Cheng-Rong Zhang

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.

Mercury is one of the most toxic elements in the environment. Recently, a number of covalent organic frameworks (COFs) were developed for simultaneous detection and removal of mercury. They rely on post-synthetically modified sulfur-based ligands for irreversible mercury binding. In addition, their rigid structures resulted in low fluorescence yields. Herein, a novel highly luminescent COF named TFPPy-CHYD with a quantum yield of 13.6% was designed by integrating a pyrene-based building block with a flexible carbohydrazide linker. The nitrogen-based ligand allows reversible and highly selective binding of Hg2+. As a sensing platform, it has an ultralow detection limit of 17 nM mercury. More importantly, TFPPy-CHYD exhibits excellent performance in removing mercury from both air and water, providing very high Hg0 and Hg2+ adsorption capacities of 232 and 758 mg g–1, respectively. This work demonstrates enormous potential of luminescent COF for metal detection and remediation. By rational introducing metal ligands, a suite of new COF materials might be synthesized for the detection and removal of other metal ions.

-c linked covalent organic frameworks (COFs) are considerably limited by the irreversibility of the C=C bond. Herein, inspired by the Claisen-Schmidt condensation reaction, two propenone-linked (C=C-C=O) COFs (named Py-DAB and PyN-DAB) are developed based on the base-catalyzed nucleophilic addition reaction of ketone-activated α-H with aromatic aldehydes. The introduction of propenone structure endows COFs with high crystallinity, excellent physicochemical stability, and intriguing optoelectronic properties. Benefitting from the rational design on the COFs skeleton, Py-DAB and PyN-DAB are applied to the extraction of radionuclide uranium. In particular, PyN-DAB shows excellent removal rates (>98%) in four uranium mine wastewater samples. We highlight that such a general strategy can provide a valuable avenue toward various functional porous crystalline materials.

Covalent organic frameworks (COFs) have shown extensive applications in energy storage, catalysis, and gas adsorption because of their regular pore structure, flexible topological connectivity, and excellent adjustable functionality. However, their potential applications in colorimetric sensing have not yet been explored. In this study, we synthesized bipyridine-containing covalent organic framework nanosheets (Tp-Bpy NSs) with a regular pore structure and abundant nitrogen-containing functional groups that function as active sites for the in situ generation of AuNPs to form AuNPs@Tp-Bpy. The anchoring of AuNPs onto Tp-Bpy NSs through coordination bonds can significantly enhance the dispersibility, stability, and catalytic activity of the AuNPs. We find that the synergistic effect of increased mimetic activity of gold amalgam and the higher access probability of Hg2+ provided by Tp-Bpy nanosheets makes the AuNPs@Tp-Bpy nanocomposite exhibit a high performance for the detection of Hg2+ with an ultralow detection limit of 0.33 nM. This sensing platform has been successfully used for the sensitive and stable detection of Hg2+ in various environmental samples. The present study extends the application of COFs and opens a new frontier for the design of novel nanocomposites for a variety of potential applications.