sulfate radical oxidation process

作者：王露[1,2];石文艳[1];陆隽鹤[2];胡保卫[1]

机构：[1]绍兴文理学院,浙江绍兴312000;[2]南京农业大学资源与环境科学学院,江苏南京210095

年份：2025

卷号：45

期号：6

起止页码：3128

中文期刊名：中国环境科学

外文期刊名：China Environmental Science

收录：北大核心2023、、EI(收录号：20252818772956)、北大核心

基金：国家自然科学基金资助项目(22306122);浙江省一般科研项目(Y202351427);绍兴市科技计划项目(2022A13005)。

语种：中文

中文关键词：硫酸根自由基;亚硝酸盐;溴离子;硝酰溴;硝基副产物;溴代副产物

外文关键词：sulfate radicals;nitrite;bromide;nitryl bromide;nitrated byproducts;brominated byproducts

中文摘要：硫酸根自由基(SO_(4)??)高级氧化技术(SR-AOPs)反应体系中含有NO_(2)^(?)和Br^(?)时,会分别生成具有“三致”毒性的硝基和溴代副产物.本研究探讨了在二者共存条件下,硝基和溴代副产物的生成机制.结果表明:苯酚在SO_(4)??硝化过程中,产生了3种硝基酚副产物,包括2-硝基酚,4-硝基酚和2,4-二硝基酚.当活化温度为60℃,苯酚,NO_(2)^(?)及过二硫酸盐(PDS)初始浓度分别为50μmol/L,100μmol/L及2mmol/L时,硝基酚的总转化率为34.5%.若反应中存在100μmol/L Br^(?),硝基酚的生成速率明显加快,相同条件下转化率增加至46.0%.原位形成的Br_(2)/HOBr迅速与NO_(2)^(?)结合,生成了一种强硝化剂—硝酰溴(BrNO_(2)).BrNO_(2)直接进攻苯酚,对促进硝基酚的生成发挥着关键性作用.值得注意的是,Br^(?)最终被释放出来,其作用相当于催化剂.同时,存在NO_(2)^(?)导致溴代副产物(如二溴乙酸)的生成速率受到抑制.因此,在SR-AOPs中,NO_(2)^(?)和Br^(?)的转化机制相互影响.二者共存时,促进了硝基酚副产物的生成,但抑制了溴代副产物.

外文摘要：Sulfate radical(SO_(4)??)-based advanced oxidation processes(SR-AOPs)are characterized by in situ generation of SO_(4)??with strong oxidation capacity,which can effectively degrade a variety of organic pollutants.However,SO_(4)??can transform nitrite(NO_(2)^(?))and bromide(Br^(?))into toxic nitrated byproducts and halogenated byproducts,respectively.In this study,the mechanisms underlying the formation of nitrated and brominated byproducts on the reaction system in which NO_(2)^(?)and Br^(?)coexist were systematically investigated.Results showed that three nitrated byproducts,including 2-nitrophenol,4-nitrophenol,and 2,4-dinitrophenol were produced during the heat-activated persulfate nitrification process.It was observed that nitrophenols accounted for approximately 34.5%of the phenol transformed under reaction conditions of[phenol]=50μmol/L,[NO_(2)^(?)]=100μmol/L,[PDS]=2mmol/L and temperature of 60℃C.Once NO_(2)^(?)was co-present,the formation rate of nitrophenol was significantly accelerated.The conversion rate increased to 46.0%under the same conditions.Br^(?)can be oxidized by SO_(4)??to form reactive bromine species,which rapidly react with NO_(2)^(?)to form a strong oxidizing agent,nitryl halide.Then nitryl halide reacts with the phenol and plays a key role in promoting the formation of nitrophenol.Note that,Br^(?)is eventually released and acts as a catalyst equivalent.Meanwhile,the presence of NO_(2)^(?)results in an inhibition of the rate of formation of brominated byproducts,such as dibromoacetic acid.Therefore,the transformation mechanisms of NO_(2)^(?)and Br^(?)influence each other in SR-AOPs.When they coexist,promote the formation of nitrophenol byproducts but inhibit brominated byproducts.