[NH2-emim]Br/[Bmim]BF4离子液体中二氧化碳的电化学还原

doi:10.11949/j.issn.0438-1157.20161814

摘要/Abstract

摘要：

以2-溴乙胺氢溴酸和N-甲基咪唑盐为原料合成了氨基功能化离子液体1-（2-胺乙基）-3-甲基咪唑溴盐（[NH₂-emim]Br），用¹H NMR和IR对所制备的离子液体进行了表征，测得25℃下[NH₂-emim]Br的黏度26.691 Pa·s、电导率0.1130 mS·cm^-1，CO₂的溶解饱和度82%（摩尔分数），将不同含量的[NH₂-emim]Br与[Emim]BF₄、[Bmim]BF₄、[Bmim]PF₆组成二元复合离子液体，并用于CO₂电化学还原研究，循环伏安研究表明，CO₂在[NH₂-emim]Br（0.5%）-[Bmim]BF₄复合离子液体中的还原峰电位较[Bmim]BF₄正移0.4 V，还原峰电流增大9倍，黏度降低为0.08227 Pa·s，电导率增大至1.317 mS·cm^-1，是一种较好的CO₂电化学还原离子液体体系。

关键词: 二氧化碳, 离子液体, 二元混合物, 电化学, 循环伏安

Abstract:

Amine-functionalized ionic liquid, 1-(2-aminoethyl)-3-methyl imidazolium bromide ([NH₂-emim]Br), was synthesized from 2-bromoethylamine hydrobromide and N-methyl imidazole salt at reflux condition and characterized by ¹H NMR and IR. Viscosity, electric conductivity and saturated carbon dioxide solubility in [NH₂-emim]Br ionic liquid measured at 25℃ were 26.691 Pa·s, 0.1130 mS·cm^-1 and 82% by molar ratio, respectively. Binary ionic liquid composites of [NH₂-emim]Br/[Emim]BF₄, [NH₂-emim]Br/[Bmim]BF₄, and [NH₂-emim]Br/[Bmim]PF₆were prepared at different mass ratios and used for electrochemical reduction of CO₂. The results of cyclic voltammetry at room temperature showed that peak current of CO₂ reduction in [NH₂-emim]Br (0.5%)-[Bmim]BF₄was increased about 9 times than that in [Bmim]BF₄ and reduction peak potential was shifted positively by 0.4 V. With viscosity decrease to 0.08227 Pa·s and electrical conductivity increase to 1.317 mS·cm^-1, the binary ionic liquid composite is a good ionic liquid system for CO₂electrochemical reduction.

Key words: carbon dioxide, ionic liquids, binary mixture, electrochemistry, cyclic voltammetry

中图分类号:

毛信表, 刘莹, 陈达, 陈赵扬, 马淳安. [NH₂-emim]Br/[Bmim]BF₄离子液体中二氧化碳的电化学还原[J]. 化工学报, 2017, 68(5): 2027-2034.

MAO Xinbiao, LIU Ying, CHEN Da, CHEN Zhaoyang, MA Chun'an. Electrochemical reduction of CO₂in [NH₂-emim]Br/[Bmim]BF₄ ionic liquid composite[J]. CIESC Journal, 2017, 68(5): 2027-2034.

参考文献 35

[1]	刘昌俊, 郭秋婷, 叶静云, 等. 二氧化碳转化催化剂研究进展及相关问题思考[J]. 化工学报, 2016, 67(1): 6-13. LIU C J, GUO Q T, YE J Y, et al. Perspective on catalyst investigation for CO2 conversion and related issues[J]. CIESC Journal, 2016, 67(1): 6-13.
[2]	孙洪志, 王倩, 宋名秀, 等. 化学利用的研究进展[J]. 化工进展, 2013, 32(7): 1666-1672. SUN H Z, WANG Q, SONG M X, et al. Progress in the chemical utilization of carbon dioxide[J]. Chemical Industry Engineering Progress, 2013, 32(7): 1666-1672.
[3]	QIAO J, LIU Y, HONG F, et al. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels[J]. ChemInform, 2014, 43(2): 631-675.
[4]	张丽, 罗仪文, 陆嘉星, 等. CO2在铜电极上的电还原行为[J]. 高等学校化学学报, 2007, 28(9): 1660-1662. ZHANG L, LUO Y W, LU J X, et al. Electrochemical behavior of CO2 on copper electrode[J]. Chemical Journal of Chinese Universities, 2007, 28(9): 1660-1662.
[5]	刘丽英, 陈洪章. 离子液体在生物催化中的应用[J]. 化工学报, 2005, 56(3): 382-386. LIU L Y, CHEN H Z. Apllications of ionic liquids in biocatalysis[J]. Journal of Chemical Industry and Engineering (China), 2005, 56(3): 382-386.
[6]	COLIN F, SORCHA S, LESLEY J. Molecular approaches to the electrochemical reduction of carbon dioxide[J]. Chemical Communications, 2012, 48(22): 1392-1399.
[7]	ZHANG F, FANG C G, WU Y T, et al. Absorption of CO2 in the aqueous solutions of functionalized ionic liquids and MDEA[J]. Chemical Engineering Journal, 2010, 160(2): 691-697.
[8]	王倩倩, 陈承镇, 张志盼, 等. 电解液组成对电化学还原效率的影响[J]. 化学反应工程与工艺, 2016, 32(4): 359-365. WANG Q Q, CHEN C Z, ZHANG Z P, et al. Effects of electrolyte solution composition on efficiency of CO2 electrochemical reduction[J]. Chemical Reaction Engineering and Technology, 2016, 32(4): 359-365.
[9]	张现萍, 黄海燕, 靳红利, 等. 水溶液中电化学还原的研究进展[J]. 化工进展, 2015, 34(12): 4139-4144. ZHANG X P, HUANG H Y, JIN H L, et al. Progress of the electrochemical reduction of CO2 in aqueous electrolyte[J]. Chemical Industry and Engineering Progress, 2015, 34(12): 4139-4144.
[10]	顾彦龙, 石峰, 邓友全. 离子液体在催化反应和萃取分离中的研究和应用进展[J]. 化工学报, 2004, 55(12): 1957-1963. GU Y L, SHI F, DENG Y Q. Research and application of ionic liquids in catalysis and separation[J]. Journal of Chemical Industry and Engineering (China), 2004, 55(12): 1957-1963.
[11]	李翠娜, 贺高红, 李祥村. 功能化离子液体用于CO2吸收和分离的研究进展[J]. 化工进展, 2011, 30(4): 709-714. LI C N, HE G H, LI X C. Progress of functionalized ionic liquids for CO2 absorption and separation[J]. Chemical Industry and Engineering Progress, 2011, 30(4): 709-714.
[12]	CAI Y Q, PENGY Q, SONG G H, et al. Amino-functionalized ionic liquid as an efficient and recyclable catalyst for Knoevenagel reactions in water[J]. Catalysis Letters, 2006, 109: 1-2.
[13]	SAEIDI S, AMIN N A S, RAHIMPOUR M R. Hydrogenation of CO2 to value-added products—a review and potential future developments[J]. Journal of CO2 Utilization, 2014, 5: 66-81.
[14]	ANNE-LISE G, NATHALIA S, MARCILEIA Z, et al. Insights on recyclable catalytic system composed of task-specific ionic liquids for the chemical fixation of carbon dioxide[J]. Green Chemistry, 2014, 16(5): 797-898.
[15]	ZENG J, ZHANG Y, SUN R, et al. Electroreduction property and MD simulation of nitrobenzene in ionic liquid[BMim][Tf2N][BMim][BF4][J]. Electrochimica Acta, 2014, 134(21): 193-200.
[16]	CAI Q H, YUAN D D, YAN C H, et al. Electrochemical activation of carbon dioxide for synthesis of dimethyl carbonate in an ionic liquid[J]. Electrochimica Acta, 2009, 54(10): 2912-2915.
[17]	AESTA M, DIBENEDETTO A.The contribution of the utilization option to reducing the CO2 atmospheric loading: research needed to overcome existing barriers for a full exploitation of the potential of the CO2 use[J]. Catalysis Today, 2004, 98(4): 455-462.
[18]	QUAN T C, LU Z, JILIN W. Fabrication and characterization of phosphoric acid doped imidazolium ionic liquid polymer composite membranes[J]. Journal of Molecular Liquids, 2015, 206(1): 10-18.
[19]	SUN J, ZHANG S J, CHEN W G, et al. Hydroxyl-functionalized ionic liquid: a novel efficient catalyst forchemical fixation of CO2 to cyclic carbonate[J]. Tetrahedron Letters, 2008, 39(34): 3588- 3591.
[20]	张晓春, 张锁江, 左勇, 等. 离子液体的制备及应用[J]. 化工进展, 2010, 22 (7): 1500-1508. ZHANG X C, ZHANG S J, ZUO Y, et al. Preparation and applications of ionic liquids[J]. Chemical Industry and Engineering Progress, 2010, 22(7): 1500-1508.
[21]	HEIMER N E, DEL SESTO R E, MENG Z, et al. Vibrational spectra of imidazolium tetrafluoroborate ionic liquids[J]. Journal of Molecular Liquids, 2006, 124(1): 84-95.
[22]	WASSERSCHEID P, KEIM W. Ionic liquids-new“solutions” for transition metal catalysis[J]. Angewantle Chemic, 2000, 39(21): 3772-3789.
[23]	PARK J, JUNG Y, KUSUMAH P, et al. Application of ionic liquids in hydrometallurgy[J]. International Journal of Molecular Sciences, 2014, 15(9): 15320-15343.
[24]	张锁江, 姚晓倩, 刘晓敏, 等. 离子液体构效关系及应用[J]. 化学进展, 2009, 7(11): 2465-2473. ZHANG S J, YAO X Q, LIU X M, et al. Structure-property relationship and application of ionic liquid[J]. Progress in Chemistry, 2009, 7(11): 2465-2497.
[25]	ATHONY J L, ANDERSON J L, MAGINN E J.Anion effects on gas solubility in ionic liquids[J]. Journal of Physical Chemistry B, 2005, 109(13): 6266-6374.
[26]	LU B, WANG X, LI Y, et al. Electrochemical conversion of CO2 into dimethyl carbonate in a functionalized ionic liquid[J]. Journal of CO2 Utilization, 2013, 8(3/4): 98-101.
[27]	ZHANG S J, CHEN Y H, ZHANG J M, et al. Solubility of CO2 in sulfonate ionic liquids at high pressure[J]. Journal of Chemical Engineering Data, 2005, 50(1): 230-233.
[28]	毛信表, 何峰强, 张寅旭, 等. 二元离子液体OMImBF4/HMImPF6中硝基苯的电化学还原[J]. 化工学报, 2016, 67(5): 1998-2004. MAO X B, HE F Q, ZHANG Y X, et al. Electrochemical reduction of nitrobenzene in binary ionic liquid of OMImBF4/HMImPF6[J]. CIESC Journal, 2016, 67(5): 1998-2004.
[29]	陈卓, 谢辉, 胡长刚. 功能离子液体[NH2 p-bim]BF4 吸收CO2的密度泛函研究[J]. 化学研究与应用, 2007, 19(12): 1322-1323. CHEN Z, XIE H, HU C G. DFT investigation on the CO2 capture by the task-specific ionic liquid of [NH2 p-bim]BF4[J]. Chemical Research and Application, 2007, 19(12): 1322-1326.
[30]	GIRARD A L, SIMON N, ZANATTA M, et al. Insights on recyclable catalytic system composed of task-specific ionic liquids for the chemical fixation of carbon dioxide[J]. Green Chemistry, 2014, 16(5): 797-808.
[31]	吴永良, 焦真, 王冠楠, 等. 用于吸收的离子液体的合成、表征及吸收性能[J]. 精细化工, 2007, 24(4): 324-340. WU Y L, JIAO Z, WANG G N, et al. Synthesis, characterization and absorption efficiency of an ionic liquid for the absorption of CO2[J]. Fine Chemicals, 2007, 24(4): 324-340.
[32]	LU B, WANG X, LI Y, et al. Electrochemical conversion of CO2 into dimethyl carbonate in a functionalized ionic liquid[J]. International Journal of CO2 Utilization, 2013, 10(3/4): 98-101.
[33]	BATES E D, MAYTON R D, NTAI I, et al. CO2 capture by a task-specific ionic liquid[J]. Journal of the American Chemical Society, 2002, 124(6): 926-927.
[34]	刘海燕, 李睿, 姜国庆, 等. 含胺功能基团离子液体吸收CO2的研究[J]. 分子科学学报, 2011, 27(5): 319-322. LIU H Y, LI R, JIANG G Q, et al. The study of CO2 absorption by a amine task-specific ionic liquid[J]. ACS Catalysis, 2016, 6(4): 2398-2392.
[35]	FIGUEIREDO M C, LEDEZMAYANEZ I, KOPER M T M. In situ spectroscopic study of CO2 electroreduction at copper electrodes in acetonitrile[J]. ACS Catalysis, 2016, 6(4): 2382-2392.

[NH₂-emim]Br/[Bmim]BF₄离子液体中二氧化碳的电化学还原

Electrochemical reduction of CO₂in [NH₂-emim]Br/[Bmim]BF₄ ionic liquid composite

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