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由半刚性三嗪六羧酸配体构建的钍有机框架:具有氧化钍轮簇的独特结构及碘吸附行为

Thorium-Organic Framework Constructed with a Semirigid Triazine Hexacarboxylic Acid Ligand: Unique Structure with Thorium Oxide Wheel Clusters and Iodine Adsorption Behavior.

作者信息

Zhang Na, Sun Li-Xian, Bai Feng-Ying, Xing Yong-Heng

机构信息

College of Chemistry and Chemical Engineering, Liaoning Normal University, Huanghe Road 850#, Dalian 116029, P. R. China.

Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, P. R. China.

出版信息

Inorg Chem. 2020 Mar 16;59(6):3964-3973. doi: 10.1021/acs.inorgchem.9b03639. Epub 2020 Mar 1.

Abstract

We successfully prepared and characterized a distinctive thorium-based MOF (metal-organic framework) Th-TTHA with thorium oxide wheel clusters under the conditions of solvothermal synthesis by utilizing thorium nitrate and semirigid triazine hexacarboxylic acid linker HTTHA (HTTHA = 1,3,5-triazine-2,4,6-triamine hexaacetic acid). To the best of our knowledge, Th-TTHA is the first thorium-based MOF assembled by semirigid triazine hexapod ligand HTTHA. It is worth mentioning that Th-TTHA exhibits a novel and distinctive arrangement of structure and topology. Th-TTHA has abundant adsorption sites such as the triazine ring that is rich in nitrogen atoms, N of NH-, and carboxyl oxygen atoms without coordination with a central metal, which drove us to explore its iodine adsorption capacity. The experimental results show that Th-TTHA shows excellent adsorption capacity for iodine, and the adsorption amount in a saturated iodine cyclohexane solution can reach 528 mg/g within 24 h. This work is greatly significant for the development of new structures of thorium-based MOFs and the expansion of its functional characteristics, which is very essential for our in-depth understanding of thorium chemistry and in the management and disposal of radionuclides and application of the nuclear fuel cycle.

摘要

我们通过利用硝酸钍和半刚性三嗪六羧酸连接体HTTHA(HTTHA = 1,3,5-三嗪-2,4,6-三胺六乙酸),在溶剂热合成条件下成功制备并表征了一种独特的基于钍的金属有机框架(MOF)Th-TTHA,其具有氧化钍轮簇。据我们所知,Th-TTHA是首个由半刚性三嗪六足配体HTTHA组装而成的基于钍的MOF。值得一提的是,Th-TTHA展现出新颖独特的结构和拓扑排列。Th-TTHA具有丰富的吸附位点,如富含氮原子的三嗪环、NH-的N以及未与中心金属配位的羧基氧原子,这促使我们探索其碘吸附能力。实验结果表明,Th-TTHA对碘表现出优异的吸附能力,在饱和碘环己烷溶液中的吸附量在24小时内可达到528 mg/g。这项工作对于基于钍的MOF新结构的开发及其功能特性的拓展具有重大意义,这对于我们深入理解钍化学以及放射性核素的管理与处置和核燃料循环的应用至关重要。

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