Reversible Anion Exchange and Catalytic Properties of Two Cationic Metal-Organic Frameworks Based on Cu(I) and Ag(I)
Reversible Anion Exchange and Catalytic Properties of Two Cationic Metal-Organic Frameworks Based on Cu(I) and Ag(I)
复制标题
DOI：
10.1021/ja102134c
复制
发表时间：
2010-05-26
影响因子：
15
通讯作者：
Oliver, Scott R. J.
中科院分区：
文献类型：
--
作者：
Fei, Honghan;Rogow, David L.;Oliver, Scott R. J.
本文报道了两种Ag（I）/Cu（I）阳离子金属有机骨架的合成、表征及其在多相催化和阴离子交换中的应用。基于Cu（I）的材料根据我们先前报道的Ag（I）阳离子拓扑结构设计。这两种结构都由具有交替金属和4，4 '-联吡啶的pi-pi堆叠链的阳离子层组成。α，ω-烷烃二磺酸盐用作阴离子模板，静电结合到阳离子层上。由于磺酸盐模板和阳离子扩展框架之间的弱相互作用，这两种材料都显示出对各种无机物种的可逆阴离子交换。事实上，基于Ag（I）的材料表现出高锰酸盐和高锰酸盐阴离子捕获的高效吸收，这是高锝酸盐捕获的模型。该材料还显示出不均匀的刘易斯酸性，可能是由于配位不饱和金属位点仅与两个bipy氮结合以及与一个磺酸盐氧的弱相互作用。讨论了交换和催化的结构与尺寸选择性和可重复使用性的影响的比较研究。
We report the synthesis and characterization of two Ag(I)/Cu(I)-based cationic metal-organic frameworks and their application in both heterogeneous catalysis and anion exchange. The Cu(I)-based material was designed from our previously reported Ag(I) cationic topology. Both structures consist of cationic layers with pi-pi stacked chains of alternating metal and 4,4'-bipyridine. alpha,omega-Alkanedisulfonate serves as an anionic template, electrostatically bonding to the cationic layers. Due to weak interaction between the sulfonate template and cationic extended framework, both materials display reversible anion exchange for a variety of inorganic species. Indeed, the Ag(I)-based material exhibits highly efficient uptake of permanganate and perrhenate anion trapping, a model for pertechnetate trapping. The materials also display heterogeneous Lewis acidity, likely due to the coordinatively unsaturated metal sites which only bind to two bipy nitrogens and a weak interaction with one sulfonate oxygen. A comparative study on the influence of structure versus size selectivity and reusability for both exchange and catalysis is discussed.