Crystalline porous
materials such as covalent organic frameworks
(COFs) are advanced materials to tackle challenges of catalysis and
separation in industrial processes. Their synthetic routes often require
elevated temperatures, closed systems with high pressure, and long
reaction times, hampering their industrial applications. Here we use
a traditionally unperceived strategy to assemble highly crystalline
COFs by electron beam irradiation with controlled received dosage,
contrasting sharply with the previous observation that radiation damages
the crystallinity of solids. Such synthesis by electron beam irradiation
can be achieved under ambient conditions within minutes, and the process
is amendable for large-scale production. The intense and targeted
energy input to the reactants leads to new reaction pathways that
favor COF formation in nearly quantitative yield. This strategy is
applicable not only to known COFs but also to new series of flexible
COFs that are difficult to obtain using traditional methods.
Conventional
aromatic compounds tend to exhibit the formation of
sandwich-shaped excimers and exciplexes between their excited and
ground states at high concentrations or in their aggregated states,
causing their fluorescence to weaken or disappear due to the aggregation-caused
quenching (ACQ) effect. This limits their applications in concentrated
solutions or solid materials. Herein, for the first time, ACQ-based
pyrene (Py) units are covalently connected to the surface of polyethylene/polypropylene
nonwoven fabric (PE/PP NWF) via electron beam preradiation-induced
graft polymerization followed by chemical modification. The matrix
can be considered a solid solvent and Py units as a solid solute,
such that the amount of Py units can be controlled by varying the
reaction time. The obtained fluorescent fabric not only exhibits remarkable
fluorescence properties with high fluorescence intensity, high quantum
yield (>90%), and excellent fluorescence stability after laundering
or in harsh chemical environments, but the fluorescence color and
intensity, quantum yield, and lifetime can also be regulated by employing
the ACQ effect. Additionally, the as-prepared fluorescent fabric can
effectively distinguish common monocyclic aromatic hydrocarbons via
a simple fluorescence response test.
We disclose the intrinsic semiconducting properties of one of the largest mixed-valent uranium clusters, [Single-crystal X-ray crystallography demonstrates that U V center is stabilized within a tetraoxo core surrounded by eight uranyl(VI) pentagonal bipyramidal centers. The oxidation states of uranium are substantiated by spectroscopic data and magnetic susceptibility measurement. Electronic spectroscopy and theory corroborate that U V species serve as electron donors and thus facilitate 1 being a n-type semiconductor. With the largest effective atomic number among all reported radiation-detection semiconductor materials, charge transport properties and photoconductivity were investigated under Xray excitation for 1: a large on-off ratio of 500 and considerable charge mobility lifetime product of 2.3 10 À4 cm 2 V À1 , as well as a high detection sensitivity of 23.4 mC Gy air À1 cm À2 .
Luminescent covalent organic frameworks (COFs) find promising applications in chemical sensing, photocatalysis, and optoelectronic devices, however, the majority of COFs are non or weakly emissive owing to the aggregation‐caused quenching (ACQ) or the molecular thermal motion‐based energy dissipation. Here, we report a previously unperceived approach to improve luminescence performance of COFs by introducing isotope effect, which is achieved through substitution of hydrogen from high‐frequency oscillators X‐H (X=O, N, C) by heavier isotope deuterium. Combining the “bottom‐up” and in situ deuteration methods generates the first deuterated COF, which exhibits an impressively 19‐fold enhancement in quantum yield over that of the non‐deuterated counterpart. These results are interpreted by theoretical calculations as the consequence of slower C/N‐D and OD⋅⋅⋅O vibrations that impede the nonradiative deactivation process. The proposed strategy is proved applicable to many other types of emissive COFs.
Zeolites are a well‐known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy‐consuming. Herein, we utilize high‐energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na‐A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na‐A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites.
The biosorption is an effective and economical method to deal with the wastewater with low concentrations of uranium. In this study, we present a systematic investigation of the adsorption properties, such as the kinetics, thermodynamics, and mechanisms, of modified rice stems. The rice stems treated with 0.5 mol/L NaOH solutions show higher removal percentage of uranium than those unmodified under the conditions of initial pH (pH = 4.0), absorbent dosage (5–8 g/L), temperature (T = 298 K), and adsorption equilibrium time (t = 180 min). The removal percentage of uranium(VI) decreases with increasing initial concentration of uranium(VI). The Langmuir isotherm model, which suggests predominant monolayered sorption, is better than Freundlich and Temkin models to elucidate the adsorption isotherm of adsorbed uranium. Kinetic analyses indicate that the uranium(VI) adsorption of the modified rice stem is mainly controlled by surface adsorption. The pseudo-second-order kinetic model, with the correlation coefficient of R2 = 0.9992, fits the adsorption process much better than other kinetic models (e.g., pseudo-second-order kinetic model, Elovich kinetic model, and intraparticle diffusion model). The thermodynamic parameters ΔG0, ΔH0, and ΔS0 demonstrate that the adsorption of uranium(VI) is an endothermic and spontaneous process, which can be promoted by temperature. The adsorption of uranium can change the morphology and the structure characteristics of the modified rice stem through interaction with the adsorption sites, such as O-H, C=O, Si=O, and P-O on the surface.
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