负载型离子液体在C-H键电氧化活化中的应用研究

doi:10.13208/j.electrochem.160315

电化学（中英文） ›› 2017, Vol. 23 ›› Issue (1): 1-6. doi: 10.13208/j.electrochem.160315

负载型离子液体在C-H键电氧化活化中的应用研究

陈姿颖，武倩倩，张健青，朱英红*，马淳安*

浙江工业大学化学工程学院，绿色化学合成技术国家重点实验室培育基地，浙江杭州 310032

收稿日期:2016-03-12 修回日期:2016-04-12 出版日期:2017-02-28 发布日期:2016-05-18
通讯作者: 朱英红，马淳安 E-mail:science@zjut. edu. cn
基金资助:
973前期研究专项（No. 2012CB722604）资助

Application of Composite Ionic Liquid in Electro-oxidation Activation of a C-H Bond

CHEN Zi-ying, WU Qian-qian, ZHANG Jian-qing, ZHU Ying-hong*, MA Chun-an*

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Received:2016-03-12 Revised:2016-04-12 Published:2017-02-28 Online:2016-05-18
Contact: ZHU Ying-hong, MA Chun-an E-mail:science@zjut. edu. cn

摘要/Abstract

摘要：

本文将1-乙基-3-甲基咪唑醋酸盐离子液体修饰在多壁碳纳米管上，制备出离子液体/碳纳米管复合材料，并研究了对甲氧基甲苯（p-MT）在该复合离子液体水溶液体系中的电氧化性能. 同时，通过循环伏安法和计时电流法考查了扫描速率、温度、反应底物浓度等因素对电氧化性能的影响，研究了p-MT在该体系中的动力学过程. 实验结果表明，p-MT在复合离子液体水溶液体系中发生不可逆的电氧化反应，且该过程受扩散控制，扩散系数为7.69×10^-10 cm²·s^-1. 适当地升高温度和增大反应底物浓度都有利于促进p-MT中C-H键选择性电氧化为相应醛基，选择性可达到95%. 通过在不同结构电解槽中进行恒电位电解研究，发现离子液体/MWCNTs复合电解质在一室型电解槽中进行p-MT电氧化的电解效率更高、对目标产物对甲氧基苯甲醛（p-MBA）的选择性也更好.

关键词: C-H键氧化, 离子液体/碳纳米管复合材料, 电氧化活化, 对甲氧基苯甲醛

Abstract:

In this paper, the ionic liquid/carbon nanotube composite material was prepared through modifying the ionic liquid 1-ethyl-3-methylimidazolium acetate to multi-walled carbon nanotubes. The electro-oxidation properties of p-methoxy toluene (p-MT) were studied using the composite as an electrolyte. The effects of scanning speed, temperature and substrate concentration were studied by cyclic voltammetry and chronoamperometry. The electrochemical kinetics of p-MT in this system was also studied. The results showed that the electrochemical oxidation of p-MT in the composite electrolyte solution was irreversible. The process was mainly controlled by diffusion, and the diffusion coefficient (D) was 7.69×10-10 cm2.s-1. Increasing the reaction temperature and the concentration of substrate could promote the electro-oxidation of the C-H bond to the corresponding aldehyde, and the selectivity of p-methoxybenzaldehyde (p-MBA) could improve to 95%. The electrolysis in one-pot was more efficiency and achieved better selectivity than that in the H-type.

Key words: the C-H bond oxidation, ionic liquid / nano composite material, Electro-oxidation activation, p-methoxybenzaldehyde

中图分类号:

O646

陈姿颖，武倩倩，张健青，朱英红，马淳安. 负载型离子液体在C-H键电氧化活化中的应用研究[J]. 电化学（中英文）, 2017, 23(1): 1-6.

CHEN Zi-ying, WU Qian-qian, ZHANG Jian-qing, ZHU Ying-hong, MA Chun-an. Application of Composite Ionic Liquid in Electro-oxidation Activation of a C-H Bond[J]. Journal of Electrochemistry, 2017, 23(1): 1-6.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.160315

https://electrochem.xmu.edu.cn/CN/Y2017/V23/I1/1

参考文献

[1] Welton T. Room-temperature ionic liquids Solvents for synthesis and catalysis[J]. Chemical reviews, 1999, 99(8): 2071-2084.

[2] Martins M A P, Guarda E A, Frizzo C P, et al. Synthesis of 1, 1, 1-trichloro [fluoro]-3-alken-2-ones using ionic liquids[J]. Journal of Molecular Catalysis A: Chemical, 2007, 266(1): 100-103.

[3] Belkhouche N E, Didi M A, Romero R, et al. Study of new organophosphorus derivates carriers on the selective recovery of M (II) and M (III) metals, using supported liquid membrane extraction[J]. Journal of Membrane Science, 2006, 284(1): 398-405.

[4] Sun Q (孙茜), Liu Y L (刘元兰), Lu J X (陆嘉星). Application of ionic liquids in electrochemistry[J]. Chemistry (化学通报), 2003, 2: 112-114.

[5] Peng C H (彭长宏), Chen X S (程晓苏), Cao J Y （曹金艳）, et al. Removal performance of arsenic by carbon nanotube adsorbents loaded with ionic liquid[J]. Journal of Central South University (Science and Technology) （中南大学学报:自然科学版）, 2010, 41(2): 416-421.

[6] Lu W, Qu L, Henry K, et al. High performance electrochemical capacitors from aligned carbon nanotube electrodes and ionic liquid electrolytes[J]. Journal of Power Sources, 2009, 189(2): 1270-1277.

[7] Bu C, Liu X, Zhang Y, et al. A sensor based on the carbon nanotubes-ionic liquid composite for simultaneous determination of hydroquinone and catechol[J]. Colloids and Surfaces B: Biointerfaces, 2011, 88(1): 292-296.

[8] Yu B, Liu Z, Ma C, et al. Ionic liquid modified multi-walled carbon nanotubes as lubricant additive[J]. Tribology International, 2015, 81: 38-42.

[9] Fukushima T, Kosaka A, Ishimura Y, et al. Molecular ordering of organic molten salts triggered by single-walled carbon nanotubes[J]. Science, 2003, 300(5628): 2072-2074.

[10] Pan W X (潘文筱), Zhang D J (张冬菊), Sun H (孙慧), et al. Theoretical study of the interaction mechanism between single-walled carbon nanotubes and imidazolium-based ionic liquids[J]. Scientia Sinica Chimica (中国科学: 化学), 2011, 41(01): 51-56.

[11] Shi R L (石瑞丽), Tao H (陶菡), Zhang Y M (张义明), et al. Progress on new-type biosensors based on ionic liquid and nanometer materials collaborative electrocatalysis[J]. New Chemical Materials (化工新型材料), 2010, 38(9): 19-22.

[12] Hu L, Hecht D S, Gruner G. Carbon nanotube thin films: fabrication, properties, and applications[J]. Chemical reviews, 2010, 110(10): 5790-5844.

[13] Yu P, Yan J, Zhao H, et al. Rational functionalization of carbon nanotube/ionic liquid bucky gel with dual tailor-made electrocatalysts for four-electron reduction of oxygen[J]. Journal of Physical Chemistry C, 2008, 112(6): 2177-2182.

[14] Kus N, Sharma A, Reva I, et al. Thermal and photoinduced control of relative populations of 4-methoxybenzaldehyde (p-anisaldehyde) conformers[J]. The Journal of Physical Chemistry A, 2010, 114(29): 7716-7724.

[15] Saha R, Ghosh A, Saha B. Kinetics of micellar catalysis on oxidation of p-anisaldehyde to p-anisic acid in aqueous medium at room temperature[J]. Chemical Engineering Science, 2013, 99: 23-27.

[16] Chen Q (陈琼), Zhu Y H (朱英红), Zhu Y (朱颖), et al. Effect of imidazole ionic liquids on the electro-oxidation of p-methoxy toluene[J]. Journal of Electrochemistry (电化学), 2014, 20(5): 465-469.

[17] Zhu Y, Zhu Y, Zeng H., et al. A promising electro-oxidation of methyl-substituted aromatic compounds to aldehydes in aqueous imidazole ionic liquid solutions[J]. Journal of Electroanalytical Chemistry, 2015, 751: 105-110.

[18] Nicholson R S, Shain I. Theory of stationary electrode polarography. Single scan and cyclic methods applied to reversible, irreversible, and kinetic systems[J]. Analytical Chemistry, 1964, 36(4): 706-723.

[19] Liu T B (刘天宝), Peng Y F (彭艳芬), Yan Y X (严永新), et al. Quantitative relationship between molecular structure and aqueous solubility of substituted benzaldehydes[J]. Journal of Wuhan University.(Natural Science Editon) (武汉大学学报: 理学版), 2012, 58(1): 40-44.

[20] Holbrey J D, Reichert W M, Nieuwenhuyzen M, et al. Liquid clathrate formation in ionic liquid–aromatic mixtures[J]. Chemical Communications, 2003 (4): 476-477.

负载型离子液体在C-H键电氧化活化中的应用研究

Application of Composite Ionic Liquid in Electro-oxidation Activation of a C-H Bond

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

[1]	沈茎, 王子明, 郑大江, 宋光铃. 钝化与过钝化状态下304不锈钢的点蚀行为研究[J]. 电化学（中英文）, 2020, 26(6): 808-814.
[2]	邢逸飞, 李娜, 温晓芳, 韩宏彦, 崔敏, 张聪, 任聚杰, 籍雪平. 基于取代型多酸复合材料的多巴胺电化学检测[J]. 电化学（中英文）, 2020, 26(6): 890-899.
[3]	杨纳川, 王玉, 帅毅, 陈康华. 低成本硫化物固态电解质Li_6-_xPS_5-_xCl_x的制备与性能研究[J]. 电化学（中英文）, 2020, 26(6): 885-889.
[4]	晋通正, 杨雨萌, 范圣慧, 卫国英, 张昭. 溶解氧及波长对光助阳极沉积CeO₂薄膜的影响[J]. 电化学（中英文）, 2020, 26(6): 868-875.
[5]	娄景媛, 尤东江, 李雪菁. 全钒氧化还原液流电池用石墨毡电极的分步氧化活化[J]. 电化学（中英文）, 2020, 26(6): 876-884.
[6]	吴凯. 锂硫电池正极材料的制备及工艺优化[J]. 电化学（中英文）, 2020, 26(6): 825-833.
[7]	俞成荣, 朱建国, 蒋聪盈, 谷宇晨, 周晔欣, 李卓斌, 邬荣敏, 仲政, 官万兵. 基于电-化-热耦合理论对称双阴极固体氧化物燃料电池堆的电流与温度场数值模拟[J]. 电化学（中英文）, 2020, 26(6): 789-796.
[8]	朱畅, 陈为, 宋艳芳, 董笑, 李桂花, 魏伟, 孙予罕. 反应条件对铜催化CO₂电还原的影响[J]. 电化学（中英文）, 2020, 26(6): 797-807.
[9]	王学良, 丛媛媛, 邱晨曦, 王盛杰, 秦嘉琪, 宋玉江. 核壳结构Ru@PtRu纳米花电催化剂的制备及碱性氢析出反应性能研究[J]. 电化学（中英文）, 2020, 26(6): 815-824.
[10]	陈品松, 胡一涛, 张信义, 沈培康. 立体构造石墨烯材料对铅酸蓄电池负极性能影响的研究[J]. 电化学（中英文）, 2020, 26(6): 834-843.
[11]	张泽阳, 孙岚, 林昌健. RGO-TiO₂纳米管阵列的制备及其光电性能[J]. 电化学（中英文）, 2020, 26(6): 844-849.
[12]	马武威, 常启刚, 史雄芳, 童延斌, 周立, 叶邦策, 鲁建江, 赵金虎. 基于纳米孔金与离子印迹聚合物结合的新型电化学传感器用于测定砷离子(III)[J]. 电化学（中英文）, 2020, 26(6): 900-910.
[13]	王存, 张维江, 何腾飞, 雷博, 史尤杰, 郑耀东, 罗伟林, 蒋方明. NCA三元锂离子电池分荷电状态循环的热特性和容量衰退研究[J]. 电化学（中英文）, 2020, 26(6): 777-788.
[14]	段明涛, 蒙延双, 张红帅. Ni₃S₂@碳纳米管复合材料的制备及其储钠性能[J]. 电化学（中英文）, 2020, 26(6): 850-858.
[15]	王怡捷, 钮东方, 张新胜. 离子液体中18-冠醚-6添加剂对三价铬电沉积的影响[J]. 电化学（中英文）, 2020, 26(6): 859-867.