离子液体负载的TEMPO/离子液体聚合物/碳黑三元复合材料在醇的电化学氧化中的应用

doi:10.13208/j.electrochem.161051

电化学（中英文） ›› 2017, Vol. 23 ›› Issue (3): 322-326. doi: 10.13208/j.electrochem.161051

• 有机电化学及电化学工业近期研究专辑（华东理工大学张新胜教授、北京化工大学曾程初教授主编） • 上一篇下一篇

离子液体负载的TEMPO/离子液体聚合物/碳黑三元复合材料在醇的电化学氧化中的应用

林鑫¹，孙草草²，刘峙嵘¹，曾程初^2*

1. 化生材学院，东华理工大学，江西，330013; 2. 生命科学与生物工程学院，北京工业大学，北京，100124

收稿日期:2016-11-15 修回日期:2017-02-13 出版日期:2017-06-29 发布日期:2017-03-02
通讯作者: 曾程初 E-mail:zengcc@bjut.edu.cn
基金资助:
国家自然科学基金项目（21272021）资助

Ionic Liquid-Supported TEMPO/Polymeric Ionic-liquid/Carbon Black Ternary Composites: Preparations and Applications in Electrochemical Oxidation of Alcohols

LIN Xin¹, SUN Cao-cao²,LIU Zhi-rong¹, ZENG Cheng-chu^2*

1. School of Chemistry, biology & Materials Science, East China University of Technology, Nanchang 330013 2. Collage of Life Science & Bioengineering, Beijing University of Technology, Beijing 100124

Received:2016-11-15 Revised:2017-02-13 Published:2017-06-29 Online:2017-03-02
Contact: ZENG Cheng-chu E-mail:zengcc@bjut.edu.cn

摘要/Abstract

摘要：

以4-羟基-2,2,6,6-四甲基哌啶氧基自由基（4-OH-TEMPO）为原料合成了负载有TEMPO结构单元的咪唑四氟硼酸盐离子液体 (TEMPO-IL-BF₄)，以双三氟甲磺酰亚胺锂 (LiTFSI) 和聚二烯丙基二甲基氯化铵 (PDDA) 为原料合成了聚合物离子液体 PDDA(Tf₂N)，将上述两种物质和碳黑（CB）按照一定比例制备得到一种三元复合材料. 以此三元复合材料为支持电解质和电催化剂，研究了其在乙腈溶液中电化学氧化对甲氧基苯甲醇等各类醇的能力及其循环使用效果. 结果表明：在电化学条件下，此三元复合材料不仅可以有效地氧化对甲氧基苯甲醇等各类醇，生成的醛的产率都在80%以上，并且经过4次循环使用，该三元复合材料的回收率均在95%以上.

关键词: 离子液体负载的TEMPO电催化剂, 聚合物支持电解质, 可回收的三元复合材料

Abstract:

To effectively recover redox catalyst and supporting electrolyte, a novel ternary composite consisting of ionic liquid-supported TEMPO, polymeric ionic-liquid and carbon black was prepared. The ionic-liquid supported redox catalyst TEMPO-IL-BF₄was firstly synthesized from 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and followed by the reaction of polydimethyldiallylammonium chloride (PDDA) and bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) to form poly[diallyldimethylammonium bis(trifluoromethanesulfonyl)imide] (PDDA(Tf₂N)). A combination of the above mentioned two synthesized materials and carbon black afforded to obtain the ternary composite, which was used as the recoverable supporting electrolyte and mediator for the electrochemical oxidation of alcohol. The results indicate that various alcohols could be oxidized efficiently to the corresponding aldehydes or ketones with the more than 80% yields in the presence of the ternary composite under electrochemical conditions. In addition, the composite could be recovered with 95% recovery after being used for 4 times in experiments. The development of the ternary composite provides an efficient and sustainable approach for the recovery of supporting electrolyte and redox catalyst.

Key words: ionic liquid-supported TEMPO as redox catalyst, polymeric ionic liquid, recoverable ternary composite

中图分类号:

O646

Support info: 国家自然科学基金项目（No. 21272021）资助

林鑫，孙草草，刘峙嵘，曾程初. 离子液体负载的TEMPO/离子液体聚合物/碳黑三元复合材料在醇的电化学氧化中的应用[J]. 电化学（中英文）, 2017, 23(3): 322-326.

LIN Xin, SUN Cao-cao,LIU Zhi-rong, ZENG Cheng-chu. Ionic Liquid-Supported TEMPO/Polymeric Ionic-liquid/Carbon Black Ternary Composites: Preparations and Applications in Electrochemical Oxidation of Alcohols[J]. Journal of Electrochemistry, 2017, 23(3): 322-326.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.161051

https://electrochem.xmu.edu.cn/CN/Y2017/V23/I3/322

参考文献

[1] Ma C A (马淳安). Introduction of organic electrochemistry (有机电化学合成导论)[M]. Beijing: Science Publisher, 2002, 5-6.

[2] Huang P Q (黄培强). Green synthesis: an emerging frontier in organic synthesis[J]. Progress in Chemistry (化学进展), 1998, 10: 265-272.

[3] Yoo S J, Li L J, Zeng C C, et al. Polymeric ionic liquid and carbon black composite as a reusable supporting electrolyte: modification of the electrode surface[J]. Angewandte Chemie International Edition, 2015, 54(12): 3744-3747.

[4] Dijksman A, Marino-González A, Mairata i Payeras A., et al. Efficient and selective aerobic oxidation of alcohols into aldehydes and ketones using ruthenium/TEMPO as the catalytic system[J]. Journal of the American Chemical Society, 2001, 123(28): 6826–6833.

[5] Rohlmann R, Stopka T, Richter H, et al. Iron-catalyzed oxidative tandem reactions with TEMPO oxoammonium salts: synthesis of dihydroquinazolines and quinolones[J]. The Journal of Organic Chemistry, 2013, 78(12): 6050-6064.

[6] Qian W X, Jin E L, Bao W L, et al. Clean and selective oxidation of alcohols catalyzed by ion-supported TEMPO in water[J]. Tetrahedron, 2006, 62 (4): 556–562.

[7] Mitsui M, Takeda K, Kobori Y, et al. Unusually large dynamic electron polarization in an O2(1Δg)−2,2,6,6-Tetramethylpiperidine-1-oxyl radical system[J]. The Journal of Physical Chemistry, 2004, 108(7): 1120-1126.

[8] Mehnert C P, Cook R A, Dispenziere N C, et al. Supported ionic liquid catalysis - a new concept for homogeneous hydroformylation catalysis[J]. Journal of the American Chemical Society, 2002, 124(44): 12932-12933.

[9] Miao W S, Chan T H. Ionic-liquid-supported peptide synthesis demonstrated by the synthesis of leu(5)-enkephalin[J]. The Journal of Organic Chemistry, 2005, 70(8): 3251-3255.

[10] Grotli M, Gotfredsen C H, Rademann J, et al. Physical properties of poly(ethylene glycol) (PEG)-based resins for combinatorial solid phase organic chemistry: a comparison of PEG-cross-linked and PEG-grafted resins[J]. Journal of Combinatorial Chemistry, 2000, 2(2): 108-119.

[11] Sun Q (孙茜), Liu Y L (刘元兰), Lu J X (陆嘉星). Application of ionic liquids in electrochemistry[J]. Chemistry Bulletin (化学通报), 2003, 66(2): 112-114.

[12] Zhu Y G, Zhu Y, Zeng H Y, 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.

[13] Yuan Y, Shi X, Liu W. Transition metal-free chemoselective aerobic oxidations of sulfides and alcohols with potassium nitrate and pyridinium tribromide or bromine[J]. Synlett, 2011, 4: 559-564.

[14] Cacchi S, Fabrizi G., Goggiamani A. Palladium-catalyzed synthesis of aldehydes from aryl iodides and acetic formic anhydride[J]. Journal of Combinatorial Chemistry, 2004, 6(5): 692–694.

[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]	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.
[14]	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.
[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.

离子液体负载的TEMPO/离子液体聚合物/碳黑三元复合材料在醇的电化学氧化中的应用

Ionic Liquid-Supported TEMPO/Polymeric Ionic-liquid/Carbon Black Ternary Composites: Preparations and Applications in Electrochemical Oxidation of Alcohols

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