pH-dependent Synthesis of Octa-nuclear Uranyl-oxalate Network Mediated by U-shaped Linkers

In this work,we report a novel octa-nuclear uranyl(U8)motif[(UO2)8O4(μ3-OH)2(μ2-OH)2]4+embedded in a uranyl-oxalate coordination polymer(compound 1)based on a U-shaped linker with extra-long xylylene chains for stabilizing the resulting high-nuclear motif through additional cross-linking connectivity.A comparison with dimeric and monomeric uranyl compounds obtained at different pH value from the same hydrothermal system reveals that,solution pH plays a vital role in formation of this octa-nuclear uranyl motif by promoting hydrolysis of uranyl source.Since high similarity of eight uranium centers in this nearly planar U8 motif here,overlapping and broadening of signals in fluorescence,infra-red(IR)and Raman spectra can be found.

Efficacious selective separation of U(Ⅵ) over Mo(Ⅵ) using novel 2,9-diamide-1,10-phenanthroline ligands: Liquid-liquid extraction and coordination chemistry

Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.

Hierarchical and self-supporting honeycomb LaNi_5 alloy on nickel foam for overall water splitting in alkaline media

Ni-based metallic foams possessing large specific surfaces and open cell structures are of specific interest as catalysts or catalyst carriers for electrolysis of water.Traditional fabrication of Nickel foam limits the element modification choices to several inert transition metals only on polymer foam precursor and subsequent preparation of foam-based catalysts in aqueous solution or organic electrolyte.To expand the modification horizon,molten salt with wide electrochemical window and fast ion diffusion can achieve the reduction of highly active elements.Herein,we reported is a general and facile method to deposit directly of highly reactive element La and prepare hierarchical honeycomb LaNi_(5) alloy on Ni foam(ho-LaNi_(5)/NF).This self-supporting electrode presents excellent electrical coupling and conductivity between the Ni foam and LaNi_(5),which provides a 3D self-supported heterostructure with outstanding electrocatalytic activity and excellent durability for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).It exhibits excellent overpotential(1.86 V)comparable to commercial coupled IrO_(2)//Pt/C(1.85 V)at a high current density of 100 m A cm^(-2).This work may pave the way for fabricating novel 3D self-supported honeycomb alloy that can be applied as electrode for usage of clean energy.

Heterostructure engineering of MoS_(2)/Mo_(2)CT_(x) nanoarray via molten salt synthesis for enhanced hydrogen evolution reaction

Two-dimensional layered transition metal carbides(MXenes),have huge potential advantage for applications in hydrogen evolution reaction(HER).However,the hindered hydrogen evolution at large current densities and the instability of MXenes during HER remains major challenges.Herein,we report the MoS_(2)/Mo_(2)CT_(x) nanoarray with aerophobic structure via molten salt synthesis.In situ vertical distribution of MoS_(2)nanoarray on the surface of Mo_(2)CT_(x) accelerates hydrogen gas release from the electrode,exhibiting significantly enhanced catalytic activity and stability to bare MoS_(2)and Mo_(2)CT_(x).The MoS_(2)/Mo_(2)CT_(x) nanoarray possesses excellent stability at100 mA/cm^(2)for 100 h with only 3%overpotential increase.Our work provides guidance for developing high-stability MXene-based catalysts by virtue of in situ bonding between nanoarray and MXene.

A large-scale screening of metal-organic frameworks for iodine capture combining molecular simulation and machine learning

We performed large-scale molecular simulation to screen and identify metal-organic framework materials for gaseous iodine capture,as part of our ongoing effort in addressing management and handling issues of various radionuclides in the grand scheme of spent nuclear fuel reprocessing.Starting from the computation-ready experimental(CoRE)metal-organic frameworks(MOFs)database,grand canonical Monte Carlo simulation was employed to predict the iodine uptake values of the MOFs.A ranking list of MOFs based on their iodine uptake capabilities was generated,with the Top 10 candidates identified and their respective adsorption sites visualized.Subsequently,machine learning was used to establish structure-property relationships to correlate MOFs’various structural and chemical features with their corresponding performances in iodine capture,yielding interpretable common features and design rules for viable MOF adsorbents.The research strategy and framework of the present study could aid the development of high-performing MOF adsorbents for capture and recovery of radioactive iodine,and moreover,other volatile environmentally hazardous species.

Silver Ion-Induced Formation of Unprecedented Thorium Nonamer Clusters via Lacuna-Construction Strategy

Herein,we report the synthesis and structures of two novel mixed-metal clusters denoted as Th_(9)Ag_(6)and Th_(9)Ag_(12).Both clusters feature unprecedented Th_(9)cores.The cores are tricapped trigonal prism moieties that are novel among actinides.Attempted alternative synthesis routes indicate that the Th_(9)clusters are accessible only through slow introduction of Ag_(+)into a solution containing a Th6 cluster modified with 2-picolinic acid.Alternative rapid addition of Ag_(+)leads to dissociation of the Th6 cluster with formation of a high-purity(ThAg)_(∞)two-dimensional layered structure material.A mechanism for cluster dissociation and reassembly to yield Th_(9)from Th6 is proposed that is consistent with spectroscopic observations and computational results.Because of Ag⋯Ag andπ–πinteractions,the Th_(9)Ag_(12)cluster exhibits high stability in air,at elevated temperature,underγ-irradiation,and in common solvents.

Germylene-Fe complexes caused by heterometallic coupling and investigation into the 3d-4p bonding

The interpretation of heterometallic bonding nature is a basic work of inorganic chemistry.By means of intermetallic substitution of germylene anions with iron halide complexes CpFe(CO)_(2)I andβ-diketiminato Fe^Ⅱchloride,the ferrogermylene complexes 3a,3b and 4a were synthesized and structurally characterized.The structural and IR characterizations show the presence of the Ge←Feπbackbonding in molecules 3a,3b and 4a.The computational works on frontier molecular orbitals and their comparison of energy states confirmed thatσdonation andπbackbonding are both weak in these molecules,despite three complexes have longer Ge-Fe bonds,whose strength decreases slightly with the degressive electron density around Fe environment in a sequence from 3a,3b to 4a.

Kinetics process of Tb(Ⅲ)/Tb couple at liquid Zn electrode and thermodynamic properties of Tb-Zn alloys formation

Electrochemical properties of rare-earth elements in the LiCl-KCl eutectic are important for the pyrometallurgical recycling process of spent nuclear fuels. In this work, the electrochemical properties of Tb(Ⅲ)/Tb(0) couple were studied by the cyclic voltammetry(CV) at a liquid Zn pool electrode. The results showed that this electrochemical reaction is quasi-reversible with mixed reversible diffusion control and the charge transfer control. The diffusion coefficient of Tb(Ⅲ) was determined to be in the order of ~10.5 cm2 s.1. Moreover, kinetic parameters, such as the standard rate constants(ks) and charge transfer coefficient(α) for the electroreduction of Tb(Ⅲ) to Tb(0) at the liquid Zn electrode, were calculated by the Nicholson method at 873 K. Additionally, it was found that Tb-Zn intermetallic compounds were easily to be formed in the measurements. Hence, the reduction process of Tb(Ⅲ)/Tb(0) couple on the Zn-coated Mo electrode was also studied to obtain more information of the Tb-Zn intermetallic compounds. Electrochemical signals stemming from various intermetallic compounds associated with TbZn12, Tb2Zn17, Tb13Zn58, Tb3Zn11, TbZn3, TbZn2 and TbZn, were observed. The thermodynamic data were thereafter estimated by applying the emf method at 823–923 K. The standard formation Gibbs energies and the standard equilibrium constant of each Tb-Zn intermetallic compounds were also calculated. Finally, enthalpies and entropies of formation and the apparent standard potentials of various Tb-Zn intermetallic compounds were also obtained.

Electrochemical properties of gadolinium on liquid gallium electrode in LiCl-KCl eutectic

This work presents the electrochemical properties of gadolinium(Gd), a significant rare earth element in spent nuclear fuel(SNF), in the LiCl-KCl eutectic. To explore thermodynamic properties of Gd at the liquid gallium(Ga) electrode, experiments were performed both on the inert tungsten(W) and liquid gallium(Ga) electrode at different temperatures in a range from 723 to 823 K, which show that the Gd metal can be oxidized to Gd(Ⅲ) by exchanging of 3 electrons. Electrochemical techniques including cyclic voltammetry(CV), open circuit potential(OCP), potentiostatic electrolysis and galvanostatic electrolysis were utilized to detect the electrochemical behavior and evaluate standard apparent potential of the Gd(Ⅲ)/Gd couple,and E(Gd(Ⅲ)/Gd)*=-3.456 + 6.2×10-4T(±0.046)( vs Cl2/Cl-) is obtained.In addition, electromotive force(EMF) and coulometric titration were employed to calculate the activity and activity coefficient of Gd in metal Ga. After calculation, the activity is 1.791×10-15at 723 K and function of activity coefficient and temperature is lgγ = 3.485-10927/T(±0.0875).

Professor Zhifang Chai:Scientific contributions and achievements

Prof.Zhifang Chai,born in October 1942,is a radioanalytical chemist working at the Institute of High Energy Physics,Chinese Academy of Sciences and Soochow University.He graduated from Fudan University in 1964.As an Alexander von Humboldt Foundation fellow,he worked at Cologne University,Germany from1980 to 1982.

Condition dependence of Zr electrochemical reactions and morphological evolution of Zr deposits in molten salt

This work presents a comprehensive study for the electrochemical behaviors of zirconium in LiCl-KCl eutectic.The effects of stirring,temperature and Zr concentration on the electrode reactions,the ZrCl_4 sublimation from the melt,microcosmic morphologies of Zr deposits(ZrCl and Zr)obtained at different potential and temperature have been investigated.The behaviors of Zr(Ⅳ),on a large concentration range from 0.13%to 2.28%in melt,show a multiple-step reaction involving Zr(Ⅳ),Zr(Ⅱ),ZrCl and Zr species.Temperature plays a crucial role on the changes of Zr(IV)reduction behavior on the solid electrode.The Zr(Ⅳ)/ZrCl couple is more easily observed at lower temperature and gradually diminishes with the increase of temperature.The Zr(Ⅳ)/Zr(Ⅱ)and Zr(Ⅱ)/Zr reactions are predominant on the W electrode at higher temperatures.At 673 K,a layered structure of insoluble ZrCl formed by potentiostatic electrolyses at 1.1 V was visualized by scanning electron microscopy-energy dispersive X-ray(SEM-EDS),while only Zr metal particles was observed at higher temperature than 773 K.An evolution of the Zr-based structure and size corresponding to the ZrCl and Zr metal based on different potentiostatic electrolysis was observed.The average particle size of the Zr metalparticles increases with the increase of temperature.

A combined DFT and molecular dynamics study of U(Ⅵ)/calcite interaction in aqueous solution

Here we present a combined DFT and molecular dynamics study of uranyl(U(VI)) interaction mechanisms with the calcite(104) surface in aqueous solution. The roles of three anion ligands(CO_3^(2-), HCO_3^-,OH^-) and solvation effect in U(VI) interaction with calcite have been evaluated. According to our calculations, water adsorbed on the calcite(1 0 4) surface prefers to exist in molecular state rather than dissociative state. Energy analysis indicate that the positively charged uranyl species prefers to form surface complexes on the surface, while neutral uranyl species may bind with the surface via both surface complexing and ion exchange reactions of U(Ⅵ)→Ca(Ⅱ). In contrast, the negatively charged uranyl species prefer to interact with the surface via ion exchange reactions of U(Ⅵ) →Ca(Ⅱ), and the one with UO_2(CO_3)_2(H_2O)^(2-)as the reactant becomes the most favorable one in energy. We also found that uranyl adsorption increases the hydrophilic ability of the(104) surface to different extents, where the UO_2(CO_3)_3Ca_2 species contributes to the largest degree of energy changes(-53 kcal/mol). Our calculations proved that the(104) surface also has the ability to immobilize U(Ⅵ) via either surface complexing or ion exchange mechanisms under different pH values.

Hierarchical assembly of uranyl metallacycles involving macrocyclic hosts

Actinide metallacycles are an emerging class of functional coordination assemblies,but multi-level assembly from metallacycle units toward hierarchical supramolecular structures are still rarely investigated.In this work,we put forward a novel supramolecular inclusion-based method through introducing two macrocyclic hosts,cucurbit[7]uril(CB[7])and cucurbit[8]uril(CB[8])to facilitate hierarchical assembly of uranyl metallacycles with higher complexity,and successfully prepare two different kinds of uranyl metallacycle-based complexes with intriguing hierarchical structures,a CB[7]-based four-member molecular necklace([4]MN)and a CB[8]-involved ring-in-ring supramolecular polymer chain.The results obtained here prove the feasibility of supramolecular inclusion for regulating coordination assembly of uranyl metallacycles and related hierarchical structures.It is believed that this method can be used to achieve the construction of actinide coordination assemblies with higher structural complexity.

Theoretical studies on the complexation of Eu(Ⅲ) and Am(Ⅲ) with HDEHP： structure, bonding nature and stability

Separation of trivalent lanthanides(Ln(Ⅲ)) and actinides(An(Ⅲ)) is a key issue in the advanced spent nuclear fuel reprocessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes(TALSPEAK) process, the organophosphorus ligand HDEHP(di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(Ⅲ) from An(Ⅲ) with the combination of a holdback reagent in aqueous lactate buffer solution. In this work, the structural and electronic properties of Eu^(3+) and Am^(3+) complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory(DFT). It was found that HDEHP can coordinate with M(Ⅲ)(M=Eu, Am) cations in the form of hydrogen-bonded dimers HL_2^-(L=DEHP), and the metal ions prefer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(Ⅲ) complexes have higher interaction energies, the HL_2^- dimer shows comparable affinity for Eu(Ⅲ) and Am(Ⅲ) according to thermodynamic analysis, which may be attributed to the higher stabilities of Eu(Ⅲ) nonahydrate. It is expected that this work could provide insightful information on the complexation of An(Ⅲ) and Ln(Ⅲ) with HDEHP at the molecular level.

A ternary mechanism for the facilitated transfer of metal ions onto metal–organic frameworks: implications for the "versatility" of these materials as solid sorbents

Although metal–organic frameworks offer a new platform for developing versatile sorption materials,yet coordinating the functionality,structure and component of these materials remains a great challenge.It depends on a comprehensive knowledge of a“real sorption mechanism”.Herein,a ternary mechanism for U(Ⅵ)uptake in metal–organic frameworks was reported.Analogous MIL-100s(Al,Fe,Cr)were prepared and studied for their ability to sequestrate U(Ⅵ)from aqueous solutions.As a result,MIL-100(Al)performed the best among the tested materials,and MIL-100(Cr)performed the worst.The nuclear magnetic resonance technique combined with energy-dispersive X-ray spectroscopy and zeta potential measurement reveal that U(Ⅵ)uptake in the three metal–organic frameworks involves different mechanisms.Specifically,hydrated uranyl ions form outer-sphere complexes in the surface of MIL-100s(Al,Fe)by exchanging with hydrogen ions of terminal hydroxyl groups(Al-OH_(2),Fe-OH_(2)),and/or,hydrated uranyl ions are bound directly to Al(Ⅲ)center in MIL-100(Al)through a strong inner-sphere coordination.For MIL-100(Cr),however,the U(Ⅵ)uptake is attributed to electrostatic attraction.Besides,the sorption mechanism is also pH and ionic strength dependent.The present study suggests that changing metal center of metal–organic frameworks and sorption conditions alters sorption mechanism,which helps to construct effective metal–organic frameworks-based sorbents for water purification.

Easily prepared and stable functionalized magnetic ordered mesoporous silica for efficient uranium extraction

Functionalized magnetic Fe_3O_4@SiO_2 composite nanoparticles were prepared by simply embedding iron oxide nanoparticles into MCM-41 through one-step synthesis process, followed by aminopropyls grafting on the mesopore channels, aiming to efficiently and conveniently uptake U(VI) from aqueous solution. The resultant material possesses highly ordered mesoporous structure with large surface area, uniform pore size, excellent thermal stability, quick magnetic response, and desirable acids resistance, confirmed by Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM), N_2 adsorption/desorption experiments, powder X-ray diffraction(PXRD), and thermogravimetric analysis(TGA). Detailed U(VI) sorption test indicated that this material is indeed an effective U(VI) sorbent with fast sorption kinetics of less than 2 h, large sorption capacity of 160 mg/g at p H 5.0±0.1, and desirable selectivity towards U(VI) ions over a range of competing metal ions. The absorbed U(VI) can be easily desorbed by 0.01 mol/L or more concentrated HNO_3 solution, and the reclaimed sorbent can be reused with no obvious decrease of sorption capacity even after 4 sorption-desorption cycles. The present results suggest the vast opportunities of this kind of magnetic composite on the solid-phase extraction of U(VI).

Facile Access to Uranium and Thorium Phosphaethynolate Complexes Supported by Tren: Experimental and Theoretical Study

The issue of covale nee of acti nide complexes remai ns con troversial to date.The in troducti on of 2-phosphaethy nolate anion into acti・nide complexes is expected to in vestigate the reaction mode and the bon ding property.Herei n,we describe the function alizatio n of An(Tren^(TIPS))CI(1:An=U;2:An=Th)precursors with NaOCP(dioxane)_(2.5) through salt-elimination method leading to the formation of the corresponding uranium and thorium phosphaethynolate species:[U(Tren^(TIPS))(OCP)]⑶and[Th(Tren^(TIPS))(OCP)](4).

Phosphonate-Decorated Covalent Organic Frameworks for Actinide Extraction: A Breakthrough Under Highly Acidic Conditions

Although solid-phase extraction is a useful approach for metal ion separation from aqueous solutions,existing sorbents suffer from low extraction effici-encies and/or instability when in contact with strong acidic media.We report here the first study on rational design and fabrication of phosphonate-decorated covalent organic frameworks,COF-IHEP1 and COF-IHEP2,for efficient and selective extraction of of uranium(VI)[U(VI)]and plutonium(IV)[Pu(IV)]from highly acidic solutions.

Towards understanding the correlation between UO_2^(2+) extraction and substitute groups in 2,9-diamide-1,10-phenanthroline

2,9-Diamide-1,10-phenanthroline(DAPhen)ligands represent a new family of tetradentate extractants given their strong affinity to actinides and the CHON principle.Among this family,N,N′-diethyl-N,N′-ditolyl-2,9-diamide-1,10-phenanthroline(Et-TolDAPhen),initially reported by us,exhibits excellent selectivity towards actinides(U,Th,Am,Pu)over lanthanides and thus can be potentially applied in the group actinide extraction(GANEX)process for the group separation of actinides.In this article,by tailoring the lengths of alkyl chains,we synthesized other four DAPhen ligands with different substitute groups in the diamide moieties,and characterized the relationship between properties and substitute groups of DAPhen ligand.The extraction results show that three of the ligands exhibit high performance in UO_2^(2+)extraction from an acidic solution and the extracted UO_2^(2+)can be easily stripped by only using ultrapure water.Spectrophotometry titration confirms that UO_2^(2+)combined with all the four ligands in 1:1 mode.The extended X-ray absorption finestructure(EXAFS)study shows that six donor atoms comprise the first equatorial shell of the UO_2^(2+)ions bonded by the DAPhen ligands,among which two nitrogen and two oxygen atoms are from the DAPhen ligand,while other two oxygen atoms are from one nitrate ions.This article promises to provide basic data for assessing the feasibility of this kind of DAPhen ligands applied in actinides separation from nuclear wastes.

Temperature-responsive alkaline aqueous biphasic system for radioactive wastewater treatment

The treatment of anionic ^(99)TcO_(4)^(-)in the waste tank with high alkalinity is still very challenging.In this work,a new temperature-responsive alkaline aqueous biphasic system(ABS)based on(tri-n–butyl)-ntetradecyl phosphonium chloride(P_(44414)Cl)was developed to remove radioactive ^(99)TcO_(4)^(-).The phase transition mechanism was studied by cloud point titration,small-angel X-ray scattering,dynamic light scattering,and molecular dynamic simulations.As the Na OH concentration or temperature increased,the P_(44414)^(+)micelle could grow and aggregate.This micelle showed a particularly high affinity toward ReO_(4)^(-)/^(99)TcO_(4)^(-)compared to other competing anions and could directly extract more than 98.6%of ^(99)TcO_(4)^(-)from simulated radioactive tank waste supernatant.Furthermore,the loaded ^(99)TcO_(4)^(-)could be easily stripped by using concentrated nitric acid rather than metal salt-based reductants.This work clearly demonstrates that the alkaline ABS is a promising separation system for solving the technetium problem in the alkaline waste tank.