纳米Ni(OH)_2微萃取和电催化敌草隆的循环伏安和量子化学法研究  

Study of nano nickel hydroxide microextractionand electrocatalysis of diuron by cyclic voltammetry and quantum chemical method

作　　者：王佳 朱永春 那宝双[1] 辛士刚 张洪波 WANG Jia;ZHU Yong-chun;NA Bao-shuang;XIN Shi-gang;ZHANG Hong-bo(College of Chemistry and Chemical Engineering,Shenyang Normal University,Shenyang 110034,China;Institute of Catalysis for Energy and Environment,Shenyang Normal University,Shenyang 110034,China)

机构地区：[1]沈阳师范大学化学化工学院,辽宁沈阳110034 [2]沈阳师范大学能源与环境催化研究所,辽宁沈阳110034

出　　处：《化学研究与应用》2018年第4期502-509,共8页Chemical Research and Application

基　　金：国家科技部国际合作重大项目资助(2004DFA02700)资助;国家自然基金(20875063)资助;辽宁教育厅(2004-c022)资助;国家电分析重点实验室(2006-06);沈阳市科技局基金(2007-GX-32)资助

摘　　要：电沉积纳米氢氧化镍于碳糊电极表面上实现了原位修饰,以循环伏安和PM7量子化学方法研究了敌草隆在纳米氢氧化镍表面形成的络合物,具有固相微萃取和电化学催化功能。循环伏安结果表明,氢氧化镍与敌草隆络合后,与在KCl溶液中的结果相比,还原峰电流增大,还原峰负移,氧化峰正移,与在NaOH溶液中的结果相比,氧化峰电流增大。表明敌草隆与镍配位形成的络合物有利于萃取富集,具有一定的氧化还原催化作用,提高峰电流。PM7量子化学半经验分子轨道方法计算络合物的热力学参数、分子轨道能量与组成。通过热力学原理分析计算所得数据,表明该络合物稳定性更大,络合作用可以自发形成,形成络合物分子的可移动电子数增加,更有利于电子转移。理论计算结果与实验结果趋于一致。The surface of acarbon paste electrode was modified with nano nickel hydroxide particle in-site by electrodeposition method.The interaction between diuron and nano nickel hydroxide particle on the electrode was studied by cyclic voltammetry and PM7 quantum chemical method.The modified electrode shows a solid phasemicro-extraction and electrocatalytic behavior to diuron.Cyclic voltammetry shows that the complex formation between nickel hydroxide and diuron results in an increase of redox peak current,negative shift of reduction peak potential,and positive shift of oxidation peak potential compared with those in KCl and sodium hydroxide solution.The peak potential shifts and solid phase nano extraction are directly related to the formation of the complex as well as the increase of the redox peak current.The thermodynamic and frontier molecular orbital data were obtained based on the molecular models of the related molecules by PM7 quantum chemistry semiempirical molecular orbital method.The calculated thermodynamic parameters show the all molecular models are stable,and the formation of the complex of nickel hydroxide and diuron is the most stable one with the negative Gibbs free energy.The molecular index of exchangable electron from the frontier orbital energy of the models shows the formed complex is more favorable for electron transfer.The calculation results are in good consistency with the experimental results qualitatively.

关 键 词：敌草隆 氢氧化镍 纳米粒子 原位修饰 PM7量子化学计算 

分 类 号：O646.5[理学—物理化学]