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可回收共价有机框架材料在水溶液中高效捕获和释放稀土元素钕

Efficient Capture and Release of the Rare-Earth Element Neodymium in Aqueous Solution by Recyclable Covalent Organic Frameworks.

作者信息

Chatterjee Puranjan, Volkov Alexander, Mi Jiashan, Niu Minghui, Sun Simin, Rossini Aaron J, Stanley Levi M, Huang Wenyu

机构信息

U.S. Department of Energy, Ames National Laboratory, Ames, Iowa 50011, United States.

Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States.

出版信息

J Am Chem Soc. 2024 Jul 24;146(29):20468-20476. doi: 10.1021/jacs.4c06609. Epub 2024 Jul 11.

Abstract

Rare-earth elements (REEs) are present in a broad range of critical materials. The development of solid adsorbents for REE capture could enable the cost-effective recycling of REE-containing magnets and electronics. In this context, covalent organic frameworks (COFs) are promising candidates for REE adsorption due to their exceptionally high surface area. Despite having attractive physical properties, COFs are heavily underutilized for REE capture applications due to their limited lifecycle in aqueous acidic environments, as well as synthetic challenges associated with the incorporation of ligands suitable for REE capture. Here, we show how the Ugi multicomponent reaction can be leveraged to postsynthetically modify imine-based COFs for the introduction of a diglycolic acid (DGA) moiety, an efficient scaffold for REE capture. The adsorption capacity of the DGA-functionalized COF was found to be more than 40 times higher than that of the pristine imine COF precursor and more than four times higher than that of the next-best reported DGA-functionalized solid support. This rationally designed COF has appealing characteristics of high adsorption capacity, fast and efficient capture and release of the REE ions, and reliable recyclability, making it one of the most promising adsorbents for solid-liquid REE ion extractions reported to date.

摘要

稀土元素(REEs)存在于广泛的关键材料中。开发用于捕获稀土元素的固体吸附剂能够实现含稀土元素磁体和电子产品的经济高效回收利用。在这种背景下,共价有机框架(COFs)因其超高的比表面积而成为稀土元素吸附的有潜力的候选材料。尽管COFs具有吸引人的物理性质,但由于它们在酸性水环境中的有限寿命以及与引入适用于捕获稀土元素的配体相关的合成挑战,COFs在稀土元素捕获应用中的利用率仍然很低。在此,我们展示了如何利用乌吉多组分反应对基于亚胺的COFs进行后合成修饰,以引入二乙醇酸(DGA)部分,这是一种用于捕获稀土元素的有效支架。结果发现,DGA功能化的COF的吸附容量比原始亚胺COF前体高出40多倍,比报道的第二好的DGA功能化固体载体高出四倍多。这种经过合理设计的COF具有高吸附容量、快速高效地捕获和释放稀土离子以及可靠的可回收性等吸引人的特性,使其成为迄今为止报道的用于固液稀土离子萃取的最有前途的吸附剂之一。

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