Hydrogen Isotope Effect Endows a Breakthrough in Photoluminescent Covalent Organic Frameworks.

Luminescent covalent organic frameworks (LCOFs) have emerged as indispensable candidates in various applications due to their greater tunable emitting properties and structural robustness compared to small molecule emitters. An unsolved issue in this area is developing highly luminescent LCOFs of which the nonradiative quenching pathways were suppressed as much as possible. Here, a robust aminal-linked COF (DD-COF) possessing perdeuterated light-emitting monomers was designed and synthesized. The solid-state photoluminescence quantum yield of the DD-COF reaches 81%, significantly outcompeting all state-of-the-art LCOFs reported so far. The exceptional luminescent efficiency is attributed to the inhibition of different pathways of nonradiative decay, especially from bond vibrations where only substitution by a heavier isotope with a lower zero-point vibration frequency works. Furthermore, the prepared deuterated COF not only boosts higher photostability under UV irradiation but also enables superior fluorescence sensing performance for iodine detection compared to nondeuterated COF.

Radiation-Induced De Novo Defects in Metal-Organic Frameworks Boost CO2 Sorption.

Defects in metal-organic frameworks (MOFs) can significantly change their local microstructures, thus notably leading to an alteration-induced performance in sorption or catalysis. However, achieving de novo defect engineering in MOFs under ambient conditions without the scarification of their crystallinity remains a challenge. Herein, we successfully synthesize defective ZIF-7 through 60Co gamma ray radiation under ambient conditions. The obtained ZIF-7 is defect-rich but also has excellent crystallinity, enhanced BET surface area, and hierarchical pore structure. Moreover, the amount and structure of these defects within ZIF-7 were determined from the two-dimensional (2D) 13C-1H frequency-switched Lee-Goldburg heteronuclear correlation (FSLG-HETCOR) spectra, continuous rotation electron diffraction (cRED), and high-resolution transmission electron microscopy (HRTEM). Interestingly, the defects in ZIF-7 all strongly bind to CO2, leading to a remarkable enhancement of the CO2 sorption capability compared with that synthesized by the solvothermal method.

Thermodynamics-Kinetics-Balanced Metal-Organic Framework for In-Depth Radon Removal under Ambient Conditions.

Radon (Rn), a ubiquitous radioactive noble gas, is the main source of natural radiation to human and one of the major culprits for lung cancer. Reducing ambient Rn concentration by porous materials is considered as the most feasible and energy-saving option to lower this risk, but the in-depth Rn removal under ambient conditions remains an unresolved challenge, mainly due to the weak van der Waals (vdW) interaction between inert Rn and adsorbents and the extremely low partial pressure (<1.8 × 10-14 bar, <106 Bq/m3) of Rn in air. Adsorbents having either favorable adsorption thermodynamics or feasible diffusion kinetics perform poorly in in-depth Rn removal. Herein, we report the discovery of a metal-organic framework (ZIF-7-Im) for efficient Rn capture guided by computational screening and modeling. The size-matched pores in ZIF-7-Im abide by the thermodynamically favorable principle and the exquisitely engineered quasi-open apertures allow for feasible kinetics with little sacrifice of sorption thermodynamics. The as-prepared material can reduce the Rn concentration from hazardous levels to that below the detection limit of the Rn detector under ambient conditions, with an improvement of at least two orders of amplitude on the removal depth compared to the currently best-performing and only commercialized material activated charcoal.

Deuterated Covalent Organic Frameworks with Significantly Enhanced Luminescence.

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.

Electron Beam Irradiation as a General Approach for the Rapid Synthesis of Covalent Organic Frameworks under Ambient Conditions.

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.

Ultrathin Space-Shift Phase-Coherent Cancellation Metasurface for Broadband Sound Absorption.

A space-shift phase-coherent cancellation acoustic metasurface is developed, which can achieve broadband low-frequency sound absorption via ultra-thin integrated structure composed of multiple units with weak absorption capability. Through a space-shift design of the channel length, the large-size required in the thickness direction for low-frequency absorption is transferred into an extremely ultra-thin space layer. The units with gradient channel length are compactly arranged in an ultra-thin layer through space folding, a coplanar sound absorption metasurface component with working bandwidth exceeding an octave and thickness of only λ/25 to λ/57 is obtained. As the construction of a special double-hole "bridge" layout, even if the elements are sparsely distributed, strong coupling interactions between the units can sustain. When a certain local phase relationship is satisfied, the coherent cancellation of sound energy can be achieved, so as to reduce the sound reflection and scattering, and enhance the absorption performance. Therefore, from the perspective of phase relationship among units, the present work provides more clear physical image and intuitive theoretical explanation for achieving excellent broadband sound absorption through parallel superposition of multiple units with weak absorption capability. The proposed ultra-thin sound absorbing metasurface can satisfy the thickness limitations and absorption performance requirements in most equipment.

Enhancing of broadband sound absorption through soft matter.

This paper proposed a metamaterial design method that uses soft matter for constructing a unique soft acoustic boundary to effectively improve broadband sound absorption performance. Specifically, attaching a flexible polyvinyl chloride (PVC) gel layer with an elastic modulus as low as a few kilopascals and a thickness of a few millimeters to the inner wall of a cavity-type sound-absorbing metamaterial structure significantly improved the absorption performance of the composite structure in low-frequency broadband ranges. The sound absorption enhancement mechanism differed from those proposed in previous research. On the one hand, the soft PVC gel layer acted as a soft acoustic boundary, substantially reducing the sound speed and reflection and producing considerable elastic strain energy at the interface between two different media to improve the sound absorption performance. On the other hand, this PVC gel layer displayed extremely low stiffness and high damping, producing an abundance of plasmon-like resonance modes in low-frequency broadband ranges, achieving a resonance absorption effect. Since this sound absorption enhancement method did not require an increase in the external dimensions or a change in the structural parameters of the original absorber and achieved robust enhancement in a wide frequency band, it displayed potential application value in various engineering fields.

Efficient Xe/Kr Separation Based on a Lanthanide-Organic Framework with One-Dimensional Local Positively Charged Rhomboid Channels.

Efficient xenon/krypton (Xe/Kr) separation has played an important role in industry due to the wide application of high-purity Xe and with regard to the safe disposal of radioactive noble gases (85Kr and 133Xe). A less energy-demanding separation technology, adsorptive separation using porous solid materials, has been proposed to replace the traditional cryogenic distillation with intensive energy consumption. As a cutting-edge class of porous materials, metal-organic frameworks (MOFs) featuring permanent porosity, designable chemical functionalities, and tunable pore sizes hold great promise for Xe/Kr separation. Here, we report a two-dimensional (2D) lanthanide-organic framework (termed LPC-MOF, [Eu(Ccbp)(NO3)(HCOO)]·DMF0.3(H2O)2.5) with one-dimensional (1D) local positively charged rhomboid channels whose size matches well with the kinetic diameter of Xe, leading to its superior Xe/Kr separation performance. Column breakthrough experiments demonstrate that LPC-MOF exhibits a high Xe/Kr selectivity of 12.4 and an Xe adsorption amount of 3.39 mmol kg-1 under simulated conditions for real used nuclear fuel (UNF)-reprocessing plants. Furthermore, density functional theory (DFT) calculations elucidate not only the intrinsic mechanisms of Xe/Kr separation at the molecular level but also the detailed influence of the local positive charge (N+) on the performance of Xe/Kr separation in the MOF system.

Progress of low-frequency sound absorption research utilizing intelligent materials and acoustic metamaterials.

In recent years, increasing attention has been paid to the impacts of environmental noises on living creatures as well as the accuracy and stability of precise instruments. Due to inherent properties induced by large wavelength, the attenuation and manipulation of low-frequency sound waves is quite difficult to realize with traditional acoustic absorbers, yet particularly critical to modern designs. The advent of acoustic metamaterials and intelligent materials provides possibilities of energy dissipation mechanisms other than viscous dissipation and heat conduction in conventional porous sound absorbers, and therefore inspires new strategies on the design of subwavelength-scale structures. This short review aims to trace the current advancement on the low-frequency sound absorption research utilizing intelligent materials and metamaterials, including Helmholtz resonators and acoustic metamaterials based on micro-perforated plates, porous media, and decorated membrane, along with the tunable absorbing structures regulated with the function of electroactive polymers or magnetically sensitive materials. The effective principles and prospects were concluded and presented for future investigations of subwavelength-scale acoustic structures.

Expanding the strong absorption band by impedance matched mosquito-coil-like acoustic metamaterials.

A mosquito-coil-like acoustic artificial structure consisting of a spiral channel and a perforated plate with excellent impedance matching is proposed, which can realize strong sound absorption within a certain frequency range. Due to the difficulty in matching the impedance of the single-hole structure with that of the sound propagation medium, the sound absorption should be poor. To overcome this shortcoming caused by the mismatched impedance, some multi-hole microstructures are designed. Moreover, since single-chamber labyrinth can only achieve single-frequency perfect sound absorption, a labyrinthine channel is divided into several chambers with each length distributing by an arithmetic progression gradient. The sound absorption bandwidth can be extended by synergetic coupling resonance among multiple chambers. By selecting different structural parameters including the number of holes, the width of the labyrinthine channel, and the depth of labyrinthine channel, sound absorption of these mosquito-coil-like structures is investigated. The results suggest that the multi-hole structures are helpful in improving the impedance matching, while the synergetic coupling resonance among multiple chambers ensures that the sound absorption coefficient of the structure can be maintained at a high level within a certain frequency range. In addition, some mosquito-coil-like sound absorption structures are fabricated by 3D printing, then the sound absorptions under vertical sound incident conditions are measured, and the strong sound absorption ability in a wide band is experimentally demonstrated. Finally, a method is proposed for adjusting the sound absorptions by proportionally zooming in or out the structure, by which the sound absorptions of the acoustic structure can be effectively shifted to lower or higher frequencies.

Shell-type acoustic metasurface and arc-shape carpet cloak.

We systematically propose a thin shell-type acoustic metasurface, which could be used to design a carpet cloak that closely covers an arc-shaped object, therefore providing the necessary support for hiding an object with any arbitrary shape. To facilitate the experimental measurement, however, the work here starts with some rotary spherical shell-type and ellipsoidal shell-type cell structures. The measured and calculated sound transmission loss (STL) results of these structures suggest that the sound insulation performances of the shell-type structure are quite different from those of the plate-type structure, indicating a possible break in the shape of the classical sound insulation curve. Considering also that cylindrical shell structures are more widely used in practice than the rotary shell structures, a number of two-dimensional bilayer cylindrical and elliptic cylindrical shell structures were, therefore, designed in this assay. Due to the asymmetry of the structure, the shell-type cells could exhibit bianisotropic sound absorption, reflection and effective parameters. Furthermore, the stiffness of the thin shell structure changed nonlinearly with the changing of the radius of curvature, with a wing shape tendency. In addition, a bilayer cylindrical shell-type acoustic metasurface and an arc-shaped carpet acoustic cloak were successively designed, wherein the phased compensation of differently shaped cell structures could be adjusted by means of a new engineering iso-phase design method. This work could provide the necessary guidance to extend existing results in the field of membrane- and plate-type acoustic metamaterials for shell-type structures, and the realization of the arc-shaped cloak could provide support for the design of a carpet acoustical cloak for use with arbitrary shapes.

Nano-MOF+ Technique for Efficient Uranyl Remediation.

The nano-MOF+ technique was employed by assembling nanoporous metal-organic framework (MOF) UiO-66 with nanoscale zero-valent iron (ZVI) particles to remove uranyl ions from aqueous solution under anoxic condition for the first time. The synthesized composite of Fe0@UiO-66-COOH exhibits a synergic effect between uranyl sorption by MOF host of UiO-66-COOH and chemical reduction by ZVI, reaching much elevated removal capacity and rate in comparison to those of the pristine UiO-66-COOH. The combined complexation and reduction mechanisms are further elucidated by the synchrotron radiation X-ray absorption near-edge structure analysis. This work highlights the bright future of the nano-MOF+ technique in the application of uranium removal, especially for the remediation of the uranium-contaminated subsurface environment.

Mechanism unravelling for ultrafast and selective 99TcO4 - uptake by a radiation-resistant cationic covalent organic framework: a combined radiological experiment and molecular dynamics simulation study.

99Tc is one of the most problematic fission products in the nuclear fuel cycle owing to its large inventory in used nuclear fuel, long half-life, potential radiation hazard, high environmental mobility of its major species 99TcO4 -, and its redox-active nature. Ideally, 99TcO4 - should be removed at the first stage, when the used fuel rods are dissolved in highly concentrated nitric acid solution, which can substantially reduce its interference with the solvent extraction process through catalytic redox reactions with the key actinides and diminish the chance of discharge into the environment as the volatile species during the waste vitrification process. However, this task cannot be achieved by any of the reported anion-scavenging materials including traditional polymeric anion-exchange resins, inorganic cationic framework materials, and recently developed cationic metal-organic framework materials, because they either are not stable under the extreme conditions of the combined high acidity and strong radiation field or do not possess the required uptake selectivity towards 99TcO4 - in the presence of a huge excess of competing anions such as NO3 - and SO4 2-. Herein, we present the first study of 99TcO4 - removal under extreme conditions by a two-dimensional conjugated cationic covalent organic framework material, SCU-COF-1. This material exhibits ultrahigh acid stability, great resistance towards both large-dose ß and γ irradiation and unprecedented 99TcO4 - uptake capabilities including extremely fast sorption kinetics (sorption equilibrium can be reached within 1 min), ultrahigh uptake capacity (702.4 mg g-1 for the surrogate ReO4 - at a slightly elevated temperature), and good anion-exchange selectivity towards 99TcO4 -. These excellent features endow SCU-COF-1 with the practical capabilities of separating 99TcO4 - from both simulant highly acidic fuel reprocessing solutions (3 M nitric acid) and low-activity waste streams at the US legacy nuclear site. The anion-exchange mechanism and the 99TcO4 - uptake selectivity are further demonstrated and clearly visualized by the molecular dynamics simulation investigations.

Correction: Mechanism unravelling for ultrafast and selective 99TcO4 - uptake by a radiation-resistant cationic covalent organic framework: a combined radiological experiment and molecular dynamics simulation study.

[This corrects the article DOI: 10.1039/C9SC00172G.].

Bilayer synergetic coupling double negative acoustic metasurface and cloak.

In this paper, we propose a bilayer plate-type lightweight double negative metasurface based on a new synergetic coupling design concept, by which the perfect absorption, double negative bands, free manipulation of phase shifts with a 2π span and acoustic cloak can be successively realized. Firstly, the synergetic behavior between resonant and anti-resonant plates is presented to construct a bilayer unit in which each component respectively provides a pre-defined function in realizing the perfect absorption. Based on this bilayer structure, a double negative band with simultaneously negative effective mass density and bulk modulus is obtained, which, as a metasurface, can obtain continuous phase shifts almost completely covering a 2π range, thus facilitating the design of a three-dimensional (3D) acoustic cloak. In addition, based on this strong sound absorption concept, a two-dimensional (2D) omnidirectional broadband acoustical dark skin, covering between 800 to 6000 Hz, is also demonstrated through the proposed bilayer plate-type structure form. The proposed design concepts and metasurfaces have widespread potential application values in strong sound attenuation, filtering, superlens, imaging, cloak, and extraordinary wave steering, in which the attributes of strong absorption, double negative parameters or continuous phase shifts with full 2π span are required to realize the expected extraordinary physical features.

Covalent Organic Framework Functionalized with 8-Hydroxyquinoline as a Dual-Mode Fluorescent and Colorimetric pH Sensor.

Real-time and accurate detection of pH in aqueous solution is of great significance in chemical, environmental, and engineering-related fields. We report here the use of 8-hydroxyquinoline-functionalized covalent organic framework (COF-HQ) for dual-mode pH sensing. In the fluorescent mode, the emission intensity of COF-HQ weakened as the pH decreased, and also displayed a good linear relationship against pH in the range from 1 to 5. In addition, COF-HQ showed discernible color changes from yellow to black as the acidity increased and can be therefore used as a colorimetric pH sensor. All these changes are reversible and COF-HQ can be recycled for multiple detection runs owing to its high hydrolytical stability. It can be further assembled into a mixed matrix membrane for practical applications.