高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (8): 1606-1613.doi: 10.7503/cjcu20190096

• 分析化学 • 上一篇    下一篇

BMIMBF4中2-氨基-3-氯-1,4-萘醌电化学捕获CO2的机理

乔雪娇, 李丹, 程龙玖, 金葆康   

  1. 安徽大学化学化工学院, 合肥 230601
  • 收稿日期:2019-02-10 修回日期:2019-07-23 出版日期:2019-08-10 发布日期:2019-07-12
  • 通讯作者: 金葆康,男,博士,教授,博士生导师,主要从事电分析化学、生物电化学和光谱电化学研究.E-mail:bkjinhf@aliyun.com E-mail:bkjinhf@aliyun.com
  • 基金资助:
    国家自然科学基金(批准号:21375001)资助.

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

QIAO Xuejiao, LI Dan, CHENG Longjiu, JIN Baokang   

  1. School of Chemistry & Chemical Engineering, Anhui University, Hefei 230601, China
  • Received:2019-02-10 Revised:2019-07-23 Online:2019-08-10 Published:2019-07-12
  • Supported by:
    Supported by the National Natural Science Foundation of China(No.21375001).

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(BMIMBF4)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BMIMBF4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(ACNQ2-)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ACNQ2-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.

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

Abstract: 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(BMIMBF4) 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 BMIMBF4. The dianion(ACNQ2-) 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 ACNQ2- 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.

Key words: in-situ FTIR spectroelectrochemistry, 2-Amino-3-chloro-1,4-naphthoquinone(ACNQ), 1-Butyl-3-methylimidazolium tetrafluoroborate, CO2, Nucleophile

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