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      Regenerable and stable sp 2 carbon-conjugated covalent organic frameworks for selective detection and extraction of uranium

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          Abstract

          Uranium is a key element in the nuclear industry, but its unintended leakage has caused health and environmental concerns. Here we report a sp 2 carbon-conjugated fluorescent covalent organic framework (COF) named TFPT-BTAN-AO with excellent chemical, thermal and radiation stability is synthesized by integrating triazine-based building blocks with amidoxime-substituted linkers. TFPT-BTAN-AO shows an exceptional UO 2 2+ adsorption capacity of 427 mg g −1 attributable to the abundant selective uranium-binding groups on the highly accessible pore walls of open 1D channels. In addition, it has an ultra-fast response time (2 s) and an ultra-low detection limit of 6.7 nM UO 2 2+ suitable for on-site and real-time monitoring of UO 2 2+, allowing not only extraction but also monitoring the quality of the extracted water. This study demonstrates great potential of fluorescent COFs for radionuclide detection and extraction. By rational designing target ligands, this strategy can be extended to the detection and extraction of other contaminants.

          Abstract

          Porous materials for uranium capture have been developed in the past, but materials for simultaneous uranium capture and detection are scarce. Here the authors develop a stable covalent organic framework capable of adsorbing and detecting uranyl ions.

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          Two-dimensional sp2 carbon-conjugated covalent organic frameworks.

          We synthesized a two-dimensional (2D) crystalline covalent organic framework (sp2c-COF) that was designed to be fully π-conjugated and constructed from all sp2 carbons by C=C condensation reactions of tetrakis(4-formylphenyl)pyrene and 1,4-phenylenediacetonitrile. The C=C linkages topologically connect pyrene knots at regular intervals into a 2D lattice with π conjugations extended along both x and y directions and develop an eclipsed layer framework rather than the more conventionally obtained disordered structures. The sp2c-COF is a semiconductor with a discrete band gap of 1.9 electron volts and can be chemically oxidized to enhance conductivity by 12 orders of magnitude. The generated radicals are confined on the pyrene knots, enabling the formation of a paramagnetic carbon structure with high spin density. The sp2 carbon framework induces ferromagnetic phase transition to develop spin-spin coherence and align spins unidirectionally across the material.
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            Thioether-Based Fluorescent Covalent Organic Framework for Selective Detection and Facile Removal of Mercury(II).

            Heavy metal ions are highly toxic and widely spread as environmental pollutants. New strategies are being developed to simultaneously detect and remove these toxic ions. Herein, we take the intrinsic advantage of covalent organic frameworks (COFs) and develop fluorescent COFs for sensing applications. As a proof-of-concept, a thioether-functionalized COF material, COF-LZU8, was "bottom-up" integrated with multifunctionality for the selective detection and facile removal of mercury(II): the π-conjugated framework as the signal transducer, the evenly and densely distributed thioether groups as the Hg(2+) receptor, the regular pores facilitating the real-time detection and mass transfer, together with the robust COF structure for recycle use. The excellent sensing performance of COF-LZU8 was achieved in terms of high sensitivity, excellent selectivity, easy visibility, and real-time response. Meanwhile, the efficient removal of Hg(2+) from water and the recycling of COF-LZU8 offers the possibility for practical applications. In addition, X-ray photoelectron spectroscopy and solid-state NMR investigations verified the strong and selective interaction between Hg(2+) and the thioether groups of COF-LZU8. This research not only demonstrates the utilization of fluorescent COFs for both sensing and removal of metal ions but also highlights the facile construction of functionalized COFs for environmental applications.
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              Diacetylene Functionalized Covalent Organic Framework (COF) for Photocatalytic Hydrogen Generation

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                Author and article information

                Contributors
                jdqiu@ncu.edu.cn
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                23 January 2020
                23 January 2020
                2020
                : 11
                : 436
                Affiliations
                [1 ]ISNI 0000 0001 2182 8825, GRID grid.260463.5, College of Chemistry, , Nanchang University, ; Nanchang, 330031 China
                [2 ]ISNI 0000 0000 8644 1405, GRID grid.46078.3d, Department of Chemistry, Waterloo Institute for Nanotechnology, , University of Waterloo, Waterloo, ; Ontario, N2L 3G1 Canada
                Author information
                http://orcid.org/0000-0002-6793-9499
                Article
                14289
                10.1038/s41467-020-14289-x
                6978342
                31974343
                28fd4cd7-e7a6-43ef-a4a7-07e6dcd1ed69
                © The Author(s) 2020

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 24 September 2019
                : 18 December 2019
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100001809, National Natural Science Foundation of China (National Science Foundation of China);
                Award ID: 21675078, 21775065, and 21976077
                Award Recipient :
                Funded by: FundRef https://doi.org/10.13039/501100004479, Natural Science Foundation of Jiangxi Province (Jiangxi Province Natural Science Foundation);
                Award ID: 20165BCB18022
                Award Recipient :
                Categories
                Article
                Custom metadata
                © The Author(s) 2020

                Uncategorized
                polymers,sensors and biosensors
                Uncategorized
                polymers, sensors and biosensors

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