Fe(Ⅵ)氧化降解1-萘酚的实验研究及密度泛函理论计算  

Experimental study and density functional theory calculation of 1-NAP oxidation degradation by Fe(Ⅵ)

作　　者：杨杰 陈中锴 张静 王嘉琪 张国凯 李亚男[1] YANG Jie;CHEN Zhongkai;ZHANG Jing;WANG Jiaqi;ZHANG Guokai;LI Yanan(College of Environmental Science and Engineering,Taiyuan University of Technology,Jinzhong 030600,China;College of Mathematics and Physics,Beijing University of Chemical Technology,Beijing 100029,China;Hebei Construction Investment Water Investment Co.,Ltd.,Shijiazhuang 050051,China;Chinasea Group Environmental Protection Engineering Co.,Ltd.,Taiyuan 030012,China)

机构地区：[1]太原理工大学环境科学与工程学院,山西晋中030600 [2]北京化工大学数理学院,北京100029 [3]河北建投水务投资有限公司,河北石家庄050051 [4]中海国亚环保工程有限公司,山西太原030012

出　　处：《化工环保》2024年第5期652-659,共8页Environmental Protection of Chemical Industry

基　　金：山西省应用基础研究计划项目(20210302123121);山西省省筹资金资助回国留学人员科研项目(2023-054)。

摘　　要：以1-萘酚(1-NAP)为目标污染物,采用Fe(Ⅵ)对其进行氧化降解,考察了降解效果的影响因素,进行了自由基分析,利用GC-MS鉴定了中间产物,基于密度泛函理论(DFT)预测了反应位点,并推测了反应路径。实验结果表明:在Fe(Ⅵ)与1-NAP(100 mg/L)的质量比为6∶1、反应液pH为9.0(硼砂缓冲溶液)的优化条件下,于12℃反应360 s,1-NAP降解率可达91.4%;Fe(Ⅴ)/Fe(Ⅳ)和·OH对1-NAP降解的贡献率分别为23.9%和14.5%。DFT计算结果表明,7、9、10号碳原子以及11号氧原子的亲电反应福井函数(f^(-))值较高,说明这些位点更易被Fe(Ⅵ)包围。Fe(Ⅵ)氧化降解1-NAP的机理包括单氧转移、双氧转移、·OH攻击以及单电子转移。As the target pollutant,1-naphthol(1-NAP)was oxidized and degraded by Fe(Ⅵ).The factors for the degradation effect were investigated and free radical analysis was performed.The intermediate product was identified by GC-MS,and the reaction site and reaction path were predicted based on the density functional theory(DFT).The experimental results show that the degradation rate of 1-NAP could reach 91.4%at 12℃for 360 s under the optimal conditions where the mass ratio of Fe(Ⅵ)to 1-NAP(100 mg/L)is 6∶1 and pH of the reaction solution is 9.0(borax buffer solution).The contribution rates of Fe(Ⅴ)/Fe(Ⅳ)and·OH to 1-NAP degradation are 23.9%and 14.5%,respectively.According to the DFT calculation results,the f^(-)values of carbon atoms 7,9,and 10 and oxygen atoms 11 are higher,indicating that these sites are more easily surrounded by Fe(Ⅵ).The mechanism of oxidative degradation of 1-NAP by Fe(Ⅵ)includes single-oxygen transfer,double-oxygen transfer,·OH attack,and single electron transfer.

关 键 词：Fe(Ⅵ) 1-萘酚 中间产物 降解路径 密度泛函理论 

分 类 号：X703[环境科学与工程—环境工程]