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

doi:10.13208/j.electrochem.170401

电化学 >

2018 , Vol. 24 >Issue 2: 103 - 110

DOI: https://doi.org/10.13208/j.electrochem.170401

研究论文

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

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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

网络出版日期: 2017-05-11

基金资助

国家自然科学青年基金项目(No. 21303053 )资助

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

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

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

Received date: 2017-04-04

Revised date: 2017-05-09

Online published: 2017-05-11

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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

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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, 2018 , 24(2) : 103 -110 . DOI: 10.13208/j.electrochem.170401

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

参考文献

[1] Aresta M, Dibenedetto A, Angelini A. The changing para-digm in CO₂ utilization[J]. Journal of CO₂ Utilization, 2013, s(3/4): 65-73.

[2] Li L, Zhao N, Wei W, et al. A review of research progress on CO₂, capture, storage, and utilization in Chinese academy of sciences[J]. Fuel, 2013, 108(11): 112-130.

[3] Zhano C C(赵晨辰), Guo J W(郭建伟)，Wang L(王莉), et al. Electrochemical reduction of CO₂ on Sn/Cu Electrode[J]. Journal of Electrochemistry(电化学), 2012, 18(2): 169-173.

[4] Yang H P, Yue Y N, Sun Q L, et al. Entrapment of a chiral cobalt complex within silver: a novel heterogeneous catalyst for asymmetric carboxylation of benzyl bromides with CO₂[J]. Chemical Communications, 2015, 51(61): 12216-12219.

[5] Wu L X, Wang H, Xiao Y, et al. Synthesis of dialkyl carbonates from CO₂ and alcohols via electrogenerated N-heterocyclic carbenes[J]. Electrochemistry Communications, 2012, 25(1): 116-118.

[6] Kornienko N, Zhao Y, Kley C S, et al. Metal-organic frameworks for electrocatalytic reduction of carbon dioxide[J]. Journal of the American Chemical Society, 2016, 137(44): 14129.

[7] Zhang S, Kang P, Ubnoske S, et al. Polyethylenimine-enhanced electrocatalytic reduction of CO₂ to formate at nitrogen-doped carbon nanomaterials[J]. Journal of the American Chemical Society, 2014, 136(22): 7845-7848.

[8] Kang X C, Zhu Q G, Sun X F, et al. Highly efficient electrochemical reduction of CO₂ to CH4 in an ionic liquid using a metal-organic framework cathode[J]. Chemical Science, 2015, 7(1): 266-273.

[9] Weng Z, Jiang J B, Wu Y S, et al. Electrochemical CO₂ reduction to hydrocarbons on a heterogeneous molecular Cu catalyst in aqueous solution[J]. Journal of the American Chemical Society, 2016, 138(26): 8076-8079.

[10] Costentin C, Drouet S, Robert M, et al. A local proton source enhances CO₂ electroreduction to CO by a molecular Fe catalyst[J]. Science, 2012, 338(6103): 90-94.

[11] Hawecker J, Lehn J M, Ziessel R. Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO)₃Cl (bipy = 2,2′-bipyridine)[J]. Journal of the Chemical Society-Chemical Communications, 1984, 6(6): 328-330.

[12] Johnson B A, Maji S, Agarwala H, et al. Activating a low overpotential CO₂ reduction mechanism by a strategic ligand modification on a ruthenium polypyridyl catalyst[J]. Angewandte Chemie International Edition, 2016, 55(5): 1857-1861.

[13] Machan C W, Sampson M D, Kubiak C P. A molecular ruthenium electrocatalyst for the reduction of carbon dioxide to CO and formate[J]. Journal of the American Chemical Society, 2015, 137(26): 8564-8571.

[14] Hammouche M, Lexa D, Momenteau M, et al. Chemical catalysis of electrochemical reactions. homogeneous catalysis of the electrochemical reduction of carbon dioxide by iron("0") porphyrins. role of the addition of magnesium cations[J]. Journal of the American Chemical Society, 1991, 113(22): 8455-8466.

[15] Khoshro H, Zare H R, Gorji A, et al. A study of the catalytic activity of symmetric and unsymmetric macrocyclic [N₄^2-] coordinated nickel complexes for electrochemical reduction of carbon dioxide[J]. Electrochimica Acta, 2014, 117(4): 62-67.

[16] Wang X Z, Tan C, Li Y Q, et al. Synthesis of ionic phosphines and corresponding ionic transition metal complexes and their applications in homogeneous catalysis[J]. Progress in Chemistry, 2015, 27(1): 27-37.

[17] Tolmachev A A, Yurchenko A A, Merculov A S, et al. Phosphorylation of 1-alkylmidazoles and 1-alkylbenzimidazoles with phosphorus(III) halides in the presence of bases[J]. Heteroatom Chemistry, 2015, 10(7): 585-597.

[18] Marchenko A P, Koidan H N, Huryeva A N, et al. N-phosphorylated imidazolium salts as precursors to 2- and 5-phosphorylated imidazoles and new imidazol-2-ylidenes featuring the PNCN unit[J]. Journal of Organic Chemistry, 2010, 75(21): 7141-7145.

[19] Schneider J, Jia H, Kobiro K, et al. Nickel(II) macrocycles: highly efficient electrocatalysts for the selective reduction of CO₂ to CO[J]. Energy & Environmental Science, 2012, 5(11): 9502-9510.

[20] Dunache E, Medeiros M J, Olivero S, et al. Nickel-catalysed electrochemical carboxylation of allylic acetates and carbonates[J]. Electrochimica Acta, 2011, 56(11): 4384-4389.

[21] Sampson M D, An D N, Grice K A, et al. Manganese catalysts with bulky bipyridine ligands for the electrocatalytic reduction of carbon dioxide: Eliminating dimerization and altering catalysis[J]. Journal of the American Chemical Society, 2014, 136(14): 5460-5471.

[22] Tong Y X(童叶翔), Yang Q Q(杨绮琴), Liu P(刘鹏). Electrochemistry of coordination compounds[M]. Guangzhou:Guangdong Science & Technology Press(广东科技出版社), 2006.

[23] Agarwal J, Shaw T W, Stanton III C J, et al. NHC-containing manganese(I) electrocatalysts for the two-electron reduction of CO₂[J]. Angewandte Chemie International Edition, 2014, 53(20): 5152-5155.

[24] Chen B L, Zhu H W, Xiao Y, et al. Asymmetric electrocarboxylation of 1-phenylethyl chloride catalyzed by electrogenerated chiral [CoI(salen)]- complex[J]. Electrochemistry Communications, 2014, 42(5): 55-59.

[25] Chabolla S A, Yin J, et al. Supramolecular assembly promotes the electrocatalytic reduction of carbon dioxide by Re(I) bipyridine catalysts at a lower overpotential[J]. Journal of the American Chemical Society, 2014, 136(41): 14598-14607.

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