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Preorganization is an effective strategy for f-element separation, but the complexity of extractant synthesis hinders large-scale application. Here the authors discuss an alternative strategy induced by in situ self-assembly that borrows principles of multivalent cooperativity from Nature to separate f-elements. [ABSTRACT FROM AUTHOR]

The fundamental problem of point defects under different phase equilibrium conditions in zircon (ZrSiO 4 ) is carried out by first-principles calculation. The formation energies with the structural deformation of various native defects, i.e., single vacancy, interstitial, Frenkel and Schottky pairs at different charge states are calculated, which agree well with the available results. We identify V O 2 + shows an important role in non-stoichiometric regime of ZrSiO 4− x ( x  < 1). When Fermi level ( ε F ) locates close to the CBM, the V Zr 4 − becomes more easily observed than V O 2 + in O-rich environment. In turn, the most abundant interstitial defects are I Zr 4 + and I Si 4 + . The non-interacting Si Frenkel-pair, made of the association of quadruply charged defect in energy of 5.947 eV, is more likely to form than other type of Frenkel-pairs. By formation the complex defects associating partial and full Schottky defects requires higher formation energy. These results provide a good reference to understand storage state as well as disposal of excess weapons-grade Pu and high-actinide wastes. [ABSTRACT FROM AUTHOR]

Dissimilatory metal-reducing bacteria (DMRB) can harvest energy for growth and activities by respiring metals, but it is so far unknown whether DMRB can acquire crystalline-phase actinides. In the present study, we used Shewanella oneidensis MR-1 to investigate microbially-mediated dissolution and reduction of U(VI) in three uranyl(VI) borate and boronate crystals (i.e., UO 2 (CH 3 BO 2 )(H 2 O) (UCBO); UO 2 B 2 O 4 (UBO); and Na[(UO 2 )B 6 O 10 (OH)]·2H 2 O (NaUBO)). Comparison of the dissolved U(VI) concentrations between samples with and without bacteria indicates that MR-1 facilitated dissolution of UCBO and UBO. Based on the assumption that only dissolved U(VI) was reduced, U(VI) reduction was substantially underestimated for UCBO and NaUBO, indicating that MR-1 directly reduced crystalline U(VI) in these two compounds. Laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis implied that interactions occurred between microbial ligands and the residual particles of uranyl compounds. We found that S. oneidensis MR-1 can mediate the dissolution and reduction of crystalline U(VI) through facilitated dissolution and consequent reduction of crystals or direct reduction of U(VI) in crystals. These results help evaluate the environmental fate of solid-phase U(VI), critical for predicting U transport and remediating U-contaminated sites. [ABSTRACT FROM AUTHOR]

During the solvothermal synthesis of a low-dimensional borate, KB 5 O 7 (OH) 2 ⋅2H 2 O, in the presence of Pu(III), single crystals of plutonium dioxide unexpectedly formed. Single crystals of PuO 2 also formed during the hydrothermal synthesis of another borate, Na 2 B 5 O 8 (OH)⋅2H 2 O, in the presence of Pu(III). The reactions were conducted at 170 °C and 150 °C, respectively, which are much lower temperature than previously reported preparations of crystalline PuO 2 . Yellow–green crystals with a tablet habit were characterized by single crystal X-ray diffraction and solid-state UV–vis–NIR absorption spectroscopy. The crystal structure was solved by direct methods with R 1 = 1.26% for 19 unique observed reflections. PuO 2 is cubic, space group Fm 3 ‾ m , and adopts the fluorite structure type. The lattice parameter was determined to be a = 5.421(5) Å giving a volume of 159.3(2) Å 3 . The absorption spectrum is consistent with Pu(IV). [ABSTRACT FROM AUTHOR]

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. Specifically, a new HKUST‐1@Cu2O heterostructure was successfully synthesized by simply irradiating a methanol solution dispersed of HKUST‐1 with gamma ray under ambient conditions. The copper source of Cu2O was directly derived from in situ radiation etching and reduction of the parent HKUST‐1, without the use of any additional copper reagents. Significantly, the resulting HKUST‐1@Cu2O heterostructure exhibits remarkable catalytic performance, with a catalytic rate constant nearly two orders of magnitude higher than that of the parent HKUST‐1. [ABSTRACT FROM AUTHOR]

As a critical radioactive anionic contaminant, traditional adsorbents primarily remove iodate (IO3−) through ion exchange or hard acid‐hard base interactions, but suffer from limited affinity and capacity. Herein, employing the synergistic effect of ion exchange and redox, we successfully synthesized a redox‐active cationic polymer network (SCU‐CPN‐6, [C9H10O2N5 ⋅ Cl]n) by merging guanidino groups with ion‐exchange capability and phenolic groups with redox ability via a Schiff base reaction. SCU‐CPN‐6 exhibits a groundbreaking adsorption capacity of 896 mg/g for IO3−. The inferior adsorption capacities of polymeric networks containing only redox (~0 mg/g) or ion exchange (232 mg/g) fragments underscore the synergistic "1+1>2" effect of the two mechanisms. Besides, SCU‐CPN‐6 shows excellent uptake selectivity for IO3− in the presence of high concentrations of SO42−, Cl−, and NO3−. Meanwhile, a high distribution coefficient indicates its exemplary deep‐removal performance for low IO3− concentration. The synergic strategy not only presents a breakthrough solution for the efficient removal of IO3− but also establishes a promising avenue for the design of advanced adsorbents for diverse applications. [ABSTRACT FROM AUTHOR]

Two‐electron oxidative addition is one of the most important elementary reactions for d‐block transition metals but it is uncommon for f‐block elements. Here, we report the first examples of intermolecular oxidative addition of E−H (E=C, N) bonds to uranium(II) centers. The transient U(II) species was formed in‐situ by reducing a heterometallic cluster featuring U(IV)‐Pd(0) bonds with potassium‐graphite (KC8). Oxidative addition of C−H or N−H bonds to the U(II) centers was observed when this transient U(II) species was treated with benzene, carbazole or 1‐adamantylamine, respectively. The U(II) centers could also react with tetracene, biphenylene or N2O, leading to the formation of arene reduced U(IV) products and uranyl(VI) species via two‐ or four‐electron processes. This study demonstrates that the intermolecular two‐electron oxidative addition reactions are viable for actinide elements. [ABSTRACT FROM AUTHOR]

In conjunction with theoretical calculations, the in vitro and in vivo uranyl binding capabilities of a bidentate picolinate (Pic) ligand and its pentadentate derivative (H2dpa) are investigated. The planar N3O2-donor configuration of H2dpa matches the typical pentagonal-bipyramid coordination geometry of uranyl, demonstrating a remarkable removal preference for uranyl in the kidneys. [ABSTRACT FROM AUTHOR]

Efficient 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. This unique structure endows COF‐316‐DM with high stability and exceptional palladium capture capacity. The robust polyarylether linkage enables COF‐316‐DM to withstand irradiation doses of 200 or 400 kGy of β/γ ray. Furthermore, COF‐316‐DM demonstrates fast adsorption kinetics, high adsorption capacity (147 mg g−1), and excellent reusability in 4 M nitric acid. Moreover, COF‐316‐DM exhibits remarkable selectivity for palladium ions in the presence of 17 interference ions, simulating high level liquid waste scenario. The superior adsorption performance can be attributed to the strong binding affinity between the thioamide groups and Pd2+ ions, as confirmed by the comprehensive analysis of FT‐IR and XPS spectra. Our findings highlight the potential of COFs with robust linkers and tailored functional groups for efficient and selective capture of metal ions, even in harsh environmental conditions. [ABSTRACT FROM AUTHOR]

A radiochemistry laboratory presents potential radiological hazards due to the handling of multiple radionuclides with various half-lives and modes of radiation emission. To minimize these hazards, appropriate safety management and radiation protection strategies should be in place. The radiochemistry laboratory at Soochow University is one such workplace that handles therapeutic radionuclides, fission products, and actinides in liquid, solid, and gas forms. This work highlights the significance of using safety precautions and radiation protection strategies before conducting experiments in such laboratories. The practical knowledge gained from a case of radioactive contamination is discussed to provide valuable experience for safely conducting radiochemistry experiments. [ABSTRACT FROM AUTHOR]

Halide perovskites (HPs) recently have emerged as one class of competitive scintillators for X‐ray detection and imaging owing to its high quantum efficiency, short decay time, superior X‐ray absorption capacity, low cost, and ease of crystal growth. The tunable structure and versatile chemical compositions of halide perovskites provide distinguishable advantages over traditional inorganic scintillators for optimizing scintillation performance. Since the first observation of the scintillation phenomenon in HPs, substantial efforts have been devoted to expanding the inventory of HP scintillators and regulating material properties. Understanding the relationship between the structure and scintillation properties of HP scintillators is essential for developing materials with improved X‐ray detection and imaging capacities. This review summarizes strategies for improving the light yield of HP scintillators and provides a roadmap for improving the X‐ray imaging performance. Additionally, methods for controlling the light propagation direction in HP scintillators are highlighted for improving X‐ray imaging resolution. Finally, we highlight the current challenge in HP scintillators and provide a perspective on the future development of this emerging scintillator. [ABSTRACT FROM AUTHOR]

Halide perovskites (HPs) recently have emerged as one class of competitive scintillators for X‐ray detection and imaging owing to its high quantum efficiency, short decay time, superior X‐ray absorption capacity, low cost, and ease of crystal growth. The tunable structure and versatile chemical compositions of halide perovskites provide distinguishable advantages over traditional inorganic scintillators for optimizing scintillation performance. Since the first observation of the scintillation phenomenon in HPs, substantial efforts have been devoted to expanding the inventory of HP scintillators and regulating material properties. Understanding the relationship between the structure and scintillation properties of HP scintillators is essential for developing materials with improved X‐ray detection and imaging capacities. This review summarizes strategies for improving the light yield of HP scintillators and provides a roadmap for improving the X‐ray imaging performance. Additionally, methods for controlling the light propagation direction in HP scintillators are highlighted for improving X‐ray imaging resolution. Finally, we highlight the current challenge in HP scintillators and provide a perspective on the future development of this emerging scintillator. [ABSTRACT FROM AUTHOR]

The development of high‐performance X‐ray detectors requires scintillators with fast decay time, high light yield, stability, and X‐ray absorption capacity, which are difficult to achieve in a single material. Here, we present the first example of a lanthanide chalcogenide of LaCsSiS4 : 1 % Ce3+ that simultaneously integrates multiple desirable properties for an ideal scintillator. LaCsSiS4 : 1 % Ce3+ demonstrates a remarkably low detection limit of 43.13 nGyair s−1 and a high photoluminescence quantum yield of 98.24 %, resulting in a high light yield of 50480±1441 photons/MeV. Notably, LaCsSiS4 : 1 % Ce3+ exhibits a fast decay time of only 29.35±0.16 ns, making it one of the fastest scintillators among all lanthanide‐based inorganic scintillators. Furthermore, this material shows robust radiation and moisture resistance, endowing it with suitability for chemical processing under solution conditions. To demonstrate the X‐ray imaging capacity of LaCsSiS4 : 1 % Ce3+, we fabricated a flexible X‐ray detector that achieved a high spatial resolution of 8.2 lp mm−1. This work highlights the potential of lanthanide chalcogenide as a promising candidate for high‐performance scintillators. [ABSTRACT FROM AUTHOR]

The development of high‐performance X‐ray detectors requires scintillators with fast decay time, high light yield, stability, and X‐ray absorption capacity, which are difficult to achieve in a single material. Here, we present the first example of a lanthanide chalcogenide of LaCsSiS4 : 1 % Ce3+ that simultaneously integrates multiple desirable properties for an ideal scintillator. LaCsSiS4 : 1 % Ce3+ demonstrates a remarkably low detection limit of 43.13 nGyair s−1 and a high photoluminescence quantum yield of 98.24 %, resulting in a high light yield of 50480±1441 photons/MeV. Notably, LaCsSiS4 : 1 % Ce3+ exhibits a fast decay time of only 29.35±0.16 ns, making it one of the fastest scintillators among all lanthanide‐based inorganic scintillators. Furthermore, this material shows robust radiation and moisture resistance, endowing it with suitability for chemical processing under solution conditions. To demonstrate the X‐ray imaging capacity of LaCsSiS4 : 1 % Ce3+, we fabricated a flexible X‐ray detector that achieved a high spatial resolution of 8.2 lp mm−1. This work highlights the potential of lanthanide chalcogenide as a promising candidate for high‐performance scintillators. [ABSTRACT FROM AUTHOR]

The crystal structures of compounds (III), (IV), (VI) and (VII) are determined by single crystal XRD. [ABSTRACT FROM AUTHOR]

Periodically arranging coordination‐distinct actinides into one crystalline architecture is intriguing but of great synthetic challenge. We report a rare example of a heterobimetallic actinide metal–organic framework (An‐MOF) by a unique reaction‐induced preorganization strategy. A thorium MOF (SCU‐16) with the largest unit cell among all Th‐MOFs was prepared as the precursor, then the uranyl was precisely embedded into the MOF precursor under oxidation condition. Single crystal of the resulting thorium‐uranium MOF (SCU‐16‐U) shows that a uranyl‐specific site was in situ induced by the formate‐to‐carbonate oxidation reaction. The heterobimetallic SCU‐16‐U exhibits multifunction catalysis properties derived from two distinct actinides. The strategy proposed here offers a new avenue to create mixed‐actinide functional material with unique architecture and versatile functionality. [ABSTRACT FROM AUTHOR]

Periodically arranging coordination‐distinct actinides into one crystalline architecture is intriguing but of great synthetic challenge. We report a rare example of a heterobimetallic actinide metal–organic framework (An‐MOF) by a unique reaction‐induced preorganization strategy. A thorium MOF (SCU‐16) with the largest unit cell among all Th‐MOFs was prepared as the precursor, then the uranyl was precisely embedded into the MOF precursor under oxidation condition. Single crystal of the resulting thorium‐uranium MOF (SCU‐16‐U) shows that a uranyl‐specific site was in situ induced by the formate‐to‐carbonate oxidation reaction. The heterobimetallic SCU‐16‐U exhibits multifunction catalysis properties derived from two distinct actinides. The strategy proposed here offers a new avenue to create mixed‐actinide functional material with unique architecture and versatile functionality. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The second example of tetravalent plutonium carboxyl‐based organic framework, 242Pu(OH)[PO[(C6H4)COO]3]·H2O, termed as PuTPO (TPO = tris(4‐carboxylphenyl)‐phosphineoxide), was reported in this work. A series of characterizations of PuTPO, such as X‐ray crystallography and solid‐state UV‐Vis‐NIR spectroscopy, were carried out to expatiate its structure and physicochemical properties. PuTPO is constructed by dimers of the plutonium‐oxygen subunit of [Pu2O16]. Characteristic peaks located at approximately 1100 nm can be considered to be the fingerprint peaks of tetravalent plutonium. While PuTPO can maintain high crystallinity within several months after synthesis, it exhibits a radiation‐induced swelling effect probed by the expansion of cell parameter of b axis after self‐irradiation from α‐decay of 242Pu. This result enriches the inventory of tetravalent plutonium compounds and provides an insight into the irradiation resistance of metal‐organic frameworks. [ABSTRACT FROM AUTHOR]

Although examples of multiple bonds between actinide elements and main‐group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis‐[M→→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U←← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M→→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine‐bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ‐Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U←← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M double dative bonds in these complexes. This study not only enriches the U←← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements. [ABSTRACT FROM AUTHOR]

Although examples of multiple bonds between actinide elements and main‐group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis‐[M→→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U←← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M→→ ${{\rm{ \mathbin{{\stackrel{\textstyle\rightarrow} { {\smash{\rightarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine‐bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ‐Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U←← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M double dative bonds in these complexes. This study not only enriches the U←← ${{\rm{ \mathbin{{\stackrel{\textstyle\leftarrow} { {\smash{\leftarrow}\vphantom{_{\vbox to.5ex{\vss}}}} } }} }}}$ M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements. [ABSTRACT FROM AUTHOR]

In this Frontier article, we pursue the sequestration of radionuclides from aqueous solution by using recently emerging metal–organic framework (MOF) materials. The design of MOF materials and their corresponding sorption properties towards radionuclides (137Cs, 90Sr, 238U, 79Se, and 99Tc) as well as their interaction mechanisms are highlighted. The present challenges and future prospects of removing radionulides with MOFs as sorbents are also demonstrated. [ABSTRACT FROM AUTHOR]

Efficient removal of iodide (I−) and iodate (IO3−) from aqueous solution is highly desirable for waste disposal and remediation of radioiodine contamination. We report here a bifunctional anion exchange resin Purolite A530E for the effective I−/IO3− adsorption, which shows a priority anion-exchange affinity for I− (99%) over IO3− (9.7%). The maximum adsorption capacity for I− is 275.16 mg·g−1 fitted by the Langmuir isotherm model, much higher than most adsorbents. Furthermore, Purolite A530E exhibits great selectivity for I− over competing anions, which endows the resin with promising I− remediation that over 99% I− can be removed from simulated Hanford groundwater (HGW). [ABSTRACT FROM AUTHOR]

The exceptional photophysical properties of 3D organic–inorganic lead halide hybrids (OILHs) endow their significant potential for usage in optoelectronics, which has sparked intense research on novel 3D OILHs and associated applications. However, constructing new 3D OILHs based on large organic cations suffers from tough challenges due to the limitation of the Goldschmidt tolerance factor rule, let alone further explorations of their practical applications. Herein, a brand‐new 3D lead chloride hybrid, (1MPZ)Pb4Cl10·H2O (1, 1MPZ = 1‐methylpiperazine) is reported, featuring a dense 3D lead chloride framework made of the corner‐, edge‐, and face‐shared lead chloride polyhedra. 1 presents a broadband white light emission with a large Stokes shift and a nanosecond photoluminescence lifetime, which originates from radiative recombination of self‐trapped excitons (STEs) induced by the highly distorted structure. Such a reabsorption‐free and fast‐decayed STEs emission coupling with the dense 3D architecture further enables 1 with effective X‐ray scintillation with good sensitivity. Impressively, 1 also shows superior environmental and radiation stability. This study provides a new 3D OILH with appealing luminescence, not only expanding the 3D OILH family but also inspiring the exploitation of their optoelectronic applications. [ABSTRACT FROM AUTHOR]

The Haber–Bosch process produces ammonia (NH3) from dinitrogen (N2) and dihydrogen (H2), but requires high temperature and pressure. Before iron-based catalysts were exploited in the current industrial Haber–Bosch process, uranium-based materials served as effective catalysts for production of NH3 from N2. Although some molecular uranium complexes are known to be capable of combining with N2, further hydrogenation with H2 forming NH3 has not been reported to date. Here, we describe the first example of N2 cleavage and hydrogenation with H2 to NH3 with a molecular uranium complex. The N2 cleavage product contains three uranium centers that are bridged by three imido μ 2-NH ligands and one nitrido μ 3-N ligand. Labeling experiments with 15N demonstrate that the nitrido ligand in the product originates from N2. Reaction of the N2-cleaved complex with H2 or H+ forms NH3 under mild conditions. A synthetic cycle has been established by the reaction of the N2-cleaved complex with trimethylsilyl chloride. The isolation of this trinuclear imido-nitrido product implies that a multi-metallic uranium assembly plays an important role in the activation of N2. [ABSTRACT FROM AUTHOR]

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high‐energy (1.5 MeV) electron beam radiation from a commercially available electron‐accelerator. Using ZIF‐8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF‐8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF‐8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes. [ABSTRACT FROM AUTHOR]

Metal organic frameworks (MOFs) are a distinct family of crystalline porous materials finding extensive applications. Their synthesis often requires elevated temperature and relatively long reaction time. We report here the first case of MOF synthesis activated by high‐energy (1.5 MeV) electron beam radiation from a commercially available electron‐accelerator. Using ZIF‐8 as a representative for demonstration, this type of synthesis can be accomplished under ambient conditions within minutes, leading to energy consumption about two orders of magnitude lower than that of the solvothermal condition. Interestingly, by controlling the absorbed dose in the synthesis, the electron beam not only activates the formation reaction of ZIF‐8, but also partially etches the material during the synthesis affording a hierarchical pore architecture and highly crystalline ZnO nanoparticles on the surface of ZIF‐8. This gives rise to a new strategy to obtain MOF@metal oxide heterostructures, finding utilities in photocatalytic degradation of organic dyes. [ABSTRACT FROM AUTHOR]

A rare case of semiconducting actinide-based metal–organic framework SCU-125 was designed and synthesized. As a result of the lack of two coordination sites in the plane of the tetrathiafulvalene tetrabenzoate (TTFTB) molecule, a defective kgd network was formed. The electrical conductivity of SCU-125 was measured to be 2.2(2) × 10−7 S cm−1 at 25 °C ± 2 °C. [ABSTRACT FROM AUTHOR]

A three-dimensional microporous thorium-based metal–organic framework (Th-BPYDC-I) that features a suitable pore size for Xe was prepared. The pore confinement effect enables high Xe uptake (2.15 mmol g−1) and good Xe/Kr selectivity (7.49). This work highlights the critical role of the size-matching rule in noble gas separation and provides an alternative option for Xe/Kr separation. [ABSTRACT FROM AUTHOR]

A novel 3D potassium-containing zirconium fluorophosphonate K2Zr[CH2(PO3)2]F2 (SZ-8) was successfully synthesized as single crystals via a solvothermal method using a mixture of nitric acid and potassium nitrate as mineralizers. SZ-8 can adsorb 110.6 and 57 mg g−1 of Eu3+ in pH 2 and pH 1 solutions respectively, highlighting its potential remediation for radionuclides with high charges. SZ-8 not only possesses superior Eu3+ removal capacity under strongly acidic conditions, but also provides a universal synthesis strategy for crystalline zirconium phosphonates with inorganic counterions. [ABSTRACT FROM AUTHOR]

A novel polymorph of ThB2O5, denoted as β-ThB2O5, was synthesised under high-temperature high-pressure (HT/HP) conditions. Via single crystal X-ray diffraction measurements, β-ThB2O5 was found to form a three-dimensional (3D) framework structure where thorium atoms are ten-fold oxygen coordinated forming tetra-capped trigonal prisms. The only other known polymorph of ThB2O5, denoted α, synthesised herein using a known borax, B2O3–Na2B4O7, high temperature solid method, was found to transform to the β polymorph when exposed to conditions of 4 GPa and ∼900 °C. Compared to the α polymorph, β-ThB2O5 has smaller molar volume by approximately 12%. Exposing a mixture of the α and β polymorphs to HT/HP conditions ex situ further demonstrated the preferred higher-pressure phase being β, with no α phase material being observed via Rietveld refinements against laboratory X-ray powder diffraction (PXRD) measurements. In situ heating PXRD measurements on α-ThB2O5 from RT to 1030 °C indicated that α-ThB2O5 transforms to the β variant at approximately 900 °C via a 1st order mechanism. β-ThB2O5 was found to exist only over a narrow temperature range, decomposing above 1050 °C. Ab initio calculations using density functional theory (DFT) with the Hubbard U parameter indicated, consistent with experimental observations, that β is both the preferred phase at higher temperatures and high pressures. Interestingly, it was found by switching from B2O3–Na2B4O7 to H3BO3–Li2CO3 flux using consistent high temperature solid state conditions for the synthesis of the α variant, β-ThB2O5 could be generated. Comparison of their single crystal measurements showed this was identical to that obtained from HT/HP conditions. [ABSTRACT FROM AUTHOR]

With the extensive usage of gadolinium-based contrast agents (GBCAs) in magnetic resonance imaging (MRI), gadolinium deposition has been observed in the brain, kidneys, liver, etc., and this is also closely related to the development of nephrogenic systemic fibrosis (NSF) in patients with renal dysfunction. Chelation, thereby promoting the elimination of deposited Gd(III), seems to be promising for alleviating these problems. Despite many ligands suitable for chelation therapy having been studied, the decorporation of transition metals (e.g. iron, copper, lead, etc.) and actinides (e.g. uranium, plutonium, etc.) has long been a primary concern, whereas the study of Gd(III) has been extremely limited. Due to their excellent metal binding abilities in vivo and therapeutic effects toward neurodegenerative diseases, bidentate hydroxypyridinone ligands are expected to be able to remove Gd(III) from the brain, kidneys, bones, and liver. Herein, the Gd(III) decorporation efficacy of a bidentate hydroxypyridinone ligand (Me-3,2-HOPO) has been evaluated. The complexation behavior between Me-3,2-HOPO and Gd(III) in solution and solid states was characterized with the assistance of potentiometric titration and X-ray diffraction techniques, respectively. Solution-based thermodynamic studies illustrate that the dominant species of complex between Gd(III) and Me-3,2-HOPO (HL) is GdL2+ (log β120 = 11.8 (3)) at pH 7.4. The structure of the Gd–Me-3,2-HOPO crystal obtained from a room temperature reaction reveals the formation of a Gd(III) dimer that is chelated by four ligands as a result of metal ion hydration and ligand complexation. Cellular Gd(III) removal assays illustrate that Me-3,2-HOPO could effectively reduce final amounts of gadolinium by 77.6% and 66.1% from rat renal proximal tubular epithelial (NRK-52E) cells and alpha mouse liver 12 (AML-12) cells, respectively. Our current results suggest the potential of bidentate HOPO ligands as an effective approach to treat patients suffering from Gd(III) toxicity. [ABSTRACT FROM AUTHOR]

Scintillators display radioluminescent properties when irradiated by high‐energy photons and therefore play an essential role in radiation detection. The current inventory of scintillators is overwhelmingly represented by achiral structures, where the radioluminescence propagates isotropically after generation. Herein, we demonstrate that chiral perovskites of (R‐3AP)PbBr3Cl⋅H2O (R‐3APP) and (S‐3AP)PbBr3Cl⋅H2O (S‐3APP) emerge as a new type of scintillator displaying a distinct property of circularly polarized radioluminescence (CPRL). A high quantum yield of 27.6 %, high luminescence dissymmetric factors (glum) of 4×10−2, and high X‐ray absorption coefficients were observed for these compounds. As proof of concept, we fabricated a polarized scintillator pair by assembling chiral scintillator crystals, which provides a new strategy to attenuate optical crosstalk between the scintillators by precisely controlling the radioluminescence propagation and improves the X‐ray imaging quality at the boundary region. [ABSTRACT FROM AUTHOR]

Scintillators display radioluminescent properties when irradiated by high‐energy photons and therefore play an essential role in radiation detection. The current inventory of scintillators is overwhelmingly represented by achiral structures, where the radioluminescence propagates isotropically after generation. Herein, we demonstrate that chiral perovskites of (R‐3AP)PbBr3Cl⋅H2O (R‐3APP) and (S‐3AP)PbBr3Cl⋅H2O (S‐3APP) emerge as a new type of scintillator displaying a distinct property of circularly polarized radioluminescence (CPRL). A high quantum yield of 27.6 %, high luminescence dissymmetric factors (glum) of 4×10−2, and high X‐ray absorption coefficients were observed for these compounds. As proof of concept, we fabricated a polarized scintillator pair by assembling chiral scintillator crystals, which provides a new strategy to attenuate optical crosstalk between the scintillators by precisely controlling the radioluminescence propagation and improves the X‐ray imaging quality at the boundary region. [ABSTRACT FROM AUTHOR]

Multi‐level memory can greatly improve information density, so it has been widely studied. In this study, a carbazole‐based donor–acceptor polymer poly[2,7‐9‐(heptadecan‐9‐yl)‐9H‐carbazole‐alt‐7H‐benzimidazo[2,1‐a]benz[de]isoquinolin‐7‐one] (PCz‐BB) is synthesized, which exhibits flash‐type ternary memory behavior. Further, CdS nanoparticles (NPs) are embedded into the prepared polymer to enhance the storage performance. The current–voltage (I–V) characteristics of memory devices based on PCz‐BB:CdS composites and the effect of the embedding ratio of CdS NPs on the memory devices are studied. It is verified that the ON2/ON1/OFF current ratios of the devices at low CdS embedding concentrations are improved, and the threshold voltages are also reduced. The memory device based on the optimal embedding concentration (3 wt% CdS) exhibits a high ON2/ON1/OFF current ratio of 18631:72:1, a low threshold voltage of −0.40/−1.20 V, and excellent stability. The mechanism of resistive switching is explained by the theory of charge traps and conductive filaments. This work provides a new avenue for high‐performance multi‐level organic electrical storage materials. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The environmental contamination of uranium will occur in scenarios such as nuclear accidents and leakage from nuclear waste storage sites, which eventually leads to the internal uranium exposure of people, causing consequential injuries of renal failure, osteosarcoma, etc. The development of uranyl specific chelating agents that could sequester uranium in vivo is in urgent need and is important for the safe and efficient development of nuclear industry. Metal organic frameworks (MOFs) already serve as efficient uranium depletion materials in solutions of a wide range of pH and ionic strength for nuclear fuel recycling, uranium extraction from seawater, as well as environmental decontamination. Herein, a chromium‐based nano‐metal organic framework (nano‐MOF) functionalized interiorly with 3,2‐HOPO ligands, MIL‐101‐HOPO, is rationally synthesized. In vitro adsorption experiments show that MIL‐101‐HOPO exhibits high adsorption selectivity and fast adsorption kinetics for uranyl. The results of in vivo uranyl decorporation assays reveal that MIL‐101‐HOPO with the decoration of HOPO ligands on the interior wall exhibits significantly increased uranyl removal ratio in kidneys comparing to the pristine nMOFs, and is more effective than the clinically used ZnNa3‐DTPA. All those results corroborate the interior functionalization of MOFs as an efficient strategy to develop promising uranyl decorporation agents. [ABSTRACT FROM AUTHOR]

Radiation protective materials are widely applied to avoid occupational hazards from either particle emissions or high-energy electromagnetic waves. Herein, we present a boron imidazolate framework (BIF) as a novel neutron shielding additive with high neutron capture cross-section elements B/Li and H. The BIF1-based epoxy resin matrix (Ep-BIF1) possesses high thermal stability and excellent resistance capacity. The neutron radiation shielding property was characterized using an Am–Be source, in which the thermal neutron shielding efficiency of Ep-BIF1 is notably higher than that of Ep-B4C with equal boron concentration, showing potential applications as an advanced efficient neutron radiation shielding composite. [ABSTRACT FROM AUTHOR]

[Display omitted] • Glucose-derived microporous carbons with different and ratios was prepared. • GC-700-2.4 showed narrow pore size distribution with < 7 Å. • GC-700-2.4 showed high Kd of Radon for 9.51 L/g at ambient temperature. • GC-700-2.4 exhibited a potential application with the economic cost. Radon (Rn) is a radioactive noble gas and one of the primary culprits of lung cancer. Developing efficient adsorbents for Rn removal is of paramount importance, yet remains a daunting challenge due to the weak interaction between Rn and the adsorbent, particularly when low concentrations of Rn are present. Herein, a renewable biomass-derived carbon material consisting of rich ultramicropores was synthesized for record-high Rn adsorption under ambient condition. By meticulously selecting the carbonization precursor, chemical activator, and pyrolysis temperature, the optimized adsorbent, GC-700-2.4, exhibits a narrow pore distribution in the ultramicroporous range (<7 Å). The dynamic adsorption coefficient (K d) of GC-700-2.4 is determined to be 9.51 L/g based on radon breakthrough experiments, which is twice the value of the commercial Rn adsorbent, coconut shell activated carbon (K d = 4.65 L/g), and outperforms all other reported Rn adsorbents under comparable conditions. The superior Rn adsorption performance of GC-700-2.4 is attributed to the narrow ultramicropores in GC-700-2.4 that show enhanced confinement effect toward Rn. Consequently, GC-700-2.4 shows promising potential for practical applications as an efficient and cost-effective Rn adsorbent. [ABSTRACT FROM AUTHOR]

A highly crystalline one-dimensional zirconium phosphate, (NH4)2[ZrF(PO4)(HPO4)] (ZrP-3), was facilely synthesized by the ionothermal method. The robust structure and rich hydrogen-bonded network make ZrP-3 an excellent proton conductor by having a proton conductivity higher than 10−2 S cm−1 at 90 °C and 95% RH. The remarkable stability makes ZrP-3 a promising solid electrolyte material for proton exchange membrane fuel cells. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: We reported the synthesis, single crystal structure, and solid‐state UV‐Vis‐NIR spectroscopy of a new transplutonium metal‐organic framework (MOFs), Am(H2O)[PO[(C6H4)COO]3], denoted as AmTPO (TPO = tris(4‐carboxylphenyl)‐phosphineoxide). AmTPO forms a three‐dimensional metal−organic framework structure with americium dimers as the secondary building unit. Clear 5f → 5f transitions attributed to trivalent americium was observed in the absorption spectrum of AmTPO ranging from 300 to 1200 nm. Notably, AmTPO can maintain the crystallinity with no observable structural degradation within several months after being synthesized, revealing a long‐term radiation resistance of this structure and the potential application of MOFs as a platform for nuclear waste disposal. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel Zr(IV)-based MOF with high-density free carboxylic groups was constructed. • The MOF demonstrates high stability and excellent uranium removal performance. • Dynamic sorption tests highlight its potential for treating radioactive wastewater. • The mechanism for its excellent ability to adsorb U(VI) was investigated. The extraction of uranium from aqueous environments, including the ocean and radioactive wastewater, represents a significant challenge with profound implications for energy resources and environmental remediation. This work presents the design and synthesis of a novel highly stable carboxylated metal–organic framework, BUT-12-3COOH, which achieves excellent U(VI) extraction ability from water. BUT-12-3COOH features high-density free carboxylic groups, exceptional chemical stability, fast kinetics, and high adsorption capacity for U(VI). Dynamic sorption experiments further demonstrated the potential of BUT-12-3COOH in treating real radioactive wastewater. The mechanisms for the U(VI) capture of BUT-12-3COOH are investigated through the combination of EDS, FT-IR, and XPS analysis. The results of this study underscore the promising utility of BUT-12-3COOH as an effective sorbent for extracting radionuclides from environmental specimens and liquid nuclear waste streams. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Halide hybrid perovskites are attracting considerable attention as highly promising candidates for directly sensing X‐ray radiation, but it is challenging to realize passive X‐ray detection without an external power supply. However, the bulk photovoltaic effect (BPVE) in ferroelectrics promotes the independent separation of photoexcited carriers. Herein, by dimensionality reconstruction of a pure‐two‐dimensional (P‐2D) monolayered perovskite (CH3OC3H9N)2PbBr4, we obtained a quasi‐two‐dimensional (Q‐2D) ferroelectric (CH3OC3H9N)2CsPb2Br7. Converting P‐2D into Q‐2D perovskite stimulates a significant BPVE associated with robust ferroelectricity, as well as an enhanced mobility lifetime product. These features show the potential of the first passive X‐ray detector based on ferroelectrics with an impressive sensitivity up to 410 μC Gy−1 cm−2 at zero bias, which is even superior to the value of the state‐of‐the‐art α‐Se detector operated at relatively high bias. [ABSTRACT FROM AUTHOR]

Halide hybrid perovskites are attracting considerable attention as highly promising candidates for directly sensing X‐ray radiation, but it is challenging to realize passive X‐ray detection without an external power supply. However, the bulk photovoltaic effect (BPVE) in ferroelectrics promotes the independent separation of photoexcited carriers. Herein, by dimensionality reconstruction of a pure‐two‐dimensional (P‐2D) monolayered perovskite (CH3OC3H9N)2PbBr4, we obtained a quasi‐two‐dimensional (Q‐2D) ferroelectric (CH3OC3H9N)2CsPb2Br7. Converting P‐2D into Q‐2D perovskite stimulates a significant BPVE associated with robust ferroelectricity, as well as an enhanced mobility lifetime product. These features show the potential of the first passive X‐ray detector based on ferroelectrics with an impressive sensitivity up to 410 μC Gy−1 cm−2 at zero bias, which is even superior to the value of the state‐of‐the‐art α‐Se detector operated at relatively high bias. [ABSTRACT FROM AUTHOR]

Low‐valent uranium‐element multiple bond complexes remain scarce, though there is burgeoning interest regarding to their bonding and reactivity. Herein, isolation of a uranium(III)‐carbon double bond complex [(Cp*)2U(CDP)](BPh4) (1) comprising a tridentate carbodiphosphorane (CDP) was reported for the first time. Oxidation of 1 afforded the corresponding U(IV) complex [(Cp*)2U(CDP)](BPh4)2 (2). The distance between U and C in 2 is 2.481 Å, indicating the existence of a typical U=C double bond, which is further confirmed by quantum chemical calculations. Bonding analysis suggested that the CDP also serves as both σ‐ and π‐donor in complex 1, though a longer U−C bond (2.666(3) Å) is observed. It implies that 1 is the first isolable mononuclear uranium(III) carbene complex. Moreover, these results suggest that CDPs are promising ligands to establish other low‐valent f‐block metal‐carbon multiple bond complexes. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The capture of highly radiotoxic 90Sr from an acidic waste solution during used fuel reprocessing and environmental remediation in a nuclear accident is desirable and challenging. Herein, we show a metal organic framework material (SNU-200) functionalized with an 18-crown-6-ether, whose specific binding site with an excellent affinity toward strontium leads to excellent Sr2+ adsorption capability under acidic conditions. This material exhibits a high adsorption capacity (44.37 mg g−1 at pH = 3), remarkable affinity (Kd = 3.63 × 104 mL g−1) and ultrahigh selectivity in the presence of interfering coexisting ions such as Na+, K+, Cs+, Mg2+, and Ca2+. [ABSTRACT FROM AUTHOR]

We disclose the intrinsic semiconducting properties of one of the largest mixed‐valent uranium clusters, [H3O+][UV(UVIO2)8(μ3‐O)6(PhCOO)2(Py(CH2O)2)4(DMF)4] (Ph=phenyl, Py=pyridyl, DMF=N,N‐dimethylformamide) (1). Single‐crystal X‐ray crystallography demonstrates that UV 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 UV 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 X‐ray excitation for 1: a large on‐off ratio of 500 and considerable charge mobility lifetime product of 2.3×10−4 cm2 V−1, as well as a high detection sensitivity of 23.4 μC Gyair−1 cm−2. [ABSTRACT FROM AUTHOR]

We disclose the intrinsic semiconducting properties of one of the largest mixed‐valent uranium clusters, [H3O+][UV(UVIO2)8(μ3‐O)6(PhCOO)2(Py(CH2O)2)4(DMF)4] (Ph=phenyl, Py=pyridyl, DMF=N,N‐dimethylformamide) (1). Single‐crystal X‐ray crystallography demonstrates that UV 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 UV 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 X‐ray excitation for 1: a large on‐off ratio of 500 and considerable charge mobility lifetime product of 2.3×10−4 cm2 V−1, as well as a high detection sensitivity of 23.4 μC Gyair−1 cm−2. [ABSTRACT FROM AUTHOR]