We report the synthesis and optical characterization of a series of metal chalcogenides, ASiSTe (A = Sr, Ba, Eu), highlighting the metal-atom substitution strategy for the discovery of a high-performance metal chalcogenide-based near-infrared (NIR) scintillator of EuSiSTe. EuSiSTe exhibits exceptionally broad NIR emission with a full width at half-maximum of 210 nm, the largest among all known Eu-based NIR emitters. EuSiSTe has a high light yield of 41697 photons/MeV and excellent resistance to hygroscopicity.
View Article and Find Full Text PDFMicronuclear batteries harness energy from the radioactive decay of radioisotopes to generate electricity on a small scale, typically in the nanowatt or microwatt range. Contrary to chemical batteries, the longevity of a micronuclear battery is tied to the half-life of the used radioisotope, enabling operational lifetimes that can span several decades. Furthermore, the radioactive decay remains unaffected by environmental factors such as temperature, pressure and magnetic fields, making the micronuclear battery an enduring and reliable power source in scenarios in which conventional batteries prove impractical or challenging to replace.
View Article and Find Full Text PDFMetal-anchored covalent organic frameworks (COFs), as a class of significant derivatives of COFs, are widely used as heterogeneous catalysts in diverse chemical reactions. However, they are typically synthesized via post-treatment strategies, which often lead to the decline of COF crystallinity, decrease of porous properties, instability in catalytic performances, generation of additional chemical waste, and consumption of excess time and energy. In this work, we demonstrate an approach to construct a metal-functionalized COF via a one-pot method induced by γ-ray radiation.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2024
Metal-organic framework (MOF) based heterostructures, which exhibit enhanced or unexpected functionality and properties due to synergistic effects, are typically synthesized using post-synthetic strategies. However, several reported post-synthetic strategies remain unsatisfactory, considering issues such as damage to the crystallinity of MOFs, presence of impure phases, and high time and energy consumption. In this work, we demonstrate for the first time a novel route for constructing MOF based heterostructures using radiation-induced post-synthesis, highlighting the merits of convenience, ambient conditions, large-scale production, and notable time and energy saving.
View Article and Find Full Text PDFTwo-dimensional covalent organic frameworks (2D COFs), featuring a large surface area and 1D pore structure, serve as promising scaffolds for anchoring functional guest compounds, which can significantly enhance their performance and thus expand their potential applications. Postsynthetic strategy for COFs functionalization is versatile but challenging because of their tedious procedure with high time and energy consumption, generation of excess reaction waste, and damage to COF crystallinity. We report in this work a general strategy for the synthesis of inorganic nanocompound-functionalized COF composites in a one-pot way.
View Article and Find Full Text PDFTwo-dimensional (2D) MXene materials with innovative properties and versatile applications have gained immense popularity among scientists. The green and environmentally friendly Lewis acid salt etching route has opened up immense possibilities for the advancement of 2D MXene materials. In this study, we precisely etched the Al element from the double A-element MAX phases Ti(SnAl)C by employing Lewis molten salt guided by redox potentials.
View Article and Find Full Text PDFSeparation of lanthanide (Ln) and minor actinide (MA) elements and mutual separation between minor actinide elements ( Am(III) and Cm(III)) represent a crucial undertaking. However, separating these elements poses a significant challenge owing to their highly similar physicochemical properties. Asymmetric N-heterocyclic ligands such as -ethyl-6-(1-pyrazol-3-yl)--(-tolyl)picolinamide (Et--Tol-A-PzPy) and -ethyl--(-tolyl)-1,10-phenanthroline-2-carboxamide (ETPhenAm) have recently received considerable attention in the separation of MAs over Ln from acid solutions.
View Article and Find Full Text PDFMAX phases are highly promising materials for electromagnetic (EM) wave absorption because of their specific combination of metal and ceramic properties, making them particularly suitable for harsh environments. However, their higher matching thickness and impedance mismatching can limit their ability to attenuate EM waves. To address this issue, researchers have focused on regulating the electronic structure of MAX phases through structural engineering.
View Article and Find Full Text PDFWe present the first example of an TcO anion entrapped within the cavity of a silver cluster, revealing an unprecedented photoinduced charge transfer phenomenon. [Ag(C≡CBu)(TcO)]·(BF) (denoted as ) was successfully synthesized and structurally characterized. Single-crystal X-ray diffraction and Raman spectroscopy reveal that the tetrahedral structure of the TcO anion sustains significant symmetry breaking with weakened Tc-O bond strength under confinement within the Ag(C≡CBu) cluster.
View Article and Find Full Text PDFDilanthanide complexes with one-electron delocalization are important targets for understanding the specific 4f/5d-bonding feature in lanthanide chemistry. Here, we report an isolable azide-bridged dicerium complex [{(Trapen)Ce}(μ-N)] [Trapen = tris (2-aminobenzyl)amine; TMS = SiMe], which is synthesized by the reaction of tripodal ligand-supported (Trapen)CeCl complex with NaN. The structure and bonding nature of are fully characterized by X-ray crystal diffraction analysis, electron paramagnetic resonance (EPR), magnetic measurement, cyclic voltammetry, X-ray absorption spectroscopy, and quantum-theoretical studies.
View Article and Find Full Text PDFThere is an urgent need for highly efficient sorbents capable of selectively removing TcO from concentrated alkaline nuclear wastes, which has long been a significant challenge. In this study, we present the design and synthesis of a high-performance adsorbent, CPN-3 (CPN denotes cationic polymeric nanotrap), which achieves excellent TcO capture under strong alkaline conditions by incorporating branched alkyl chains on the N3 position of imidazolium units and optimizing the framework anion density within the pores of a cationic polymeric nanotrap. CPN-3 features exceptional stability in harsh alkaline and radioactive environments as well as exhibits fast kinetics, high adsorption capacity, and outstanding selectivity with full reusability and great potential for the cost-effective removal of TcO/ReO from contaminated water.
View Article and Find Full Text PDFPlain simulations and enhanced sampling unveil a novel siderocalin (Scn) recognition mode for An-Ent (where An = actinides and Ent = enterobactin) complexes and identify a "seesaw" relationship between actinide affinity to Ent and Scn recognition to an An-Ent complex. Electrostatic interactions predominantly govern competitive binding in both processes. Additionally, hydrolysis-induced negative charge, water expulsion-driven entropy, and Ent's conformational adaptability collectively enhance high-affinity recognition.
View Article and Find Full Text PDFDefects 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 Co gamma ray radiation under ambient conditions.
View Article and Find Full Text PDFEfficient adsorption of palladium ions from acid nuclear waste solution is crucial for ensuring the safety of vitrification process for radioactive waste. However, the limited stability and selectivity of most current adsorbents hinder their practical applications under strong acid and intense radiation conditions. Herein, to address these limitations, we designed and synthesized an aryl-ether-linked covalent organic framework (COF-316-DM) grafted dimethylthiocarbamoyl groups on the pore walls.
View Article and Find Full Text PDFStorage phosphors displaying defect emissions are indispensable in technologically advanced radiation dosimeters. The current dosimeter is limited to the passive detection mode, where ionizing radiation-induced deep-trap defects must be activated by external stimulation such as light or heat. Herein, we designed a new type of shallow-trap storage phosphor by controlling the dopant amounts of Ag and Bi in the host lattice of CsNaInCl.
View Article and Find Full Text PDFA highly sensitive detection of ultraviolet (UV) radiation is required in a broad range of scientific research, chemical industries, and health-related applications. Traditional UV photodetectors fabricated by direct wide-band-gap inorganic semiconductors often suffer from several disadvantages such as complicated manufacturing procedures, requiring multiple operations and high-cost instruments to obtain a readout. Searching for new materials or simple strategies to develop UV dosimeters for quantitative, accurate, and on-site detection of UV radiation dose is still highly desirable.
View Article and Find Full Text PDFIts high coordination number and tendency to cluster make Th suitable for constructing metal-organic frameworks (MOFs) with novel topologies. In this work, two novel thorium-based heterometallic MOF isomers (IHEP-17 and IHEP-18) were assembled from a Th cluster, a multifunctional organic ligand [4-(1-pyrazol-4-yl)benzoic acid (HPyba)], and Cu/Ni cations via the one-pot solvothermal synthesis strategy. The framework features a 6,12-connected new topology net and contains two kinds of supramolecular cage structures, ThM and ThM, suitable for guest exchange.
View Article and Find Full Text PDFEfficient transfer of charge carriers through a fast transport pathway is crucial to excellent photocatalytic reduction performance in solar-driven CO reduction, but it is still challenging to effectively modulate the electronic transport pathway between photoactive motifs by feasible chemical means. In this work, we propose a thermally induced strategy to precisely modulate the fast electron transport pathway formed between the photoactive motifs of a porphyrin metal-organic framework using thorium ion with large ionic radius and high coordination number as the coordination-labile metal node. As a result, the stacking pattern of porphyrin molecules in the framework before and after the crystal transformations has changed dramatically, which leads to significant differences in the separation efficiency of photogenerated carriers in MOFs.
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