催化学报

催化学报 ›› 2018, Vol. 39 ›› Issue (1): 63-70.DOI: 10.1016/S1872-2067(17)62916-4

• 论文 • 上一篇    下一篇

基于氨基酸的Cu(II)-色氨酸MOF催化剂上环氧化物与CO2环加成反应

Gyeong Seon Jeonga, Amal Cherian Kathalikkattila,b, Robin Babua, Yongchul Greg Chunga, Dae Won Parka   

  1. a 釜山大学化学与生物分子工程部, 釜山609-735, 韩国;
    b 都柏林大学三一学院化学系, 都柏林, 爱尔兰
  • 收稿日期:2017-08-17 修回日期:2017-09-15 出版日期:2018-01-18 发布日期:2018-01-19
  • 通讯作者: Dae Won Park
  • 基金资助:

    韩国国家基金研究会.

Cycloaddition of CO2 with epoxides by using an amino-acid-based Cu(II)-tryptophan MOF catalyst

Gyeong Seon Jeonga, Amal Cherian Kathalikkattila,b, Robin Babua, Yongchul Greg Chunga, Dae Won Parka   

  1. a Division of Chemical and Biomolecular Engineering, Pusan National University, Busan 609-735, Korea;
    b School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland
  • Received:2017-08-17 Revised:2017-09-15 Online:2018-01-18 Published:2018-01-19
  • Contact: 10.1016/S1872-2067(17)62916-4
  • Supported by:

    This work was supported by National Research Foundation of Korea (NRF 2016R1D1A1B-03931325).

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摘要：

由天然的/生物单元（氨基酸）构成的金属有机框架材料（MOFs）具有自然属性和丰富的酸/碱位和官能团，因而可用于CO2化学中.本文报道了氨基酸系含铜MOF （CuTrp，Trp=L-色氨酸）的催化效率.以甲醇为溶剂，在室温采用直接混合法合成了CuTrp催化剂，该方法具有很高的能量效率.采用X射线衍射、红外光谱、热重分析、电感耦合等离子体发射光谱法、扫描电镜和BET分析等手段对该催化剂进行了表征.采用环氧化物与CO2环加成制备环状碳酸酯反应评价了CuTrp催化剂活性.结果表明，在无溶剂条件下，CuTrp催化剂可与四丁基溴化铵助催化剂发生协同作用.通过条件实验确定了优化的反应条件，并基于该实验结果和前期的密度泛函理论计算结果提出了反应机理.另外，CuTrp催化剂在水中也表现出令人满意的稳定性，可重复使用三次以上而活性无明显下降.

关键词: 金属有机框架材料, 氨基酸, 铜-色氨酸, 直接混合, 二氧化碳, 环状碳酸酯

Abstract:

Metal organic frameworks (MOFs) constructed from natural/biological units (amino acids) are prospective candidates as catalysts in CO2 chemistry owing to their natural origin and high abundance of Lewis acid/base sites and functional groups. Herein, we report the catalytic efficiency of an amino-acid-based Cu-containing MOF, denoted as CuTrp (Trp=L-tryptophan). The CuTrp catalyst was synthesized by direct mixing at room temperature using methanol as a solvent-a synthetic route with notable energy efficiency. The catalyst was characterized using various physicochemical techniques, including XRD, FT-IR, TGA, XPS, ICP-OES, FE-SEM, and BET analysis. The catalytic activity of CuTrp was assessed in the synthesis of cyclic carbonates from epoxides and CO2. The CuTrp operated in synergy with the co-catalyst tetrabutylammonium bromide under solvent-free conditions. Several reaction parameters were studied to identify the optimal reaction conditions and a reaction mechanism was proposed based on experimental evidence and previous density functional theory studies. The CuTrp also exhibited satisfactory stability in water and could be reused more than three times without any significant loss of activity.

Key words: Metal organic frameworks, Amino acid, Copper tryptophan complex, Direct mixing, Carbon dioxide, Cyclic carbonate