双二苯基-1-甲基咪唑膦氯化镍的制备及其电催化还原CO2的研究

doi:10.13208/j.electrochem.170401

电化学（中英文） ›› 2018, Vol. 24 ›› Issue (2): 103-110. doi: 10.13208/j.electrochem.170401

双二苯基-1-甲基咪唑膦氯化镍的制备及其电催化还原CO₂的研究

张历朴，钮东方，张新胜^*

华东理工大学化学工程联合国家重点实验室，上海 200237

收稿日期:2017-04-04 修回日期:2017-05-09 出版日期:2018-04-28 发布日期:2017-05-11
通讯作者: 张新胜 E-mail:xszhang@ecust.edu.cn
基金资助:
国家自然科学青年基金项目(No. 21303053 )资助

Preparation of Ni(dpim)₂Cl₂ Complex for the Electrocatalytic Reduction of CO₂

ZHANG Li-pu, NIU Dong-fang, ZHANG Xin-sheng^*

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2017-04-04 Revised:2017-05-09 Published:2018-04-28 Online:2017-05-11
Contact: ZHANG Xin-sheng E-mail:xszhang@ecust.edu.cn

摘要/Abstract

摘要：

以二苯基-1-甲基咪唑膦（dpim）为配体制备了一种新型的配合物催化剂Ni(dpim)₂Cl₂. 循环伏安研究表明，Ni(dpim)₂Cl₂配合物在氮气气氛下表现出两步还原的电化学行为，在-0.7 V下为两电子的不可逆还原，在-1.3 V下为单电子准可逆还原. 向电解液中通入CO₂后，在-1.3 V下的还原峰变得不可逆，且其峰电流从0.48 mA·cm^-2增大到0.55 mA·cm^-2. 在质子源（CH₃OH）存在的条件下，该还原峰电流可继续增大到0.72 mA·cm^-2. 该研究结果表明，Ni(dpim)₂Cl₂配合物对CO₂还原具有良好的电催化性能，且其电催化还原过程符合ECE机理. 在-1.3 V下恒电位电解得到的还原产物主要为CO，催化转换频率（Turnover of Frenquency, TOF）为0.17 s^-1.

关键词: 双二苯基-1-甲基咪唑膦氯化镍, 甲醇, 二氧化碳, 电催化

Abstract:

A new Ni(dpim)₂Cl₂complex using 2-(diphenylphosphino)-1-methylimidazole (dpim) as ligand was prepared and served as a catalyst for the electrochemical reduction of CO₂. The electrochemical redox behavior of Ni(dpim)₂Cl₂ in CH₃CN/TPABF₄solution under nitrogen atmosphere showed the two-electron irreversible reduction at -0.7 V and one-electron quasi-reversible reduction at -1.3 V. After bubbling CO₂ into the electrolyte, the reduction peak appeared at -1.3 V became irreversible and the peak current increased from 0.48 mA·cm^-2 to 0.55 mA·cm^-2. Moreover, the peak current at -1.3 V could further increase to 0.72 mA·cm^-2 in the presence of proton source (CH₃OH). These observations indicate that the Ni(dpim)₂Cl₂ exhibited a good electrocatalytic performance toward CO₂reduction and the electrocatalytic reduction process followed the ECE mechanism. The reduction products obtained by the potentiostatic electrolysis (at -1.3 V) were identified to be mainly CO with the catalytic conversion frequency of 0.17 s^-1.

Key words: Ni(dpim)₂Cl₂, methanol, CO₂, electrocatalysis

中图分类号:

O646

张历朴，钮东方，张新胜. 双二苯基-1-甲基咪唑膦氯化镍的制备及其电催化还原CO₂的研究[J]. 电化学（中英文）, 2018, 24(2): 103-110.

ZHANG Li-pu, NIU Dong-fang, ZHANG Xin-sheng. Preparation of Ni(dpim)₂Cl₂ Complex for the Electrocatalytic Reduction of CO₂[J]. Journal of Electrochemistry, 2018, 24(2): 103-110.

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https://electrochem.xmu.edu.cn/CN/Y2018/V24/I2/103

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双二苯基-1-甲基咪唑膦氯化镍的制备及其电催化还原CO₂的研究

Preparation of Ni(dpim)₂Cl₂ Complex for the Electrocatalytic Reduction of CO₂

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