BMIMBF4中2-氨基-3-氯-1,4-萘醌电化学捕获CO2的机理  

Mechanism of Electrochemical Capture of CO2 via Redox Cycle of 2-Amino-3-chloro-1,4-naphthoquinone in BMIMBF4

作　　者：乔雪娇 李丹[1] 程龙玖[1] 金葆康[1] QIAO Xuejiao;LI Dan;CHENG Longjiu;JIN Baokang(School of Chemistry&Chemical Engineering,Anhui University,Hefei 230601,China)

机构地区：[1]安徽大学化学化工学院

出　　处：《高等学校化学学报》2019年第8期1606-1613,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21375001)资助~~

摘　　要：利用循环伏安法(CV)和现场红外光谱电化学技术研究了2-氨基-3-氯-1,4-萘醌(ACNQ)在1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF 4)中电化学捕获CO2的机理.研究结果表明,当体系中不存在CO2时,ACNQ在BMIMBF 4中经历可逆的两步一电子过程;当体系中引入CO2时,电化学还原过程中形成的二价阴离子(ACNQ^2-)作为亲核试剂,可攻击CO2的亲电子碳中心,形成稳定的CO2加合物.对电化学捕获CO2的化学计量进行了评估,结果表明,1摩尔的ACNQ^2-可捕获1摩尔的CO2.结合B3LYP方法在6-311++G^***水平上计算分析了反应中CO2加合物可能的结构.The mechanism of electrochemical capture of CO2 via redox cycle of 2-amino-3-chloro-1,4-naphthoquinone(ACNQ) in 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF 4 ) was investigated by cyclic voltammetry(CV) and in-situ Fourier transform infrared(FTIR) spectroelectrochemistry techniques. In the absence of CO2, ACNQ undergoes a reversible two-step one-electron process in BMIMBF 4 . The dianion (ACNQ^ 2- ) formed during electrochemical reduction can be used as nucleophiles to attack the eletrophilic carbon center of CO2 and form a stable CO2 adduct when CO2 is introduced. Furthermore, the stoichiometry of CO2 electrochemical capture was evaluated. The result indicates that 1 mol of ACNQ^2- can capture 1 mol of CO2. Also, the possible structures of CO2 adducts in the reaction were calculated by the B3LYP method at the 6-311++G^*** level.

关 键 词：现场红外光谱电化学 2-氨基-3-氯-1 4-萘醌 1-丁基-3-甲基咪唑四氟硼酸盐 二氧化碳 亲核试剂 

分 类 号：O657.1[理学—分析化学]