物理化学学报 >> 2010, Vol. 26 >> Issue (04): 939-945.doi: 10.3866/PKU.WHXB20100406

催化和表面结构 上一篇    下一篇

金属有机骨架化合物催化合成不对称有机碳酸酯

周印羲, 梁曙光, 宋金良, 吴天斌, 胡素琴, 刘会贞, 姜涛, 韩布兴   

  1. 中国科学院化学研究所, 分子科学中心, 北京分子科学国家实验室, 北京 100190
  • 收稿日期:2009-11-18 修回日期:2009-12-24 发布日期:2010-04-02
  • 通讯作者: 姜涛, 韩布兴 E-mail:Jiangt@iccas.ac.cn; Hanbx@iccas.ac.cn

Synthesis of Asymmetrical Organic Carbonates Catalyzed by Metal Organic Frameworks

ZHOU Yin-Xi, LIANG Shu-Guang, SONG Jin-Liang, WU Tian-Bin, HU Su-Qin, LIU Hui-Zhen, JIANG Tao, HAN Bu-Xing   

  1. Beijing National Laboratory for Molecular Sciences, Centre for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China
  • Received:2009-11-18 Revised:2009-12-24 Published:2010-04-02
  • Contact: JIANG Tao, HAN Bu-Xing E-mail:Jiangt@iccas.ac.cn; Hanbx@iccas.ac.cn

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摘要：

金属有机骨架化合物(MOFs)是通过过渡金属和有机配体的自组装形成的一类新型材料, 具有高表面积、多孔性、孔尺寸可调等优点, 在催化、分离和气体储存等方面得到广泛应用. 用三种不同方法制备了金属有机骨架化合物, 并用扫描电镜(SEM)、X射线衍射(XRD)和红外(IR)光谱等方法进行了表征. 结果表明, 用不同方法制备的MOFs表现出不同的结构和形貌, 用直接混合法制备的MOFs是有效的催化碳酸二乙酯与醇酯交换制备有机碳酸酯的多相催化剂. 系统地考察了反应时间、反应温度、催化剂用量和底物摩尔比对反应的影响, 结果表明, 碳酸二乙酯与芳香醇、脂环醇、脂肪醇和杂环醇均能以100%选择性高产率地合成有机碳酸酯, 固体催化剂经简单离心分离可重复使用至少2次.

关键词: 金属有机骨架化合物, 配位聚合物, 酯交换, 碳酸二乙酯, 不对称碳酸酯

Abstract:

Metal organic frameworks (MOFs) are a new class of materials that are formed by the copolymerization of organic ligands with transition metals. Because of their properties such as high surface areas, microporosity, and the ability to tune pore size, many applications have recently been developed in catalysis, separation, and gas storage. We prepared MOFs by three different methods and characterized them with scanning electron microscopy (SEM), X-ray diffraction (XRD), and infrared (IR) spectroscopy. MOFs prepared via the three methods are completely different in morphology and microstructure. We demonstrate that the MOFs prepared via the “direct mixing”method are very effective heterogeneous catalyst for the transesterification of diethyl carbonate with alcohols to prepare organic carbonates. We studied the effects of the amount of MOFs, the reaction time, and the reaction temperature on product yield. Asymmetric organic carbonates can be produced with moderate to high yields and 100% selectivity via the reaction of diethyl carbonate with aromatic, cyclic, heterocyclic, or aliphatic alcohols. The solid catalyst can be recovered simply by centrifugation and reused for at least two cycles.

Key words: Metal organic framework, Coordination polymer, Transesterification, Diethyl carbonate, Asymmetrical organic carbonate