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Research Article

De novo synthesis of bifunctional conjugated microporous polymers for synergistic coordination mediated uranium entrapment

Boxuan Yu1,2,3,§, Lei Zhang1,4,§, Gang Ye1,5( ), Qingzhi Liu4,6, Jiongli Li2,3, Xudong Wang2,3, Jing Chen1,5, Shengming Xu1,5( ), Shengqian Ma4,†( )
Collaborative Innovation Center of Advanced Nuclear Energy Technology, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China
Beijing Institute of Graphene Technology, Beijing 100094, China
Beijing Institute of Aeronautical Materials, Beijing 100085, China
Department of Chemistry, University of South Florida, 4202 E. Fowler Avenue, Tampa, FL 33620, USA
Beijing Key Lab of Radioactive Waste Treatment, Tsinghua University, Beijing 100084, China
College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao 266109, China

§ Boxuan Yu and Lei Zhang contributed equally to this work.

† Present address: Department of Chemistry, University of North Texas, 1508 W. Mulberry St, Denton, TX 76201, USA

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Abstract

This work reports a de novo synthesis of novel bifunctional conjugated microporous polymers (CMPs) exhibiting a synergistic-effect involved coordination behavior to uranium. It is highlighted that the synthetic strategy enables the engineering of the coordination environment within amidoxime functionalized CMP frameworks by specifically introducing ortho-substituted amino functionalities, enhancing the affinity to uranyl ions via forming synergistic complexes. The CMPs exhibit high Brunauer-Emmett-Teller (BET) surface area, well-developed three-dimensional (3D) networks with hierarchical porosity, and favorable chemical and thermal stability because of the covalently cross-linked structure. Compared with the amino-free counterparts, the adsorption capacity of bifunctional CMPs was increased by almost 70%, from 105 to 174 mg/g, indicating evidently enhanced binding ability to uranium. Moreover, new insights into coordination mechanism were obtained by in-depth X-ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculation, suggesting a dominant role of the oxime ligands forming a 1:1 metal ions/ligands (M/L) coordination model with uranyl ions while demonstrating the synergistic engagement of the amino functionalities via direct binding to uranium center and hydrogen-bonding involved secondary-sphere interaction. This work sheds light on the underlying principles of ortho-substituted functionalities directed synergistic effect to promote the coordination of amidoxime with uranyl ions. And the synthetic strategy established here would enable the task-specific development of more novel CMP-based functional materials for broadened applications.

Keywords

conjugated microporous polymersuraniumadsorptionsynergistic coordinationdensity functional theory

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Nano Research
Volume 14 Issue 3,
March 2021
Pages 788-796
DOI: 10.1007/s12274-020-3217-7
Cite this article:
Yu B, Zhang L, Ye G, et al. De novo synthesis of bifunctional conjugated microporous polymers for synergistic coordination mediated uranium entrapment. Nano Research, 2021, 14(3): 788-796. https://doi.org/10.1007/s12274-020-3217-7
Topics:
Density functional theoryHydrogen bonds Metal ionsMetalsMicroporosity UraniumUranium compoundsX-ray photoelectron spectroscopy

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Received: 07 September 2020
Revised: 19 October 2020
Accepted: 29 October 2020
Published: 01 March 2021
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature
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