Spectroelectrochemistry of EuCl3 in Four Molten Salt Eutectics; 3 LiCl−NaCl, 3 LiCl−2 KCl,LiCl−RbCl,and 3 LiCl−2 CsCl; at 873 K

Key electrochemical properties affecting pyroprocessing of nuclear fuel were examined in four eutectic melts using Eu^3+/2+ as a representative probe. We report the electrochemical and spectroelectrochemical behavior of EuCl₃ in four molten salt eutectics (3 LiCl?NaCl, 3 LiCl?2 KCl, LiCl?RbCl and 3 LiCl?2 CsCl) at 873 K. Cyclic voltammetry was used to determine the reduction potential for Eu^3+/2+ and the applied potentials for spectroelectrochemistry. Single step chronoabsorptometry and thin‐layer spectroelectrochemistry were used to obtain the number of electrons transferred, reduction potentials and diffusion coefficients for Eu³⁺ in each eutectic melt. The reduction potentials determined by thin‐layer spectroelectrochemistry were essentially the same as those obtained using cyclic voltammetry. The diffusion coefficient for Eu³⁺ was the largest in the 3 LiCl?NaCl melt, showed a negative shift in the 3 LiCl?2 KCl melt, and was the smallest in the LiCl?RbCl and 3 LiCl?2 CsCl eutectic melts. The basic one‐electron reversible electron transfer for Eu^3+/2+ was not affected by melt composition.     

Boron carbon nitride nanostructures from salt melts: tunable water-soluble phosphors

A simple, high yield, chemical process is developed to fabricate layered h-BN nanosheets and BCNO nanoparticles with a diameter of ca. 5 nm at 700 °C. The use of the eutectic LiCl/KCl salt melt medium enhances the kinetics of the reaction between sodium borohydride and urea or guanidine as well as the dispersion of the nanoparticles in water. The carbon content can be tuned from 0 to 50 mol % by adjusting the reactant ratio, thus providing precise control of the light emission of the particles in the range 440-528 nm while reaching a quantum yield of 26%. Because of their green synthesis, low toxicity, small size, and stability against aggregation in water, the as-obtained photoluminescent BCNO nanoparticles show promise for diagnostics and optoelectronics.     

Dechlorination of molten chloride waste salt from electrorefining via ion-exchange using pelletized ultra-stable H-Y zeolite in a fluidized particle reactor

Dechlorination of eutectic LiCl–KCl based electrorefiner (ER) salt is reported via ion-exchange reaction with protonated ultrastable Y-type (USHY) zeolite bound into mechanically fluidized 45–250 μm diameter particles. Evidence of exchange of cations from the salt (Li⁺, K⁺, and fission product cations) into the zeolite lattice replacing H⁺ ions was found based on a change in unit cell size, ICP-MS, XRD and TEM–EDS in addition to detection of HCl off gas. Ion exchange reaction was carried out at 625 and 650 °C, temperatures above the melting point of eutectic LiCl–KCl. Experiments were carried out to optimize zeolite drying temperature, estimate maximum ion-exchange capacity, and determine the thermal stability of USHY zeolite. The results indicate over 90% dechlorination can be achieved without zeolite structure collapse at 625 °C. This provides a promising route to stabilizing waste from radioactive chloride salts into dechlorinated waste forms for permanent geologic disposal.

     

Investigation of the evaporation of rare earth chlorides in a LiCl–KCl molten salt

Uranium dendrites which were deposited at a solid cathode of an electrorefiner contained a certain amount of salts. These salts should be removed for the recovery of pure metal using a cathode processor. In the uranium deposits from the electrorefining process, there are actinide chlorides and rare earth chlorides in addition to uranium chloride in the LiCl–KCl eutectic salt. The evaporation behaviors of the actinides and rare earth chlorides in the salts should be investigated for the removal of salts in the deposits. Experiments on the salt evaporation of rare earth chlorides in a LiCl–KCl eutectic salt were carried out. Though the vapor pressures of the rare earth chlorides were lower than those of the LiCl and KCl, the rare earth chlorides were co-evaporized with the LiCl–KCl eutectic salt. The Hertz–Langmuir relation was applied for this evaporation, and also the evaporation rates of the salt were obtained. The co-evaporation of the rare earth chlorides and LiCl–KCl eutectic were also discussed.     

The solid–liquid separation characteristics of pure LiCl–KCl eutectic salt using different types of crucibles

Uranium deposits were recovered at the solid cathode of an electrorefining system, and deposited uranium dendrite normally contains about 30–40 wt% LiCl–KCl eutectic salts. Therefore, a separation of the eutectic salts from deposited uranium is essential for reusing these salts and uranium. A process such as distillation was employed for cathode processing due to the advantages of a minimal generation of secondary waste, a compact unit process, and simple and low-cost equipment. However, the realization of a wide evaporation area or high distillation temperature is limited by various factors such as the material or structure of a distiller. Also, the electrical energy flow from outside has a lot of consumption to maintain the high temperature. Hence, in this study, solid–liquid separation experiments are proposed to increase the throughput of the salt removal process by the separation of the liquid salt prior to the distillation of the LiCl–KCl eutectic salt. The solid–liquid separation of salt was carried out in a vertical type distiller. The behavior of the solid–liquid separation of pure eutectic salt was investigated as a function of temperature, pressure, sieve size, and crucible shape. From the experimental results using pure eutectic salts, the amount of salt separation was achieved at more than 94 wt%. The rate of solid–liquid separation of salt using 600 °C is higher than that of 500 °C under the same condition. The influence of a vacuum for solid–liquid separation can be disregarded, and the separation rate of a 100 mesh was higher than that of a 150 mesh. In addition, the rate of separation for salts using a porous crucible is higher than that in a non-porous crucible.     

Foreword

Electrochemical behaviors of U⁴⁺ in LiCl–KCl–UF₄ eutectic and deposition of U metal were investigated. It was found that the presence of F^? has influence on the diffusion of U³⁺ and U⁴⁺ as comparing to data obtained in pure chloride molten salts. Electrochemical deposition of U was carried out by using pulse current electrolysis. Characterization results indicate that U metal was obtained at the cathode, implying U metal can be directly deposited from LiCl–KCl–UF₄ eutectic in this case and the extractive ratio is calculated to be 98%. Our results demonstrate feasible separation of U from LiCl–KCl–UF₄ molten salt by electrochemical method.     

Selective Solid–Liquid and Liquid–Liquid Extraction of Lithium Chloride Using Strapped Calix[4]pyrroles

LiCl is a classic “hard” ion salt that is present in lithium‐rich brines and a key component in end‐of‐life materials (that is, used lithium‐ion batteries). Its isolation and purification from like salts is a recognized challenge with potential strategic and economic implications. Herein, we describe two ditopic calix[4]pyrrole‐based ion‐pair receptors ( 2 and 3 ), that are capable of selectively capturing LiCl. Under solid–liquid extraction conditions, using 2 as the extractant, LiCl could be separated from a NaCl/KCl salt mixture containing as little as 1 % LiCl with circa 100 % selectivity, while receptor 3 achieved similar separations when the LiCl level was as low as 200 ppm. Under liquid–liquid extraction conditions using nitrobenzene as the non‐aqueous phase, the extraction preference displayed by 2 is KCl>NaCl>LiCl. In contrast, 3 exhibits high selectivity towards LiCl over NaCl and KCl, with no appreciable extraction being observed for the latter two salts.     

混合熔盐法低温合成Sm2Ti2S2O5及其光催化分解水产氢

以TiO2、TiS2及Sm2O3为前驱体,分别加入LiCl-KCl与LiCl-CsCl的最低共熔混合物作为熔盐,在较低温度下成功合成了Sm2Ti2S2O5(STSO)颗粒。通过对比不同温度下所制备产物的X射线衍射图,首次表明STSO的热力学结晶温度在520℃左右,远低于之前报道的650℃的最低合成温度。扫描电子显微镜照片显示,采用2种混合熔盐制备的STSO都呈片状形貌;同一合成温度下,采用LiCl-CsCl熔盐制备的STSO的厚度小于LiCl-KCl所得产物。采用出射光波长大于420 nm的氙灯作为光源,在含有Na2S-Na2SO3空穴牺牲剂的溶液中,所制备的STSO颗粒表现出最高35μmol·h-1的光催化分解水产氢活性以及20 h以上的产氢稳定性。     

LaCl3-KCl-LiCl三元系统相图的研究

利用DTA研究了LaCl3-KCl-LiCl三元系统相图。发现该相图由二个赝三元相图构成。相图中有五个液相面, 七条二次结晶线, 三个三元无变点, 它们分别为低共熔点E1[W(LaCl3)=0.115, W(KCl)=0.474, W(LiCl)=0.411, 345℃],E2[W(LaCl3)=0.494, W(KCl)=0.216, W(LiCl)=0.290, 410℃]和三元转熔点P[W(LaCl3)=0.600, W(KCl)=0.108, W(LiCl)=0.292, 429℃]。     

UV–vis absorption spectroscopic study for on-line monitoring of uranium concentration in LiCl–KCl eutectic salt

UV–vis absorption spectroscopy of uranium in LiCl–KCl eutectic salt at 773 K was studied for the on-site use in pyrochemical process. Uranium(III) chloride was electrochemically prepared from uranium metal in LiCl–KCl eutectic salt at 773 K by using chronopotentiometry. Three absorption peak positions were selected and calibrated for the quantitative analysis of uranium in the molten salt medium. The molar absorptivity and minimum detectable concentration for the selected wavelength were obtained with a confidence level of 99%.     

Bottom-up Synthesis of Single-Crystalline Poly (Triazine Imide) Nanosheets for Photocatalytic Overall Water Splitting

Poly (triazine imide) (PTI/Li⁺Cl⁻), one of the crystalline versions of polymeric carbon nitrides, holds great promise for photocatalytic overall water splitting. In principle, the photocatalytic activity of PTI/Li⁺Cl⁻ is closely related to the morphology, which could be reasonably tailored by the modulation of the polycondensation process. Herein, we demonstrate that the hexagonal prisms of PTI/Li⁺Cl⁻ could be converted to hexagonal nanosheets by adjusting the binary eutectic salts from LiCl/KCl or NaCl/LiCl to ternary LiCl/KCl/NaCl. Results reveal that the extension of in-plane conjugation is preferred, when the polymerisation was performed in the presence of ternary eutectic salts. The hexagonal nanosheets bears longer lifetimes of charge carriers than that of hexagonal prisms due to lower intensity of structure defects and shorter hopping distance of charge carriers along the stacking direction of triazine nanosheets. The optimized hexagonal nanosheets exhibits a record apparent quantum yield value of 25 % (λ=365 nm) for solar hydrogen production by one-step excitation overall water splitting.     

From Heptazines to Triazines – On the Formation of Poly(triazine imide)

Poly(triazine imide), a 2D extended carbon nitride network compound that is obtained from ionothermal synthesis in LiCl/KCl or LiBr/KBr salt melt has been known for over a decade. We now have investigated the formation process of this material starting from various triazine‐ and heptazine‐based precursors as well as the differences between ionothermal and conventional synthesis via thermal condensation. Independent of chosen starting material, melem (triamino‐s‐heptazine) is initially formed from the starting material as the imminent precursor to poly(triazine imide). We elucidate the impact of various different carbon nitride precursor compounds on the formation process, propose a mechanism for the back reaction of heptazines to triazines, and rationalize the occurring processes.     

Salt clean-up for recycling by electrolysis with a cathode-perforated ceramic container assembly

Pyroprocessing is a promising way for the recovery of actinide elements from the used nuclear fuel. Electro-refining is a key technology of pyroprocessing and the electro-refining is generally composed of two recovery steps—deposit of uranium onto a solid cathode and the recovery of actinide elements by a liquid cathode. After the electro-refining process, it is necessary to remove the solutes from the molten salt for the salt regeneration. In this study, it was attempted to clean up a molten salt with a solid cathode- perforated ceramic container assembly and a glassy carbon anode. LiCl–KCl eutectic salt was used as a medium of the electrolytic bath. Uranium and cerium were used as solutes, where uranium was used as a surrogate for the actinide elements. The initial contents of uranium and cerium in the salt were varied in the range of 0–5 wt%. Electrolysis experiments were carried out by passing a constant current between the anode and cathode at 500 °C. The solute contents were measured using ICP-AES spectroscopy. The initial cathode potential was about ?1.6 V. This value decreased with increasing time in the salt. The solutes in the saline phase were successfully recovered onto the cathode.     

Automated chromatographic separation coupled on-line to ICP-MS measurements for the quantification of actinides and radiostrontium in soil samples

The uranium (III) ions behaviour in fused 3LiCl–2KCl eutectic versus the Cl^?/Cl₂ reference electrode in the temperature range of 723–823 K on the liquid cadmium electrode by transient electrochemical techniques on the tungsten or molybdenum electrodes was studied. The mechanism of electrochemical reduction on cadmium cathode and the influence of temperature, cathode current density and the duration of electrolysis were studied. The activity coefficients and the base thermodynamic properties of uranium in fused U–Cd/3LiCl–2KCl system were calculated.     

Theoretical study of mechanism of cycloaddition reaction between dichloro‐germylene carbene (Cl2GeC:) and aldehyde

The mechanism of the cycloaddition reaction between singlet dichloro‐germylene carbene and aldehyde has been investigated with MP2/6‐31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by zero‐point energy and CCSD (T)//MP2/6‐31G* method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The channel (A) consists of four steps: (1) the two reactants (R1, R2) first form an intermediate INT2 through a barrier‐free exothermic reaction of 142.4 kJ/mol; (2) INT2 then isomerizes to a four‐membered ring compound P2 via a transition state TS2 with energy barrier of 8.4 kJ/mol; (3) P2 further reacts with aldehyde (R2) to form an intermediate INT3, which is also a barrier‐free exothermic reaction of 9.2 kJ/mol; (4) INT3 isomerizes to a germanic bis‐heterocyclic product P3 via a transition state TS3 with energy barrier of 4.5 kJ/mol. The process of channel (B) is as follows: (1) the two reactants (R1, R2) first form an intermediate INT4 through a barrier‐free exothermic reaction of 251.5 kJ/mol; (2) INT4 further reacts with aldehyde (R2) to form an intermediate INT5, which is also a barrier‐free exothermic reaction of 173.5 kJ/mol; (3) INT5 then isomerizes to a germanic bis‐heterocyclic product P5 via a transition state TS5 with an energy barrier of 69.4 kJ/mol. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Raman Spectroscopic Study of Rare Earth Chlorides in Alkali Chloride Eutectic Melts

Raman spectra of rare earth (REE: rare earth elements) trichloride (REE = Y, La, Ce, Pr, Sm, Gd, Dy, or Yb) dissolved in alkali chloride eutectic melts (LiCl‐KCl, LiCl‐RbCl, and LiCl‐CsCl) were measured at 793 K. The spectra showed polarized peaks centered around 240–270 cm^–1, which were identified as the totally symmetric stretching vibration (ν₁) of the octahedral REECl₆^3–. The ν₁ frequency increased with the polarizing power of the trivalent REE ions. The change in the ν₁ frequency was found to be larger for lighter lanthanides. This was attributable to the distortion of the O_h symmetry of REECl₆^3–.     

Selective salt transport through a crosslinked poly(L-glutamic acid) membrane for KCl/LiCl mixed systems

Selective salt transport of KCl over LiCl has been studied for a crosslinked poly(L -glutamic acid) membrane immersed in 80 vol.-% ethanol. The permeabilities (P_s) and solubilities were measured for various mixing ratios of the salts. The highest permselectivity (P_s (KCl)/P_s (LiCl) = 4,3) has been obtained at a LiCl mole fraction of 0,2. It is similar to that obtained in single salt systems.     

Size Effects of the Anions in the Ionothermal Synthesis of Carbon Nitride Materials

Semiconducting carbon nitride polymers are used in metal-free photocatalysts and in opto-electronic devices. Conventionally, they are obtained using thermal and ionothermal syntheses in inscrutable, closed systems and therefore, their condensation behavior is poorly understood. Here, the synthetic protocols and properties are compared for two types of carbon nitride materials – 2D layered poly(triazine imide) (PTI) and hydrogen-bonded melem hydrate – obtained from three low-melting salt eutectics taken from the systematic series of the alkali metal halides: LiCl/KCl, LiBr/KBr, and LiI/KI. The size of the anion plays a significant role in the formation process of the condensed carbon nitride polymers, and it suggests a strong templating effect. The smaller anions (chloride and bromide) become incorporated into triazine (C₃N₃)-based PTI frameworks. The larger iodide does not stabilize the formation of a triazine-based polymer, but instead it leads to the formation of the heptazine (C₆N₇)-based hydrogen-bonded melem hydrate as the main crystalline phase. Melem hydrate, obtained as single-crystalline powders, was compared with PTI in photocatalytic hydrogen evolution from water and in an OLED device. Further, the emergence of each carbon nitride species from its corresponding salt eutectic was rationalized via density functional theory calculations. This study highlights the possibilities to further tailor the properties of eutectic salt melts for ionothermal synthesis of organic functional materials.     

Synthesis,structure, electrical properties,and band structure calculations of TiAsTe

The new compound TiAsTe has been synthesized by the reaction of the elements in a LiCl/KCl flux at 923 K. The compound crystallizes with four formula units in space group Immm of the orthorhombic system in a cell at 153 K of a = 3.5730(8) A, b = 5.249(1) A, c = 12.794(3) A, V = 240.0(1) A(3). The structure, which is of the NbPS structure type, is a three-dimensional extended framework built from bicapped TiAs(4)Te(4) trigonal prisms. It may be considered to comprise infinity (2) [TiTe] slabs perpendicular to [001] that are interspersed with linear infinity (1)[As] chains running along [010]. The As-As distances alternate at 2.554(2) and 2.695(2) A. Electrical and thermopower measurements indicate that TiAsTe is an n-type metallic compound. Density functional theory calculations help rationalize the chemical bonding and physical properties.     

Effect of alkali halide salt additives on the structure of poly(vinyl alcohol) films cast from aqueous solutions

The molecular structures of poly(vinyl alcohol) films cast from polymer aqueous solutions (1 mol/L) containing 0.1 mol/L of LiCl, NaF, NaCl, KCl, CsCl, KBr, and KI salts are studied via FTIR spectroscopy. The addition of any of these salts except LiCl leads to an increase in the degree of crystallinity of poly(vinyl alcohol) in a film by a factor of 1.3–1.6. In contrast, LiCl significantly decreases the crystallinity of the polymer. It is found that, in the IR spectra of the films containing salt additives, the position of the maximum in the band of the stretching vibrations of OH groups of the polymer is shifted relative to its position in the IR spectra of the films free of salt additives. The magnitude and direction of this band shift depend on the types (anion or cation) and radii of ions comprising salts. The observed effects are interpreted in terms of existing ideas on the interactions of salt ions with the OH groups of water and other hydroxyl-containing molecules.