锕系元素在熔盐体系中的电化学及萃取特性研究进展

熔融盐是一类非水溶剂,分为高温熔盐、室温熔盐和低温熔盐。 作为反应介质和电解介质,因其优良性能,可以溶解很多难溶于水的活泼金属。 近年来,该领域的研究热点是将熔盐作为干法后处理的电解质分离和回收锕系元素。 本文综述了锕系元素在高温熔盐中的电化学行为、热力学等物理特性,介绍了近几年室温离子液体(RTILs)的研究进展及锕系元素在RTILs中萃取特性的最新研究成果,展望了熔盐体系未来的研究方向。     

A Hybrid Anion for Ionic Liquid and Battery Electrolyte Applications: Half Triflamide,Half Carbonate

The synthesis of a new imide type anion, methylcarbonate(trifluoromethylsulfonyl)imide (MCTFSI) is described and the physicochemical properties of its sodium and N‐butyl‐N‐methyl pyrrolidinium salts as well as structural information obtained by X‐ray diffraction studies of the sodium salt are discussed in terms of charge delocalisation, coordination chemistry and electrochemical behaviour with respect to the analogous imdides bis(trifluoromethanesulfonyl)imide (TFSI) and bis(fluorosulfonyl)imide (FSI). The insight obtained from studying the new anion informs and reemphasizes the concept of weakly coordinating anions and coordination chemistry in designing electrolyte salts.     

A theoretical investigation of gadolinium (III) solvation in molten salts

The solvation of lanthanides [here Gd(III)] in molten LiCl and KCl has been studied using a classical solvation approach, based on clusters of increasing size. In particular, density-functional calculations have been carried out on charged and neutral clusters, containing up to 35 chlorine halide molecules. A number of properties have been then evaluated and analyzed, including structural, vibrational, and thermochemical data. Special attention has also been devoted to the analysis of the local structure of the solvent surrounding the Gd3+ cation, a problem deeply investigated by experimentalists. Our results show that the charged clusters are not suitable to model the first solvation shell in such species, since their structures are strongly affected by the large electrostatic contribution. In contrast, more reliable simulations are obtained using the neutral clusters. In the latter, the coordination of Gd(III) in molten salts is computed to be 8 or 6, according to the salt LiCl or KCl. Furthermore, a good agreement is found with the experimental structural data and Raman spectra. Finally, preliminary results of potential interest for the estimation of solvation thermodynamics, a key parameter for exploiting molten salt chemistry, are reported for neutral clusters.     

Contemporary Chemistry of Berkelium and Californium

The merging of small-scale syntheses and rapid crystallization methods have provided access to crystalline samples of berkelium (Z=97) and californium (Z=98) coordination complexes and compounds that can be interrogated with a suite of spectroscopic tools and structural elucidation approaches that have come online over the last 20 years. The combination of this experimental data with relativistic theoretical methods that capture the effects of spin-orbit coupling and scalar relativistic effects have allowed us to understand the electronic structure of berkelium and californium compounds at a level of detail that was not previously possible. The harbinger of this new era of post-curium chemistry was the synthesis and characterization of [Cf{B₆O₈(OH)₅}]. This compound possesses a structure type that is distinct from earlier actinide borates, a reduction in coordination number for californium, contracted Cf−O bond lengths, a substantially reduced magnetic moment with respect to the calculated free-ion moment and, most importantly, vibronically coupled broadband photoluminescence. Ligand-field analysis also showed that the splitting of the ground state was larger than typically found in the f-block elements, and when taken together places its overall electronic structure as a hybrid of d- and f-block components. The discovery of the unusual properties of this compound has led to the development of large families of 4f and 5f coordination complexes, in an effort to uncover the underlying origin of the electronic structure oddities, and whether there really is a sharp onset of these changes at californium. This in turn pushed the development of far more challenging berkelium chemistry (from a radiologic standpoint) because the half-life of the isotopes decreases from 351 years for ²⁴⁹Cf to 330 days for ²⁴⁹Bk. This short review details some of the chemistry that has been reported over the last 15 years, and its consequences for understanding the periodic table.     

Self-assembled microspheres from f-block elements and nucleoamphiphiles

Hollow microspheres featuring a hybrid lipid-cation multilamellar shell are prepared by hydration of a nucleoside based amphiphile with an aqueous solution containing either actinide or lanthanide salts. The physico-chemical data collected clearly indicate that the formation of these microspheres is a consequence of the following concomitant stabilizing factors: (i) hydrophobic interactions, (ii) nucleobase dimer formation and (iii) phosphate/f-block element salt binding.     

Coordination chemistry of actinides in molten salts

The problems of actinide molten salt coordination chemistry are considered in terms of spectroscopic parameters as functions of melt composition and temperature. Parameters connected with energy, intensity and fine structure of 5f-5f transitions have been obtained for molten alkali metal chlorides, fluorides and chloride-fluoride mixtures. The regularities of variation of both actinide-chlorine distances and actinide fluorocomplex stability have been studied.     

熔盐体系及有关应用的新进展

介绍近年来熔盐体系的概况,着重室温熔盐的发展.熔盐在电化学制备合金和功能材料、能源、分析和分离、用作反应介质和催化剂、环境保护等方面应用前景良好.     

绿色化学与铬盐工业的新一代产业革命

本文介绍了铬盐生产的绿色化学研究的内容和方法, 所开拓的熔盐液相氧化-高浓介质单向分离-介稳态相分离-碳化循环转化的多相反应与分离系统的绿色化学新原理, 资源深度利用-反应介质内循环-零排放的完整绿色工业化学体系。     

Alfred Werner: Overlooked Genius of the Periodic System

2019, which was proclaimed by the United Nations as the International Year of the Periodic Table, sees one hundred years since Alfred Werner, the first Swiss to receive a Nobel Prize in chemistry, passed away. The undoubted father of coordination chemistry, he is also well-known for influencing many other fields of chemistry, including organic, inorganic, organometallic, bioinorganic, and stereochemistry. However, one of his more rare and unique contributions to chemistry, his 1905 version of the periodic system, to this day remains overlooked. The simple and elegant idea which he used to construct his periodic table has not been communicated to the English-speaking world, because Alfred Werner published his only original paper on the periodic table in German. Werner's simple mathematical approach lead to overwhelming success with anticipating the future f-block. He managed to predict almost perfectly the number of lanthanides, which was hotly debated at that time. Werner's genius vision was considerably ahead of its time. It was not until the 1940s and the discovery of actinide series when the idea of representing the elements as a 32-column periodic table finally became justified.     

Over one century after discovery: pyrylium salt chemistry emerging as a powerful approach for the construction of complex macrocycles and metallo-supramolecules

Over one century after its discovery, pyrylium salt chemistry has been extensively applied in preparing light emitters, photocatalysts, and sensitizers. In most of these studies, pyrylium salts acted as versatile precursors for the preparation of small molecules (such as furan, pyridines, phosphines, pyridinium salts, thiopyryliums and betaine dyes) and poly(pyridinium salt)s. In recent decades, pyrylium salt chemistry has emerged as a powerful approach for constructing complex macrocycles and metallo-supramolecules. In this perspective, we attempt to summarize the representative efforts of synthesizing and self-assembling large, complex architectures using pyrylium salt chemistry. We believe that this perspective not only highlights the recent achievements in pyrylium salt chemistry, but also inspires us to revisit this chemistry to design and construct macrocycles and metallo-supramolecules with increasing complexity and desired function.

This perspective summarizes the representative efforts of synthesizing and self-assembling large, complex architectures using pyrylium salt chemistry.     

Removal behavior of Cs from molten salt by using zeolitic materials

Radioactive molten salt generated from a pyrochemical process to separate reusable U and TRU elements is one of problematic wastes to manage for a final disposal. For the minimization of final waste, it is desirable to selectively remove radionuclides from the waste salts. In this paper, structural change of some zeolites in a series of molten salt systems and its removal behavior of CsCl was investigated. Zeolite-4A(LTA) was transformed into LiAlSiO₄ and Li-sodalite with the mol-fraction of LiCl in LiCl–KCl system at 650 °C while it was not changed in NaCl–KCl at 750 °C, regardless of mol-fraction of metal chloride. Other commercial zeolite with specific structure (FAU) had the same trends on the structural stability in molten salt system. From the Cs removal experiments, the decomposed zeolitic materials in molten salt lost their removal ability of Cs. In conclusion, a new selective material or method should be investigated or developed for obtaining the validity on the separation of group I and II radionuclides from a molten waste salt because the zeolite 4A is unstable in the LiCl system and it also showed a low capacity in the LiCl–KCl phase. This paper gives basic information on the removal of radionuclides from molten systems by using zeolitic materials.     

Study on a separation method of radionuclides (Ba, Sr) from LiCl salt wastes generated from the electroreduction process of spent nuclear fuel

In this paper, a separation method of radionuclides (Ba, Sr) from LiCl salt wastes generated from the electroreduction process of spent nuclear fuel was studied to recover pure LiCl salts and reduce radioactive wastes. The method consisted of chemical conversion process of BaCl₂ and SrCl₂ in LiCl molten salts by using lithium compounds and vacuum distillation process of LiCl salts. In the chemical conversion, BaCl₂ and SrCl₂ in LiCl molten salts were mainly converted into (Ba,Sr)CO₃ or (Ba,Sr)SO₄. Contents of Ba and Sr in LiCl salts recovered from the vacuum distillation process were equal to about 0.01 of initial concentrations of Ba and Sr in LiCl molten salts. These results will be utilized to recycle the LiCl salt wastes.     

Electrochemical synthesis of ammonia in molten salts

Ammonia is important feedstock for both fertilizer production and carbon-free liquid fuel.Many techniques for ammonia formation have been developed,hoping to replace the industrial energy-intensive Haber-Bosch route.Electrochemical synthesis of ammonia in molten salts is one promising alternative method due to the strong solubility of N~(3-) ions,a wide potential window of molten salt electrolytes and tunable electrode reactions.Generally,electrochemical synthesis of ammonia in molten salts begins with the electro-cleavage of N_2/hydrogen sources on electrode surfaces,followed by diffusion of N~(3-)/H~+-containing ions towards each other for NH_3 formation.Therefore,the hydrogen sources and molten salt composition will greatly affect the reactions on electrodes and ions diffusion in electrolytes,being critical factors determining the faradaic efficiency and formation rate for ammonia synthesis.This report summarizes the selection criteria for hydrogen sources,the reaction characteristics in various molten salt systems,and the preliminary explorations on the scaling-up synthesis of ammonia in molten salt.The formation rate and faradaic efficiency for ammonia synthesis are discussed in detail based on different hydrogen sources,various molten salt systems,changed electrolysis conditions as well as diverse catalysts.Electrochemical synthesis of ammonia might be further enhanced by optimizing the molten salt composition,using electrocatalysts with well-defined composition and microstructure,and innovation of novel reaction mechanism.     

Results and perspectives in the chemistry of side-chain-functionalized cyclopentadienyl compounds

Cyclopentadienyl (Cp) compounds of s-, p-, d-, and f-block elements with donor functionalities in the side-chain of the Cp fragment have attracted a lot of attention during the last decade. In this article, the structure and reactivity of representative compounds with tethered NR₂, OR, PR₂, SR, and CH=CHR groups are described; one, two (in 1,3 position) or five donors are attached with C_n or SiC_n spacers to the Cp fragment. Intra- or intermolecular donor—acceptor interactions can be classified with the help of the HSAB concept. A ‘hard—soft’ coordination promotes hemilability and causes interesting effects concerning reactivity. Side-chain-functionalized compounds find application in catalysis, CVD and related techniques, molecular recognition, organometallic chemistry in water, and dendrimer synthesis. Perspectives in these fields are presented.     

Paramagnetic metal complexes of diamido donor ligands

Recently, considerable attention has been given to the use of multi-dentate amido ligands in the coordination chemistry of a range of transition metals as a means of accessing novel structural motifs and unusual reactivity. Presented herein is a perspective on transition and f-block metal complexes containing diamido donor ligands of the general form [NDN](2-) (D = NR, O, PR). Particular focus is given to paramagnetic metals, which have in general been studied much less than their diamagnetic counterparts despite their potential to exhibit unique structures and diverse reactivity patterns, in addition to their magnetic properties.     

f-Block Phospholyl and Arsolyl Chemistry

The f-block chemistry of phospholyl and arsolyl ligands, heavier p-block analogues of substituted cyclopentadienyls (Cp^R, C₅R₅) where one or more CR groups are replaced by P or As atoms, is less developed than for lighter isoelectronic C₅R₅ rings. Heterocyclopentadienyl complexes can exhibit properties that complement and contrast with Cp^R chemistry. Given that there has been renewed interest in phospholyl and arsolyl f-block chemistry in the last two decades, coinciding with a renaissance in f-block solution chemistry, a review of this field is timely. Here, the syntheses of all structurally characterised examples of lanthanide and actinide phospholyl and arsolyl complexes to date are covered, including benzannulated derivatives, and together with group 3 complexes for completeness. The physicochemical properties of these complexes are reviewed, with the intention of motivating further research in this field.     

熔盐电化学创新研究——武汉大学电化学研究中心熔盐电化学研究工作简介

简要介绍近3年武汉大学电化学研究中心在熔盐电化学方面的若干研究进展:1)熔盐电解固态化合物制备单质硅及其合金以及无机功能材料;2)适于高温熔盐的全密封长寿命Ag/AgCl参比电极和可负载微量粉末的金属腔(坑)工作电极新技术;3)“三相界线电化学”新概念以及描述三相界线在薄层固态化合物电解还原过程中扩展变化的薄层模型.     

Ionization state and ion migration mechanism of room temperature molten dialkylimidazolium fluorohydrogenates

The ionization state of room temperature molten salts, alkylimidazolium fluorohydrogenates (RMIm(HF)(2.3)F: R = alkyl group, M =methyl group), was evaluated from the observed diffusion coefficient and viscosity, using the Stokes-Einstein relation. Assuming that the dissociation degree of the salt is acceptable for representation of the ionic state of the molten salts, the larger the cation size with elongation of the alkyl chain was, the higher the dissociation degree of the salt. Further, we proposed that an idea of the "degree of ordering of cations and anions" was more suitable to represent the ionization state without solvent species. On the basis of this idea, the smaller the cation size of RMIm(HF)(2.3)F salt was, the higher the ordering of the ion, indicating formation of domain particles of aggregated ions as a unit of mobile species such as A(AX)m+ and X(AX)n- for A+ X- salt. It was found that highly ordered particles, with large numbers for m and n, showed a high diffusion coefficient.     

Versatile Carborane Cages:A New Class of Metallacarboranes Incorporating the η7-Carboranyl Ligand

The chemistry of metallacarboranes has witnessed an explosive growth since the first metallacarborane was reported in 1965. A large number of metallacarboranes of s-,p-, d-,and f-block elements are known; however, the highest hapticity of carboranyl ligands in these compounds has been six. We have recently discovered a brand new bonding mode for carborane molecules, and some recent findings in our laboratory will be presented in this paper.     

Conjugated polymer/molten salt blend optimization

Light-emitting electrochemical cells with low current threshold can be realized through mixing conjugated polymers and molten salts. Current drive capability is proportional to the overall interface perimeter of the planar, discotic molten salt domains inserted into the polymer matrix. Electric force microscopy indicates that this interface perimeter exhibits a specific dependence on the molten salt content in the active layer, with a well-defined maximum. We show that this maximum corresponds to an optimal current drive.