【作者】 李峰； 王文娟； 孟茹； 李丹； 王家佳； 王伟； 金葆康；

【Author】 Feng Li;Wenjuan Wang;Ru Meng;Dan Li;Jiajia Wang;Wei Wang;Baokang Jin;Department of Chemistry,Anhui University;School of Chemistry and Chemical Engineering,Yancheng Institute of Technology;

【机构】 安徽大学化学化工学院； 盐城工学院化学化工学院；

【摘要】 采用循环伏安法、整体电解法和现场红外光谱电化学法研究了对硝基氯苯（PNCB）在质子惰性溶剂中的电化学行为。在没有CO₂存在的情况下,PNCB的电化学行为在-0.4～-1.4 V扫描范围中是可逆的一步单电子传递过程,而一旦引入CO₂则转变为完全不可逆的四电子传递过程。通过单晶衍射、¹³C-NMR、¹H-NMR和FTIR,确定了CO₂存在下唯一的电解产物为4,4’-二氯偶氮苯（DAB）。在没有质子供体的情况下,实现了低电位下PNCB的电化学降解,同时将CO₂电化学转化为CO₃^2-。基于循环伏安法（CVA）和导数循环伏安法（DCVA）技术,建立了双电位阶跃时间分辨红外扫描电化学技术（DPS TR IRSEC）来跟踪电化学还原过程中CO₂的吸附行为。因此,基于上述研究结果,提出了一种PNCB在CO₂存在下新的电化学机理,为实现氯代硝基苯的电化学降解提供理论依据。更多还原

【Abstract】 The electrochemical behavior of p-nitrochlorobenzene（PNCB） in the aprotic solvent was investigated by cyclic voltammetry,bulk electrolysis and in situ FT-IR spectroelectrochemistry.In the absence of CO₂,the electrochemical behavior of PNCB is reversibly one-step single-electron transfer during the scan between-0.4 and-1.4 V,but with adding CO₂,which is transformed into completely irreversible four-electrons transfer process.The only electrolysis product indicating high selectivity in the presence of CO₂ is confirmed as 4,4’-dichloroazobenzene（DAB） by X-ray single crystal diffraction,¹³C-NMR,¹H-NMR and FTIR.In the absence of proton donor,the electrochemical degradation of PNCB at low potential is achieved,and CO₂ is electrochemically converted to CO32-simultaneously.Based on cyclic voltabsorptometry（CVA） and derivative cyclic voltabsorptometry（DCVA） techniques,double potential step time-resolved IR scanning electrochemical technique（DPS TR IRSEC） was developed to illustrate the adsorption behavior of CO₂ in the electrochemical reduction process.Therefore,a new electrochemical mechanism of PNCB in the presence of CO₂ has been proposed based on the above results,which will be beneficial for theoretical research.更多还原