期刊
NANO RESEARCH
卷 14, 期 3, 页码 788-796出版社
TSINGHUA UNIV PRESS
DOI: 10.1007/s12274-020-3217-7
关键词
conjugated microporous polymers; uranium; adsorption; synergistic coordination; density functional theory
类别
资金
- National Natural Science Foundation of China [21922604, 51673109]
- Innovative Research Team in University [IRT13026]
- U.S. National Science Foundation [CBET-1706025]
- Robert A. Welch Foundation [B-0027]
This study reports a novel de novo synthesis of bifunctional conjugated microporous polymers with coordination behavior to uranium. The introduction of ortho-substituted amino functionalities enhances the affinity to uranyl ions and increases the adsorption capacity by almost 70%. XPS analysis and DFT calculation suggest a dominant role of oxime ligands in coordination with uranyl ions and show the synergistic engagement of amino functionalities in promoting coordination with uranyl ions.
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.
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