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一种用于高容量和选择性阴离子捕获的新范例:阳离子材料的晶态到晶态转变。

A new paradigm for anion trapping in high capacity and selectivity: crystal-to-crystal transformation of cationic materials.

机构信息

University of California, Santa Cruz, Department of Chemistry and Biochemistry, 1156 High Street, Santa Cruz, California 95064, USA.

出版信息

J Am Chem Soc. 2011 Jul 27;133(29):11110-3. doi: 10.1021/ja204577p. Epub 2011 Jun 30.

Abstract

We describe a new methodology to the selective trapping of priority pollutants that occur inherently as oxo-anions (e.g., perchlorate, chromate, arsenate, pertechnetate, etc.) or organic anions (e.g., salicylate, pharmaceuticals, and their metabolites, which are often chlorinated into potentially more harmful compounds). The typical approach to trapping anions is exchange into cationic hosts such as resins or layered double hydroxides. Both capacity and selectivity are limited by the equilibrium of the process and moreover are often subject to interference, e.g. by carbonate that is always present in water from atmospheric CO(2). Our approach takes advantage of the metastability of our cationically charged materials to instead trap by recrystallization to a new structure. Exceptionally high adsorption capacities for permanganate and perrhenate--studied as models for pertechnetate--were found for a Ag(I)-based cationic extended framework. The exchange capacity reached 292 and 602 mg/g, respectively, over five times the exchange capacity compared to conventional layered double hydroxides. Our cationic material can also selectively trap these and other toxic oxo-anions when nontoxic anions (e.g., nitrate, carbonate) were present in an over 100-fold excess concentration.

摘要

我们描述了一种新的方法,用于选择性捕获天然存在的氧阴离子(例如高氯酸盐、铬酸盐、砷酸盐、锝酸盐等)或有机阴离子(例如水杨酸盐、药物及其代谢物,它们通常会被氯化为潜在更有害的化合物)作为优先污染物。捕获阴离子的典型方法是将其交换到阳离子宿主中,例如树脂或层状双氢氧化物。容量和选择性都受到该过程平衡的限制,而且往往会受到干扰,例如总是存在于大气 CO2 水中的碳酸盐。我们的方法利用我们带正电荷的材料的亚稳性,通过重结晶到新结构来进行捕获。对于基于 Ag(I)的阳离子扩展骨架,我们发现了对高锰酸盐和高铼酸盐(作为锝酸盐的模型进行研究)的异常高吸附容量。交换容量分别达到 292 和 602 mg/g,是传统层状双氢氧化物的交换容量的五倍以上。当存在 100 倍以上过量浓度的无毒阴离子(例如硝酸盐、碳酸盐)时,我们的阳离子材料也可以选择性地捕获这些和其他有毒的氧阴离子。

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