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.
The development of
anhydrous proton-conducting materials is critical
for the fabrication of high-temperature (>100 °C) polymer
electrolyte
membrane fuel cells (HT-PEMFCs) and remains a significant challenge.
Covalent organic frameworks (COFs) are an emerging class of porous
crystalline materials with tailor-made nanochannels and hold great
potential for ion and molecule transport, but their poor chemical
stability poses great challenges in this respect. In this contribution,
we present a bottom-up self-assembly strategy to construct perfluoroalkyl-functionalized
hydrazone-linked 2D COFs and systematically investigate the effect
of different lengths of fluorine chains on their acid stability and
proton conductivity. Compared with their nonfluorous parent COFs,
fluorinated COFs possess structural ultrastability toward strong acids
as a result of enhanced hydrophobicity (water contact angle of 144°).
Furthermore, the superhydrophobic 1D nanochannels can serve as robust
hosts to accommodate large amounts of phosphonic acid for fast and
long-term proton conduction under anhydrous conditions and a wide
temperature range. The anhydrous proton conductivity of fluorinated
COFs is 4.2 × 10–2 S cm–1 at 140 °C after H3PO4 doping, which is
4 orders of magnitude higher than their nonfluorous counterparts and
among the highest values of doped porous organic frameworks so far.
Solid-state NMR studies revealed that H3PO4 forms
hydrogen-boding networks with the frameworks and perfluoroalkyl chains
of COFs, and most of the H3PO4 molecules are
highly dynamic and mobile while the frameworks are rigid, which affords
rapid proton transport. This work paves the way for the realization
of the target properties of COFs through predesign and functionalization
of the pore surface and highlights the great potential of COF nanochannels
as a rigid platform for fast ion transportation.
One-pot extraction combined with the metal-free photochemical aerobic oxidative deep-desulfurization of fuels in deep eutectic solvents was successfully achieved.
The selectivity for sulfur removal from oils is an important topic. In this work, the selectivity for different sulfur removal methods has been studied by conceptual density functional theory (CDFT) at the B3LYP/6-31111G(3df,2p) level of theory. In principle, the selectivity is directly related to the mechanisms of sulfur removal. It cannot be precisely elucidated until the mechanisms are totally known. However, current work shows that relationships can be constructed between CDFT and the selectivity. That is, for hydrodesulfurization, good descriptors will be ionization energy, hardness, and bond lengths of SAC; for adsorptive desulfurization, the hardness is a good descriptor; for oxidative desulfurization, good descriptors are electron density and Fukui function. And for extractive desulfurization (nonmetal-based ionic liquids), electron affinity and electrophilicity may be good descriptors. In addition, structures and frontier orbitals of various sulfides have also been discussed. It is hoped that these relationships between CDFT and selectivity can give useful information to develop highly efficient sulfur removal methods for specific sulfides, like 4,6-dimethyldibenzothiophene, and 4-methyldibenzothiophene.
Novel carbon-doped porous boron nitride has been successfully prepared by using [Bmim]BF4as a soft template and the carbon source. The metal-free porous C-BN displayed one of the highest adsorption capacities for dibenzothiophene reported up to now.
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