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Hematite is an excellent catalyst for solar water splitting but its practical performance is still low. In this work, a hetero phase of β-Fe 2 O 3 was firstly introduced in α-Fe 2 O 3 to optimize the internal structure, which can synergistically work with oxygen vacancy to enhance the charge extraction, facilitate the charge transport, and suppress the electron-hole recombination. As a result, the obtained hematite exhibits a high initial photocurrent of 2.72 mA/cm2 at 1.23 V vs. RHE, and can be well coupled with various further modifications such as P, Hf, and FeNiOOH to achieve an excellent photocurrent of 5.24 mA/cm2 at 1.23 V vs. RHE with a good stability over 100 h. Moreover, it can realize a benchmark solar-to-hydrogen conversion efficiency of 5.3% when connected to a commercial Si solar cell. The low cost, efficient, and stable hematite-based photoanodes may pave the way for practical solar water splitting. [Display omitted] • β-Fe 2 O 3 in hematite has been firstly reported to improve the PEC performance. • Hetero phase and oxygen vacancy can effectively enhance the bulk charge utilization. • It can achieve a high and stable photocurrent of 5.24 mA/cm2 at 1.23 V RHE. • A benchmark solar-to-hydrogen conversion efficiency of 5.3% can be obtained. [ABSTRACT FROM AUTHOR]

Flexible X-Ray Detector, Lanthanide Chalcogenide Scintillator, Luminescence, X-Ray Imaging Keywords: Flexible X-Ray Detector; Lanthanide Chalcogenide Scintillator; Luminescence; X-Ray Imaging EN Flexible X-Ray Detector Lanthanide Chalcogenide Scintillator Luminescence X-Ray Imaging 1 1 1 08/09/23 20230814 NES 230814 B Scintillators b . In their Communication (e202306465), Xing Dai, Shu-Xian Hu, Yaxing Wang et al. report the chalcogenide-based scintillator LaCsSiS SB 4 sb :1%Ce SP 3+ sp showing multiple properties, such as high light yield, fast decay time, low detection limit, and good radiation/moisture resistance. [Extracted from the article]

Thorium is not only a promising candidate for developing next generation nuclear fuel but also a potential radioactive contaminant. Efficient detection of thorium contamination is critically important in both nuclear science and environmental protection. We present here a 3D luminescent europium organic framework [Eu2(FDC)3(DMA)2]·4H2O (compound 1), which exhibits excellent hydrolytic stability and features highly selective detection capacity (KSV = 6.68 × 104) towards radioactive Th4+ ions among the selected monovalent, divalent and tervalent metal ions in aqueous solution. The detection limit of the material towards Th4+ is 3.49 × 10−5 mol L−1 which is close to the WHO standard. The detection capability and the sensing mechanism were demonstrated by Th4+ uptake kinetics, energy-dispersive spectroscopy mapping, absorption spectroscopy, luminescence lifetime, and competitive adsorption measurements. Compound 1 represents a rare case of a MOF based Th4+ probe. [ABSTRACT FROM AUTHOR]

Abstract We report here the investigation of using a luminescent europium organic framework, [Eu 2 (MTBC)(OH) 2 (DMF) 3 (H 2 O) 4 ]·2DMF·7H 2 O (denoted as compound 1), for detecting of both Cu2+ and UO 2 2+ with high sensitivity. Based on the spectroscopy analysis, compound 1 could selectively respond to Cu2+ and UO 2 2+ ions among other selected monovalent, divalent, trivalent metal cations based on a turn-off mechanism. The detection limit of compound 1 towards Cu2+ ion was as low as 17.2 μg/L, which is much lower than the maximum tolerable concentration of Cu2+ in drinking water (2 mg/L) defined by United States Environmental Protection Agency. On the other hand, the detection limit towards UO 2 2+ ions is 309.2 μg/L, which could be used for detecting uranium in relative severely contaminated areas. The concentration-dependent luminescence intensity evolution process could be fully understood by the absorption kinetics and isotherm investigations. Furthermore, the quenching mechanism was elucidated by the UV-vis, excitation, luminescence, and lifetime studies. Compound 1 , as the first MOF based luminescence probe for both Cu2+ and UO 2 2+ ions, provides insight into developing MOF-based multifunctional sensors for both nonradioactive and radioactive elements. Graphical abstract fx1 Highlights • A new lanthanide metal organic framework was used for both radioactive UO 2 2+ and nonradioactive Cu2+ detection. • The detection limits toward UO 2 2+ and Cu2+ are 17.2 ppb and 309.2 ppb respectively. • The material could be used for directly detecting UO 2 2+ and Cu2+ contamination in a wide concentration range. • The detection mechanism was systematically investigated by bath experiments, spectroscopy and lifetime studies. [ABSTRACT FROM AUTHOR]

99Tc contamination at legacy nuclear sites is a serious and unsolved environmental issue. The selective remediation of 99TcO4− in the presence of a large excess of NO3− and SO42− from natural waste systems represents a significant scientific and technical challenge, since anions with a higher charge density are often preferentially sorbed by traditional anion‐exchange materials. We present a solution to this challenge based on a stable cationic metal‐organic framework, SCU‐102 (Ni2(tipm)3(NO3)4), which exhibits fast sorption kinetics, a large capacity (291 mg g−1), a high distribution coefficient, and, most importantly, a record‐high TcO4− uptake selectivity. This material can almost quantitatively remove TcO4− in the presence of a large excess of NO3− and SO42−. Decontamination experiments confirm that SCU‐102 represents the optimal Tc scavenger with the highest reported clean‐up efficiency, while first‐principle simulations reveal that the origin of the selectivity is the recognition of TcO4− by the hydrophobic pockets of the structure. Capturing radioactive species: A robust 3D cationic metal‐organic framework material, SCU‐102, exhibits fast sorption kinetics, large uptake capacity, high distribution coefficient, and a record‐high TcO4− uptake selectivity. The material offers a solution to the long‐term challenge of 99Tc decontamination from complex natural water systems at legacy nuclear sites. [ABSTRACT FROM AUTHOR]

Three (3,4)-connected uranyl–organic frameworks (UOFs) with pto and tbo topologies were synthesized. The UOF with a pto net possesses a 2-fold interpenetrating network and exhibits 2D interconnected channels. The UOF with a tbo net is constructed from two types of ultralarge nanocages. All these compounds can efficiently remove large cationic dye crystal violet (CV) through a cation exchange mechanism. [ABSTRACT FROM AUTHOR]

Summary of main observation and conclusion: We present a new method for generating europium oxalate compounds by decomposing of N‐methyl 2‐pyrrolidone in HNO3 media. The reaction exhibits high selectivity towards Eu3+ over UO22+, which suggests that these conditions could be applied to a selective crystallization based separation system for trivalent lanthanides and hexavalent actinides. In this work, a new method for the separation of trivalent Eu3+ and hexavalent UO22+ in initial high‐acidity HNO3 solution is presented. N‐Methyl 2‐pyrrolidone was added in the HNO3 solution where Eu3+ and UO22+ coexisted, then the solution was heated. Eu3+ will react with oxalic acid and dimethylamine produced by N‐methyl 2‐pyrrolidone and form compound NH2(CH3)2[Eu(C2O4)2(H2O)], while UO22+ remains in the solution. This method provide a new strategy for separation of trivalent Eu3+ and hexavalent UO22+. [ABSTRACT FROM AUTHOR]

The structures of Ti-oxo clusters were thought to be rigid given the high stability of Ti–O–Ti bonds. A Ti32-oxo nanoring, Ti32(μ2-O)8(μ3-O)8(L)16(gly)32(glyH)16·12(glyH2)·29(IPA) (L = 4-aminobenzoic acid, glyH2 = ethylene glycol, IPA = isopropanol) (1), experiences an unexpected single-crystal-to-single-crystal desolvation process upon exposure to air, affording another new crystalline phase Ti32-oxo cluster (1-Dry) with a shrunk ring size. [ABSTRACT FROM AUTHOR]

Abstract In the present study, the macroscopic sorption behaviors and microscopic immobilization mechanisms of Ni(II) at cryptomelane/water interfaces were explored using the combination of batch sorption technique, desorption procedure, theoretical simulation, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS) analyses. The good simulation of the pseudo-second-order model on the sorption kinetics data suggests a driving force of chemical sorption rather than mass transport or physical interaction. The sorption trends and uptake mechanisms are obviously related to the solution pH, with cation exchange or outer-sphere surface complexation at an acidic pH of 4.0, inner-sphere surface complexation in both the edge-shared (ES) and double corner-shared (DCS) modes at a neutral pH of 7.0, and precipitation of α-Ni(OH) 2 (s) phase at a highly alkaline pH of 10.0. The gradual increase of Ni(II) sorption amount with solution temperature rising from 293 K to 333 K is consistent with the increased ratio of the weak DCS configuration. The research findings herein can help us better understand the migration and transformation trends of Ni(II) in the manganese mineral-riched aquatic environment. Graphical abstract Image 1 Highlights • Interaction mechanisms of Ni(II) with cryptomelane were explored by combining multiple techniques. • Relative contributions of different uptake processes were verified from ligand extraction data. • Ni(II) binding modes were clearly identified with theoretical simulation and spectroscopic analyses. • Temperature rising enhanced the sorption amount of Ni(II) in double corner-shared binding mode. • Research findings facilitated the assessment of Ni(II) migration and fate in Mn-riched environment. [ABSTRACT FROM AUTHOR]

Deferiprone (3-hydroxy-1,2-dimethyl-4(1H)-pyridone, DFP), which is a drug clinically used for removing heavy metals in vivo, was explored for its removal efficiency towards uranium. The reaction of uranyl nitrate hexahydrate with DFP at room temperature yielded the compound [(UO2)(H2O)(C7NO2H8)2]·4H2O (1), which crystallizes from a mixed solution of methanol and water (pH = 7.0). X-ray diffraction shows that the stable complexation of uranyl occurs from the coordination of two bidentate DFP ligands perpendicular to the O=U=O unit with a fifth coordinating oxygen atom coming from one water molecule, resulting in a pentagonal bipyramidal geometry. The formation constants of uranyl and DFP complexes were measured and the species distribution diagram illustrates that UO2L2 (94.6%) is the dominant uranyl-DFP complex in 0.1 M KCl solution at physiological pH = 7.4. The results from both crystallographic and potentiometric studies imply that the metal : ligand ratio is 1 : 2. The effectiveness of using DFP to remove uranium was examined at the cellular level, and the results suggest that it can significantly reduce the cellular uptake and increase the cellular release of U(vi) in renal proximal tubular epithelial cells (NRK-52E). [ABSTRACT FROM AUTHOR]

Bis(2-propyloxy)calix[4]arene-crown-6 ( L1 ) is a ligand with high affinity in the extraction of Cs(I). In this work, acrylamido and propionamido groups are decorated at the opposite site of 2-propyloxy on the phenyl ring of L1 , giving rise to the derivatives L2 and L3 , respectively. Complexation of all the three ligands with Cs(I) is characterized by NMR, spectrophotometric titration, crystal structure and DFT calculation. Both the NMR and spectrophotometric analysis suggest more significant variation of electron density on the phenyl rings in L2 and L3 than that in L1 in complexation with Cs(I). The stability constants (log β ) of the complexes are calculated to be 6.0 ± 0.1, 6.2 ± 0.1 and 6.3 ± 0.1 for Cs- L1 , Cs- L2 and Cs- L3 , respectively, by fitting of the absorption spectra. As reflected by the crystal structures and DFT calculations, the complexed cesium cation interacts with the crown ether moiety, the two rotated phenyl rings and the acrylamido/propionamido groups in L2 / L3 , which can be regarded as an intramolecular triple cooperative effect. Extraction of Cs(I) from aqueous solution is performed, and the distribution ratio is in line with the findings in stability constant and interaction energy. This work contributes to further improvement of the extraction of cesium cation by 1,3-alternate calix[4]arene-crown-6. [ABSTRACT FROM AUTHOR]

Abstract: The combination of high atomic number and high oxidation state in UVI materials gives rise to both high X‐ray attenuation efficiency and intense green luminescence originating from ligand‐to‐metal charge transfer. These two features suggest that UVI materials might act as superior X‐ray scintillators, but this postulate has remained substantially untested. Now the first observation of intense X‐ray scintillation in a uranyl–organic framework (SCU‐9) that is observable by the naked eye is reported. Combining the advantage in minimizing the non‐radiative relaxation during the X‐ray excitation process over those of inorganic salts of uranium, SCU‐9 exhibits a very efficient X‐ray to green light luminescence conversion. The luminescence intensity shows an essentially linear correlation with the received X‐ray intensity, and is comparable with that of commercially available CsI:Tl. SCU‐9 possesses an improved X‐ray attenuation efficiency (E>20 keV) as well as enhanced radiation resistance and decreased hygroscopy compared to CsI:Tl. [ABSTRACT FROM AUTHOR]

Abstract: The combination of high atomic number and high oxidation state in UVI materials gives rise to both high X‐ray attenuation efficiency and intense green luminescence originating from ligand‐to‐metal charge transfer. These two features suggest that UVI materials might act as superior X‐ray scintillators, but this postulate has remained substantially untested. Now the first observation of intense X‐ray scintillation in a uranyl–organic framework (SCU‐9) that is observable by the naked eye is reported. Combining the advantage in minimizing the non‐radiative relaxation during the X‐ray excitation process over those of inorganic salts of uranium, SCU‐9 exhibits a very efficient X‐ray to green light luminescence conversion. The luminescence intensity shows an essentially linear correlation with the received X‐ray intensity, and is comparable with that of commercially available CsI:Tl. SCU‐9 possesses an improved X‐ray attenuation efficiency (E>20 keV) as well as enhanced radiation resistance and decreased hygroscopy compared to CsI:Tl. [ABSTRACT FROM AUTHOR]

A uranyl phosphonate framework, (UO2)2(1,3-pbp)(H2O)2·2H2O (UPF-1) (1,3-pbp = 1,3-phenylenebis(phosphonic acid)), experiences a thermally induced order–disorder transition, leading to a negative linear correlation between the photoluminescence intensity and temperature, and may find application as a luminescent thermometer. [ABSTRACT FROM AUTHOR]

Abstract: Actinide based metal–organic frameworks (MOFs) are unique not only because compared to the transition‐metal and lanthanide systems they are substantially less explored, but also owing to the uniqueness of actinide ions in bonding and coordination. Now a 3D thorium–organic framework (SCU‐11) contains a series of cages with an effective size of ca. 21×24 Å. Th4+ in SCU‐11 is 10‐coordinate with a bicapped square prism coordination geometry, which has never been documented for any metal cation complexes. The bicapped position is occupied by two coordinated water molecules that can be removed to afford a very unique open Th4+ site, confirmed by X‐ray diffraction, color change, thermogravimetry, and spectroscopy. The degassed phase (SCU‐11‐A) exhibits a Brunauer–Emmett–Teller surface area of 1272 m2 g−1, one of the highest values among reported actinide materials, enabling it to sufficiently retain water vapor, Kr, and Xe with uptake capacities of 234 cm3 g−1, 0.77 mmol g−1, 3.17 mmol g−1, respectively, and a Xe/Kr selectivity of 5.7. [ABSTRACT FROM AUTHOR]

Abstract: Actinide based metal–organic frameworks (MOFs) are unique not only because compared to the transition‐metal and lanthanide systems they are substantially less explored, but also owing to the uniqueness of actinide ions in bonding and coordination. Now a 3D thorium–organic framework (SCU‐11) contains a series of cages with an effective size of ca. 21×24 Å. Th4+ in SCU‐11 is 10‐coordinate with a bicapped square prism coordination geometry, which has never been documented for any metal cation complexes. The bicapped position is occupied by two coordinated water molecules that can be removed to afford a very unique open Th4+ site, confirmed by X‐ray diffraction, color change, thermogravimetry, and spectroscopy. The degassed phase (SCU‐11‐A) exhibits a Brunauer–Emmett–Teller surface area of 1272 m2 g−1, one of the highest values among reported actinide materials, enabling it to sufficiently retain water vapor, Kr, and Xe with uptake capacities of 234 cm3 g−1, 0.77 mmol g−1, 3.17 mmol g−1, respectively, and a Xe/Kr selectivity of 5.7. [ABSTRACT FROM AUTHOR]

In the present work, the titanate nanotubes (TNTs) were synthesized via the hydrothermal approach and the phytic acid decorated TNTs (PA/TNTs) were prepared by using the one-pot method. Batch technique was adopted to explore the removal performance of TNTs and PA/TNTs towards Eu(III) under various environmental conditions. At pH 4.0 and 5.5, the sorption of Eu(III) on TNTs decreased with increasing NaNO 3 concentration, while the removal of Eu(III) by PA/TNTs was independent of ionic strength. The saturated Eu(III) sorption capacities of TNTs and PA/TNTs were calculated to be 9.52 × 10 −4 and 9.57 × 10 −4 mol/g at pH 5.5 and 298 K, being higher than a variety of previously reported adsorbents. PA/TNTs also exhibited high selectivity for capturing Eu(III) from a simulated wastewater containing multiple competing metal ions. According to the Fourier transform infrared spectroscopy (FTIR), solid fluorescence and X-ray photoelectron spectroscopy (XPS) analysis, the predominant removal mechanisms of TNTs and PA/TNTs towards Eu(III) at pH 5.5 were ion exchange/outer-sphere surface complexation and inner-sphere surface complexation, respectively. These experimental findings demonstrated the wide application prospects of TNTs and PA/TNTs for the highly efficient purification of Eu(III)-bearing wastewater. [ABSTRACT FROM AUTHOR]

Deep eutectic mixtures were deployed for the preparation of porous layered [Sn3Se7]n2n− single crystals. The perforation on the layers accentuates the negative temperature dependence of its band gap, resulting in remarkable thermochromic performance. Substitution of the hydroxo group by the methyl group provides an enhanced hydrophobicity for the organic template, leading to an anhydrous product with a remarkably improved thermal stability and thus reversible thermochromic properties. [ABSTRACT FROM AUTHOR]

Although no evident hydrogen-bond network appears, an ultrahigh proton conductivity of 2.91 × 10−2 S cm−1 at 363 K and 90% RH with an ultralow activation energy of 0.10 eV was observed in an anionic lanthanide-organic framework Na2[Eu(SDB)2(COO)]·0.375DMF·0.4H2O (1); both values approach the records among all reported proton-conducting MOF materials. This suggests that the proton conduction process in 1 is reminiscent of the Grotthuss mechanism, which together reveals an effective proton transportation pathway associated with aligned Na+ and their coordinated water. [ABSTRACT FROM AUTHOR]

A new 1-D zirconium phosphonate [(CH3)2NH2]2[Zr(CH2(HPO3)(PO3))2] (SZ-5) was synthesized via a solvothermal reaction and its single crystal structure was elucidated. SZ-5 exhibits efficient strontium exchange capability with high uptake capacity and selectivity, as further demonstrated by the radioactive Sr-90 removal from a real contaminated seawater sample with an extremely high ionic strength. In addition, the measured proton conductivity at 90 °C and 90% relative humidity (RH) is 5.65 × 10−4 S cm−1. The efficient ion-exchange ability and the moderate proton conductivity suggest the potential applications of SZ-5 in fuel cells or in the remediation of contaminated water. [ABSTRACT FROM AUTHOR]

The present study sheds some light on the long‐standing debate concerning the coordination properties between uranyl ions and the amidoxime ligand, which is a key ingredient for achieving efficient extraction of uranium. Using X‐ray absorption fine structure combined with theoretical simulation methods, the binding mode and bonding nature of a uranyl–amidoxime complex in aqueous solution were determined for the first time. The results show that in a highly concentrated amidoxime solution the preferred binding mode between UO22+ and the amidoxime ligand is η2 coordination with tris‐amidoximate species. In such a uranyl–amidoximate complex with η2 binding motif, strong covalent interaction and orbital hybridization between U 5f/6d and (N, O) 2p should be responsible for the excellent binding ability of the amidoximate ligand to uranyl. The study was performed directly in aqueous solution to avoid the possible binding mode differences caused by crystallization of a single‐crystal sample. This work also is an example of the simultaneous study of local structure and electronic structure in solution systems using combined diagnostic tools. [ABSTRACT FROM AUTHOR]

We present a depleted uranium-based metal organic framework, UO2(C8H3O6N)·DMF, that exhibits highly sensitive and selective detection towards Fe3+ ions in aqueous media with an extremely low detection limit of 6.3 ppb. This work offers insight into exploring the potential applications of actinide-based metal organic frameworks in the area of chemical sensing with intrinsic advantages of high selectivity and sensitivity. [ABSTRACT FROM AUTHOR]

When exposed to water, the two-dimensional uranyl–organic layered compound [(CH3)2NH2][(UO2)(BCPBA)]·2DMF·H2O (H3BCPBA = 3,5-bis (4′-carboxylphenoxy) benzoic acid) gradually undergoes a complete single-crystal-to-single-crystal phase transition to [(CH3)2NH2][(UO2)(BCPBA)]·3.4H2O, resulting in an enhanced ligand–ligand interaction between the adjacent layers. This process gives rise to initial quenching of the uranyl photoluminescence followed by subsequent recovery of the photoluminescence with a much elevated intensity, as a unique case of aggregation-induced emission in an extended solid system, further confirmed by DFT analysis on bonding. [ABSTRACT FROM AUTHOR]

Bis(trifluoromethylsulfonyl)imide (NTf 2 − ) and hexafluorophosphate (PF 6 − ) are the most frequently used anions for hydrophobic ionic liquids (ILs) which have been considered as promising solvents in the extraction of cesium ions. The interactions of NTf 2 − and PF 6 − with Cs + were explored in this work. The results of DFT calculation indicated that both Cs + and Cs(18C6) + prefer to interact with two NTf 2 − or PF 6 − anions in gas phase, where 18C6 is 18-crown-6. The complex of Cs(NTf 2 ) 2 − was observed in electrospray ionization mass spectrometry (ESI-MS), and the complexes of [Cs(18C6)NTf 2 ] 2 and [Cs(18C6)PF 6 ] 2 were crystallized in which Cs(18C6) + interacted with two anions. The interactions of NTf 2 − with cesium resulted in a synergistic effect between dicyclohexano-18-crown-6 (DCH18C6) and NTf 2 − in the extraction of Cs + using n -octanol as diluent. However, DFT calculation revealed that the complex Cs(DCH18C6) + interacted with one NTf 2 − anion was more thermodynamically stable than that with two anions in organic phase, different from that in gas phase. [ABSTRACT FROM AUTHOR]

In this study, the inorganic-organic hybrid of PA/TNTs was synthesized and characterized by using multiple analysis techniques. Batch experiments were conducted to investigate the removal performance of PA/TNTs towards U(VI). The sorption kinetics procedure achieved equilibrium within 6 h. The maximum sorption capacity at 293 K and pH 5.0 was calculated to be 1.16 × 10 −3 mol/g. In addition, the PA/TNTs composite showed a higher sorption selectivity towards U(VI) over many other metal ions. The ionic strength experiments, desorption results, X-ray diffraction (XRD), solid fluorescence, extended X-ray adsorption fine structure (EXAFS) and Fourier transform infrared spectroscopy (FTIR) analysis suggested the predominant sorption mechanism was inner-sphere complexation rather than ion exchange or precipitation. Overall, the synthesized PA/TNTs composite could be utilized as a cost-effective material for the removal of U(VI) from wastewater. [ABSTRACT FROM AUTHOR]

[Display omitted] • A three-step uranium oxide reduction recovery process has been developed. • The uranium recovered by this process achieved a purity of over 99.9% • The overall recovery rate of uranium reached 98.6%. • Heavy metal concentrations in wastewater meet WHO guidelines by this process. Resource utilization of uranium from the nuclear wastewater is of significance, and the facile strategy to recover high purity uranium oxide directly from wastewater is urgent to develop. Herein, a three-step uranium oxide reduction recovery process (URRP), that is integrated solid–liquid separation (SLS) and electrochemical purification (EP) together with solid-phase uranium re-recovery (SUR), is designed and applied for uranium reduction and purification. The SEM and ICP results were used to determine the carbonate system as the optimal separation system and the Ti electrode as the optimal electrochemical purification electrode. The single electron transfer process of uranyl ions in carbonate was established using cyclic voltammetry. Such three-step recovery process achieves a high-efficient recovery of uranium with a purity of over 99.9% in complex wastewater systems, and an improved return rate of uranium as high as 98.6%. Furthermore, the concentration of metal ions in wastewater is reduced to the standard set by the World Health Organization. Such a URRP offers a very promising solution for the treatment of wastewater and the recovery of high purity uranium. [ABSTRACT FROM AUTHOR]

Precise detection of low-dose X- and γ-radiations remains a challenge and is particularly important for studying biological effects under low-dose ionizing radiation, safety control in medical radiation treatment, survey of environmental radiation background, and monitoring cosmic radiations. We report here a photoluminescent uranium organic framework, whose photoluminescence intensity can be accurately correlated with the exposure dose of X- or γ-radiations. This allows for precise and instant detection of ionizing radiations down to the level of 10−4 Gy, representing a significant improvement on the detection limit of approximately two orders of magnitude, compared to other chemical dosimeters reported up to now. The electron paramagnetic resonance analysis suggests that with the exposure to radiations, the carbonyl double bonds break affording oxo-radicals that can be stabilized within the conjugated uranium oxalate-carboxylate sheet. This gives rise to a substantially enhanced equatorial bonding of the uranyl(VI) ions as elucidated by the single-crystal structure of the γ-ray irradiated material, and subsequently leads to a very effective photoluminescence quenching through phonon-assisted relaxation. The quenched sample can be easily recovered by heating, enabling recycled detection for multiple runs. [ABSTRACT FROM AUTHOR]

Precise detection of low-dose X- and γ-radiations remains a challenge and is particularly important for studying biological effects under low-dose ionizing radiation, safety control in medical radiation treatment, survey of environmental radiation background, and monitoring cosmic radiations. We report here a photoluminescent uranium organic framework, whose photoluminescence intensity can be accurately correlated with the exposure dose of X- or γ-radiations. This allows for precise and instant detection of ionizing radiations down to the level of 10−4 Gy, representing a significant improvement on the detection limit of approximately two orders of magnitude, compared to other chemical dosimeters reported up to now. The electron paramagnetic resonance analysis suggests that with the exposure to radiations, the carbonyl double bonds break affording oxo-radicals that can be stabilized within the conjugated uranium oxalate-carboxylate sheet. This gives rise to a substantially enhanced equatorial bonding of the uranyl(VI) ions as elucidated by the single-crystal structure of the γ-ray irradiated material, and subsequently leads to a very effective photoluminescence quenching through phonon-assisted relaxation. The quenched sample can be easily recovered by heating, enabling recycled detection for multiple runs. [ABSTRACT FROM AUTHOR]

Uranium is not only a strategic resource for the nuclear industry but also a global contaminant with high toxicity. Although several strategies have been established for detecting uranyl ions in water, searching for new uranium sensor material with great sensitivity, selectivity, and stability remains a challenge. We introduce here a hydrolytically stable mesoporous terbium(III)-based MOF material compound 1, whose channels are as large as 27 Å × 23 Å and are equipped with abundant exposed Lewis basic sites, the luminescence intensity of which can be efficiently and selectively quenched by uranyl ions. The detection limit in deionized water reaches 0.9 µg/L, far below the maximum contamination standard of 30 µg/L in drinking water defined by the United States Environmental Protection Agency, making compound 1 currently the only MOF material that can achieve this goal. More importantly, this material exhibits great capability in detecting uranyl ions in natural water systems such as lake water and seawater with pH being adjusted to 4, where huge excesses of competing ions are present. The uranyl detection limits in Dushu Lake water and in seawater were calculated to be 14.0 and 3.5 µg/L, respectively. This great detection capability originates from the selective binding of uranyl ions onto the Lewis basic sites of the MOF material, as demonstrated by synchrotron radiation extended X-ray adsorption fine structure, X-ray adsorption near edge structure, and first principles calculations, further leading to an effective energy transfer between the uranyl ions and the MOF skeleton. [ABSTRACT FROM AUTHOR]

This study highlights the simultaneous sequestration of U(VI) and arsenate at the goethite/water interface. The uptake trends and speciation of these two components were related with molar arsenate/U(VI) ratio, solution pH, contact order and aging time. A metastable [UO(HAsO)·HO] was observed after 3 days and then this solid completely transformed into Na(UOAsO)·3HO after 7 days. The disodium ethylenediamine tetraacetate ligand gave rise to the complete dissolution of Na(UOAsO)·3HO phase and the release of U(VI) and arsenate back into the solution. The experimental findings facilitated us better comprehend the migration and fate of coexisting U(VI) and arsenate in the aquatic environment. [ABSTRACT FROM AUTHOR]

Uranium (U(VI)) pollution comes from the development and utilization of natural minerals. Based on a new concept of ecological restoration of uranium pollution into natural minerals, a new artificial mineralized process was proposed to immobilize uranium (U(VI)) for wastewater decontamination. In this work, three systems of Mg 3 (PO 4) 2 + UO 2 2+, Mg2+ + PO 4 3− + UO 2 2+ and Mg2+ + PO 4 3− + Mg 3 (PO 4) 2 + UO 2 2+ were designed. Batch experiments and theoretical calculation were conducted to study the U(VI) immobilization effectiveness and artificial mineralization mechanisms. U(VI) removal efficiencies reached up to 96% in the pH value of 5.0 in the three systems. Both precipitation and surface adsorption contributed to favorable U(VI) removal in Mg 3 (PO 4) 2 + UO 2 2+, but resulting in U desorption. Precipitation of Mg2+, PO 4 3− and UO 2 2+ into saleeite (Mg(UO 2) 2 (PO 4) 2 ·10H 2 O) crystal contributed to UO 2 2+ immobilization in the Mg2+ + PO 4 3− + UO 2 2+ and Mg2+ + PO 4 3− + Mg 3 (PO 4) 2 + UO 2 2+ systems, resulting in the negligible U desorption. It is due to the crystallization of the Mg(UO 2) 2 (PO 4) 2 ·10H 2 O through precipitation of Mg2+ and PO 4 3− with UO 2 2+ in acidic medium. PHREEQC and Visual MINTEQ fitting confirmed the favorable precipitation of Mg2+ and PO 4 3− with UO 2 2+ into saleeite in acidic medium. Thus, the U(VI) immobilization effectiveness and artificial mineralization mechanism were understood, providing a promising strategy of artificial induced mineralization of Mg(UO 2) 2 (PO 4) 2 ·10H 2 O for U(VI) decontamination in wastewater. [Display omitted] • Artificially mineralization is proposed for immobilizing uranium. • Formation of Saleéite and chernikovite is the fate of uranium immobilization. • Theorical fitting confirmed the mineralization of dissolved Mg2+ and PO 4 3− with UO 2 2+. • The leaching rate of saleéite and chernikovites is negligible. • P/U and Mg/U molar ratios determined the artificially mineralization process. [ABSTRACT FROM AUTHOR]

Barium cerate doped with tetravalent Th is successfully synthesized by a traditional Pechni method. The BaCe 0.7 Th 0.1 Y 0.2 O 3−δ (BCT71) composites were applied to an anode supported coin single cell consisting of Ni-BCT71 anode/BCT71 electrolyte/ BCT71-La 0.7 Sr 0.3 FeO 3−δ cathode. The assembled cell is tested from 600 °C to 700 °C with humidified hydrogen (∼3% H 2 O) as the fuel and the static air as the oxidant. An open-circuit potential of 0.93 V and a maximum power density of 104 mW cm −2 are obtained for the single cell with an interface resistance of 0.98 Ω cm 2 at 700 °C. [ABSTRACT FROM AUTHOR]

The equatorial coordination nature of the uranyl unit has resulted in only three uranyl borate 3D framework compounds reported so far formed from boric acid flux reactions conducted at 190 °C while all others are 2D layers. Here in this work, by increasing the reaction temperature to 250 °C, a new potassium uranyl borate K[(UO2)B6O10(OH)] (KUBO-4) framework compound is synthesized that shares the same layer topology with the previously reported 2D layered KUBO-1. The 3D structure of KUBO-4 is achieved by interlayer hydroborate condensation. The KUBO-4 was further characterized with single crystal XRD, SHG and fluorescence spectra, and TG/DSC measurements. A deep understanding regarding the dissolution behaviours of uranyl borate is achieved via solubility studies of the KUBO-1 and KUBO-4 performed using a combination of ICP-MS, powder XRD, and fluorescence spectroscopy techniques. The results confirm the lack of stability of borates in aqueous solutions with the presence of coordinating ligands in the environment regardless of the structure types. [ABSTRACT FROM AUTHOR]

It is shown that UVO2+ ions can reside at UVIO22+ lattice sites during mild reduction and crystallization process under solvothermal conditions, yielding a complicated and rare mixed-valent uranium phosphonate compound that simultaneously contains UIV, UV, and UVI. The presence of uranium with three oxidation states was confirmed by various characterization techniques, including X-ray crystallography, X-ray photoelectron, electron paramagnetic resonance, FTIR, UV/Vis-NIR absorption, and synchrotron radiation X-ray absorption spectroscopy, and magnetism measurements. [ABSTRACT FROM AUTHOR]

Cooperative performance of mixed-valent Eu2+/Eu3+ in single-compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu2+ oxidation. Using the tunable nature of the metal-ion nodes in metal-organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu2+/Eu3+ with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic- and sensitized-emissions of Eu2+ and Eu3+, and long-lived luminescence from charge transfer. Color rendering can be easily achieved by fine-tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu2+/Eu3+ emissions provides outstanding properties for applications as self-calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb3+ into the MOFs results in white light, utilizing all Eu2+,Tb3+, and Eu3+ emissions in a single crystalline lattice. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ni-Co LDO could be obtained by calcination of Ni-Co LDH. • The morphology of the Ni-Co LDO can be adjusted by the calcination temperature. • The Ni-Co LDO-500 prefer removing uranium to Ni-Co LDH. • Electrostatic attraction, surface complexation and memory effect contributed to U(VI) recovery. • Ni-Co LDO-500 showed good stability and excellent regeneration ability. The utilization and development of nuclear energy has resulted in the discharge of uranium-containing wastewater. Layer double hydroxides (LDHs) and oxides (LDOs) were reported for efficient extracting U(VI) from wastewater. In this work, nickel–cobalt layered double oxide (Ni-Co LDO-X, X represents the calcination temperature) with excellent electrostatic attraction and complexation was synthesized via calcination of nickel–cobalt layered double hydroxide (Ni-Co LDH) under air atmosphere for extracting U(VI) comparing to Ni-Co LDH. Scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and zeta potential analysis were conducted to characterize the Ni-Co LDO-X. Batch adsorption experiments were carried out to investigate the U(VI) extraction properties. The U(VI) adsorption capacity on Ni-Co LDO-500 increased over 3 times compared to that of Ni-Co LDH. The process of uranium removed by Ni-Co LDO-500 conforms to the Langmuir model, the calculated maximum adsorption capacity is 707.91 mg/g. The results suggested that the excellent U(VI) adsorption ability on Ni-Co LDO-500 mainly dominated by the memory effect, electrostatic interaction, and complexation on the outer-sphere surface. Ni-Co LDO-500 has excellent regeneration ability in five adsorption/desorption experiments. The Ni-Co LDO-500 had favorable ability in removing uranium in actual wastewater with the residual concentration being lower than 0.05 mg/L. The above results highlight that the Ni-Co LDO-500 is promising to be used for the decontamination of uranium in actual uranium-containing wastewater. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ni-MOF can achieve selectively capture towards Xe/Kr through the window-cage structure with parallel aromatic rings. • The Xe loading capacity of Ni-MOF is the highest among all MOFs without open metal sites. • VdWs Calculations demonstrate the sorption selectivity of Xe over Kr within Ni-MOF originates from a special sandwiched π-Xe-π interaction. Efficient capture and separation of xenon (Xe) and krypton (Kr) from nuclear fuel reprocessing plants is of great significance for the control of discharge of gaseous radioisotopes into the environment. However, due to the similar size and chemically inert spherical properties of Xe/Kr, the discovery of an adsorbent with both high adsorption capacity and high selectivity remains a challenge. Here, we report a microporous MOF (Ni-MOF, [Ni 2 IINiIII(μ 3 -OH)(bdc) 3 (tpt)]·guest) featuring two different cavities with an appropriate triangular hole window size. One is composed of parallel aromatic rings with spacings of approximately 4.3 Å comparable to the kinetic diameter of Xe (4.047 Å), affording excellent binding affinity for Xe while the larger one with narrow pore window provides sufficient space for gas adsorption. The Ni-MOF material exhibits an exceptionally high Xe uptake of 5.43 mmol/g and Xe/Kr selectivity of 7.66 at 298 K and 1 bar. The adsorption capacity is the highest among all MOFs without open-metal-sites. Furthermore, the sorption selectivity of Xe over Kr within Ni-MOF originates from a special sandwiched π-Xe-π interaction revealed by Van der Waals interaction calculations. [ABSTRACT FROM AUTHOR]

The example of phase transformation from a centrosymmetric space group at low temperature (LT) to a chiral space group at high temperature (HT) is reported, which was clearly resolved in a single-crystal-to-single-crystal manner in a 3D uranyl(vi) phosphonate compound [TMA][(UO2)2(1,3-pbpH)(1,3-pbpH2)] (1) (TMA+ = tetramethylammonium cation; 1,3-pbpH4 = 1,3-phenylenebis(phosphonic acid)). [ABSTRACT FROM AUTHOR]

Three thorium(iv)-based metal–organic hybrid compounds with 2D layered and 3D framework structures exhibiting graphene-like (6,3) sheet topologies were prepared with linkers with threefold symmetry. These compounds contain rare and relatively anisotropic coordination environments for low-valent actinides that are similar to those often observed for high-valent actinide ions. [ABSTRACT FROM AUTHOR]

The solvothermal reaction of thorium nitrate and tris-(4-carboxylphenyl)phosphine oxide in DMF affords a centrosymmetric porous thorium organic framework compound [Th(TPO)(OH)(H2O)]·8H2O (1). In contrast, the ionothermal reaction of the same reagents in the ionic liquid 1-butyl-2,3-dimethylimidazolium chloride results in the formation of a rare example of a chiral and porous thorium organic framework compound, [C9H17N2][Th(TPO)Cl2]·18H2O (2), which is derived solely from achiral starting materials. The geometries of the Th(iv) centers in compounds 1 and 2 are both atypical for low valent actinides, which can be best described as a ten-coordinate spherical sphenocorona and an irregular muffin, respectively. A large cavity of 17.5 Å (max. face to face) × 8 Å (min. face to face) with a BET surface area of 623 m2 g−1 in compound 2 is observed. The poor stability indicated by thermal gravimetric analysis and the water-resistance test for compound 2 may be due to the unique anisotropic coordination geometry for thorium. Temperature-dependent luminescence studies for both compounds indicate that the trends in the intensity vary as the Th–Th distance and the coordination environments of Th(iv) centers change. [ABSTRACT FROM AUTHOR]

The limited long-term hydrolytic stability of rapidly emerging 3D-extended framework materials (MOFs, COFs, MOPs, etc.) is still one of major barriers for their practical applications as new solid-state electrolytes in fuel cells. To obtain hydrolytically stable materials, two H2PO4−-exchanged 3D inorganic cationic extended frameworks (CEFs) were successfully prepared by a facile anion-exchange method. Both anion-exchanged CEFs (YbO(OH)P and NDTBP) show significantly enhanced proton conductivity when compared with the original materials (YbO(OH)Cl and NDTB) with an increase of up to four orders-of-magnitude, reaching 2.36×10−3 and 1.96×10−2 S cm−1 at 98 % RH and 85 °C for YbO(OH)P and NDTBP, respectively. These values are comparable to the most efficient proton-conducting MOFs. In addition, these two anion-exchanged materials are stable in boiling water, which originates from the strong electrostatic interaction between the H2PO4− anion and the cationic host framework, showing a clear advance over all the acid-impregnated materials (H2SO4@MIL-101, H3PO4@MIL-101, and H3PO4@Tp-Azo) as practical solid-state fuel-cell electrolytes. This work offers a new general and efficient approach to functionalize 3D-extended frameworks through an anion-exchange process and achieves water-stability with ultra-high proton conductivity above 10−2 S cm−1. [ABSTRACT FROM AUTHOR]

The solvothermal reaction of [tris-(4-carboxylphenyl)phosphineoxide] (H3TPO) with UO2(NO3)2·6H2O in DMF affords a uranium-based chiral, microporous, metal–organic framework compound [(CH3)2NH2][UO2(TPO)]·4DMF·12.5H2O (SCU-3) that exhibits the highest void volume (68.8%) and second-harmonic generation (SHG) efficiency (1.54 KDP) for an actinide compound reported to date. The combination of large channels and the coordination capabilities of P=O moieties in the structure enables SCU-3 to capture large amounts of Th(iv) from aqueous solutions, providing a new strategy for preparing heterobimetallic 5f/5f compounds, and may lead to applications in nuclear waste management. [ABSTRACT FROM AUTHOR]

The ionothermal reactions of uranyl nitrate and 1,3-pbpH4 (1,3-pbpH4 = 1,3-phenylenebis(phosphonic acid) ligand in ionic liquids of [C4mim][Dbp], [C4mpyr][Br], and [Etpy][Br], respectively, afforded three new uranyl phosphonates, namely [C4mim][(UO2)2(1,3-pbpH)(1,3-pbpH)·Hmim] (1), [UO2(1,3-pbpH2)H2O·mpr] (2), and [Etpy][UO2(1,3-pbpH2)F] (3). Compound 1 exhibits a rare example of a chiral uranyl phosphonate 3D framework structure built from achiral building units of tetragonal bipyramidal uranium polyhedra and 1,3-pbp ligands. The structure adopts a network with channels extending along the b axis, which are filled with C4mim+ and protonated 1-methylimidazole. In sharp contrast, compounds 2 & 3 both show pillared topology composed of uranyl pentagonal bipyramid polyhedra and phosphonate ligands. The layers are neutral in compound 2 with N-methylpyrrole molecules in the interlayer space, while compound 3 adopts anionic layer, and the charge is compensated with N-ethyl-pyridinium cations between the layers. Although compounds 1, 2, and 3 were synthesized under identical conditions with sole variation of the ionic liquid species, the resulting structures show a rich diversity in the local coordination environment of uranyl ions, the protonation of the phosphonate ligand, the conformation of ionic liquid ions, and the overall arrangement of the structure. All compounds were characterized by absorption, temperature dependent fluorescence, as well as infrared and Raman spectroscopies. [ABSTRACT FROM AUTHOR]

Under hydrothermal condition, the decomposition of methanesulfonic acid to sulfate anion is observed, resulting in the formation of a novel thorium sulfate fluoride compound ThF 2 (SO 4 )(H 2 O) ( 1 ). This complex is structurally characterized by single crystal X-ray diffraction, revealing a three-dimensional structure crystallized in the monoclinic space-group P 2 1 / n , where thorium cation is nine coordinated by four SO 4 2− oxygen atoms, four bridging F − , and one H 2 O molecule. The crystal lattice parameters are a = 6.9065(7) Å, b = 6.9256(7) Å, c = 10.5892(11) Å, β = 96.755(2)°, V = 502.98(9) Å 3 , Z = 4. The temperature dependent UV–Vis–NIR absorption spectra and fluorescence spectra were collected from 77 K to 300 K, where the intensities of the peaks varied as a function of temperature. The Raman vibrational spectrum of the samples collected from 100 to 2000 cm −1 shows identical SO 4 2− vibration modes. [ABSTRACT FROM AUTHOR]

Two new uranyl phosphonates were synthesized by using p -xylenediphosphonic acid ( pmb H 4 ) to react with uranyl salts in Emim or BMMim ([EMim][PF 6 ] = 1-ethyl-3-methylimidazolium hexafluorophosphate; [BMMim]Cl = 1-butyl-2,3-dimethylimidazolium chloride) at elevated temperature, namely [EMim][UO 2 ( pmb H 2 ) 0.5 ( pmb H 2 ) 0.5 (ox) 0.5 ] ( 1 ) and [BMMim] 2 [(UO 2 ) 2 (pmb H 2 )( pmb )] ( 2 ). Both compounds adopt two dimensional structures, consisting of an anionic layer of uranyl phosphonate, with cations filled in the interlayer spaces. The spectroscopic properties of the compounds were studied extensively using UV–Vis absorption, temperature dependent fluorescence, Raman and IR spectroscopies. The UV–Vis absorption spectrum contains typical peaks of uranyl complexes at around 320 nm and 420 nm, which are originated from the charge transfer transitions from O 2p orbitals to the U 5f/6d orbitals. Both compounds adopt five strong emission peaks, whose intensities increase with the decrease of temperature, as observed in the temperature dependent fluorescence spectra. In Raman and IR spectra, the peaks corresponding to the stretch of C–H/O–H, P–O/P O, and O U O bonds could all be located and assigned. [ABSTRACT FROM AUTHOR]

Uranyl ion exists at trace levels in the environment and can cause severe adverse effects to human health. Therefore, it is desirable to develop analytical methods that can determine the trace uranyl ion in aqueous medium. We report here a new method using a thermo–responsive polymeric fluorescent sensor. Specifically, 5,10,15,20–tetrakis(4–carboxyphenyl)–porphyrin terminated poly( N –isopropylacrylamide) (TCPP–PNIPAM) was synthesized by controlled free radical polymerization for the detection of uranyl ion. The maximum fluorescence intensity at ~658 nm of TCPP–PNIPAM increases with molecular weights and is also closely related to the temperature. The polymeric sensor is sensitive to pH (1.0~5.0) with a fast responsive time (~3 min). Under optimized experimental conditions, the sensor exhibits a stable response for uranyl ion with high selectivity over a concentration range from 1.0×10 –3 to 1.0×10 –7 mol/L. For the trace uranyl ion (such as 1.0×10 –8 or 10 –9 mol/L), the determination could be successfully achieved after concentrating 100 times by centrifugation above 32 °C. The properties enable the polymeric sensor to have great potential for environmental application. [ABSTRACT FROM AUTHOR]

Uranium (U) immobilization from wastewater by zero valent iron (ZVI) was widely concerned through reduction and surface adsorption. Releasing of U due to re-oxidation of U(IV) into U(VI) limited the application of ZVI in U decontamination. In this work, a kind of biochar supported nano zero valent iron (Fe/BC(900)) was obtained by carbothermal reduction of starch mixed with ferric nitrate at 900 °C. U immobilization behavior by Fe/BC(900) in the presence of phosphate (P) was investigated. The U immobilization reaction was adjusted by controlling the sequence of U, Fe/BC(900) and P. U immobilization efficiency was enhanced to 99.9% in the presence of P. Reaction sequence of U, Fe/BC(900) and P influenced the U immobilization efficiency, which followed the order of (U-P)+Fe/BC(900)>(U- Fe/BC(900))+P>U+Fe/BC(900)>(P-Fe/BC(900))+U. P and nZVI both contributed to enhancing U immobilization through precipitation of uranyl-P and reductive co-precipitate (U(IV)) in a wide pH range. The released Fe ions could precipitate with uranyl and phosphate. Consumption of P and nZVI in the (P-Fe/BC(900))+U system limited U immobilization ability. The precipitate is highly dependent on U, P and Fe elements. U desorption in (U-P)+Fe/BC(900) system was not observed with stability. [Display omitted] • Enhanced immobilization of uranium by Fe/BC(900) in the presence of phosphate. • Reaction sequence of uranium, phosphate and Fe/BC(900) determined the uranium immobilization. • Consumption of nZVI by phosphate limited uranium immobilization. • Co-immobilization of uranium and phosphate on Fe/BC(900). • Uranium immobilization with neglected desorption in the presence of phosphate. [ABSTRACT FROM AUTHOR]

Uranium (U) immobilization from wastewater by zero valent iron (ZVI) was widely concerned through reduction and surface adsorption. Releasing of U due to re-oxidation of U(IV) into U(VI) limited the application of ZVI in U decontamination. In this work, a kind of biochar supported nano zero valent iron (Fe/BC(900)) was obtained by carbothermal reduction of starch mixed with ferric nitrate at 900 °C. U immobilization behavior by Fe/BC(900) in the presence of phosphate (P) was investigated. The U immobilization reaction was adjusted by controlling the sequence of U, Fe/BC(900) and P. U immobilization efficiency was enhanced to 99.9% in the presence of P. Reaction sequence of U, Fe/BC(900) and P influenced the U immobilization efficiency, which followed the order of (U-P)+Fe/BC(900)>(U- Fe/BC(900))+P>U+Fe/BC(900)>(P-Fe/BC(900))+U. P and nZVI both contributed to enhancing U immobilization through precipitation of uranyl-P and reductive co-precipitate (U(IV)) in a wide pH range. The released Fe ions could precipitate with uranyl and phosphate. Consumption of P and nZVI in the (P-Fe/BC(900))+U system limited U immobilization ability. The precipitate is highly dependent on U, P and Fe elements. U desorption in (U-P)+Fe/BC(900) system was not observed with stability. [Display omitted] • Enhanced immobilization of uranium by Fe/BC(900) in the presence of phosphate. • Reaction sequence of uranium, phosphate and Fe/BC(900) determined the uranium immobilization. • Consumption of nZVI by phosphate limited uranium immobilization. • Co-immobilization of uranium and phosphate on Fe/BC(900). • Uranium immobilization with neglected desorption in the presence of phosphate. [ABSTRACT FROM AUTHOR]

[Display omitted] • ZJU-X6 is a 3-fold interlocking cationic MOF and could capture 99TcO 4. • ZJU-X6 exhibited superior sorption ability and reusability toward 99TcO 4. • PDF and crystal structure clearly elucidated the sorption mechanism. Technetium-99 is one of most problematic radionuclides with a long half-life, high environmental mobility and solubility, which exists mainly in the form of anionic pertechnetate (99TcO 4 -). Searching for sorbents that hold efficient and selective elimination of radioactive 99TcO 4 - from aqueous solution is still a big challenge and further visualizing it in the sorbents is extremely difficult. Herein, we utilized an elongated organic neutral pyridyl ligand linked with Ni2+ to yield a novel 3-fold interlocking cationic metal–organic framework (ZJU-X6). Unexpectedly, the structure of ZJU-X6 held unique displaceable water pairs on the Ni2+ node in comparison to cationic metal–organic framework constructed by Ni2+. Attainable Ni2+ nodes distinctly improved the positive charge density of the framework, affording high sorption capacity, excellent selectivity, and removal depth toward 99TcO 4 -. Pair distribution functions (PDF) were applied to analyze the changes of atom distances in materials before and after capturing ReO 4 -, clearly showing that ReO 4 - entered into the body of ZJU-X6. More detailed sorption mechanism was atomically elucidated by obtaining the single crystal structure of 99TcO 4 --incorporated ZJU-X6. It is found that the water pairs were replaced by 99TcO 4 - and each Ni2+ coordinated with two 99TcO 4 - through oxygen atoms. In addition, each 99TcO 4 - engaged in multiple C–H...O hydrogen bonding with H atoms of aromatic rings that enhanced the trapping of 99TcO 4 -. [ABSTRACT FROM AUTHOR]

The reaction products of LnCl3 (Ln: Y, La-Lu) and AnCl3 (An: Pu, Am, Cm) with molten boric acid are characterized by single crystal XRD, UV/VIS/NIR spectroscopy, and DFT quantum chemical calculations. [ABSTRACT FROM AUTHOR]