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结合软模板法和合成后方法合理设计具有介孔的偕胺肟化金属有机框架用于高效铀萃取

Combining Soft-Templating and Post-Synthetic Methods for the Rational Design of an Amidoximated Metal-Organic Framework with Mesopores for Efficient Uranium Extraction.

作者信息

Li Jin, Wang Na, Lei Xue, Chen Kexin, Wang Yougan, Li Zhijian, Chen Zhao, Deng Chunhui

机构信息

Jiangxi Provincial Key Laboratory of Organic Functional Molecules, Institute of Organic Chemistry, Jiangxi Science and Technology Normal University, Nanchang 330013, China.

Center for Medical Research and Innovation, Shanghai Pudong Hospital, Fudan University Pudong Medical Center, Department of Chemistry, Institutes of Biomedical Sciences, Fudan University,Shanghai200433, China.

出版信息

ACS Appl Mater Interfaces. 2025 Sep 3;17(35):49953-49964. doi: 10.1021/acsami.5c06581. Epub 2025 Aug 19.

Abstract

Recently, metal-organic frameworks (MOFs) have been widely studied for uranium extraction from seawater to resolve the shortage of uranium resources. However, traditional MOF-based adsorbents are microporous structures, which are unfavorable to the mass transfer of guest molecules and the modification of functional groups. Herein, a novel mesoporous MOF (meso-UiO-66-NH-CN) is designed by the synergy of perchlorate and Pluronic F127, which gives meso-UiO-66-NH-CN with more accessible active sites and high mass transfer rates. Subsequently, mesoporous amidoximated MOFs (meso-UiO-66-NH-AO) were constructed via a one-step postsynthetic amidoximation, improving the stability and uranium selectivity of the material. The effect of acetic acid on the synthetic process is further investigated to regulate the inherent characteristics of meso-UiO-66-NH-AO. The mesopore structure endows meso-UiO-66-NH-AO with a rapid adsorption rate ( = 1.32 × 10 g mg min), and the modification of the amidoxime group gives the material high adsorption capacity ( = 312.5 mg g) and brilliant selectivity ( = 213 × 10 mL g). Meanwhile, meso-UiO-66-NH-AO exhibits a clear uranium adsorption performance in natural seawater. This work aims to provide a theoretical guideline for designing hierarchically porous MOFs and reveals their promising prospects for effective uranium extraction in seawater.

摘要

近年来,金属有机框架材料(MOFs)因可从海水中提取铀以解决铀资源短缺问题而受到广泛研究。然而,传统的基于MOF的吸附剂为微孔结构,不利于客体分子的传质以及官能团的修饰。在此,通过高氯酸盐与普朗尼克F127协同作用设计出一种新型介孔MOF(介孔-UiO-66-NH-CN),这赋予介孔-UiO-66-NH-CN更多可及活性位点和高传质速率。随后,通过一步后合成偕胺肟化构建了介孔偕胺肟化MOFs(介孔-UiO-66-NH-AO),提高了材料的稳定性和铀选择性。进一步研究了乙酸对合成过程的影响,以调控介孔-UiO-66-NH-AO的固有特性。介孔结构赋予介孔-UiO-66-NH-AO快速的吸附速率(= 1.32 × 10 g mg min),偕胺肟基团的修饰赋予该材料高吸附容量(= 312.5 mg g)和出色的选择性(= 213 × 10 mL g)。同时,介孔-UiO-66-NH-AO在天然海水中展现出明显的铀吸附性能。这项工作旨在为设计分级多孔MOFs提供理论指导,并揭示其在海水中有效提取铀的广阔前景。

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