全固态钠离子电池硫系化合物电解质

全固态钠离子电池具有资源丰富、安全性高等优势,作为未来大规模储能的重要选择而成为近年来先进二次电池前沿研究热点。钠离子硫系化合物电解质室温离子电导率高、弹性模量高、容易冷压成型,能增强电极/电解质界面接触、减小界面阻抗、缓冲电极材料在充放电过程中的应力/应变,是全固态钠离子电池的研究重点。本文对钠离子硫系化合物固态电解质的结构及性质进行了总结,讨论了硫系化合物电解质的本征特性、与电极的界面稳定性,并介绍了硫系化合物全固态钠离子电池的研究现状,最后分析了硫系化合物电解质面临的挑战及今后的发展方向。     

Efficient and green syntheses of novel γ-aminophosphonate and phosphine oxide derivatives

Two synthetic protocols leading to novel γ-aminophosphonate and phosphine oxide derivatives, by reductive amination of γ-phosphonylketones, are reported. The first method involved a two-step procedure. Imine intermediates were first isolated from the p-toluenesulfonic acid-catalyzed reaction of primary amines with γ-ketophosphonates and phosphine oxides, then reduced with NaBH₄ in refluxing ethanol. The second method consists of a one-pot procedure which includes the condensation of γ-ketophosphonates and phosphine oxides with primary amines, in the presence of molecular sieves, followed by reduction with NaBH₄. These methods offer significant advantages over prior reports, such as efficiency, generality, and good yields. Furthermore, they are green protocols avoiding hazardous hydrides and solvents.     

Formation of lithium,sodium and potassium complexes with 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol (taci)

Single crystals of (1,3‐diamino‐5‐azaniumyl‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)lithium(I) diiodide dihydrate, [Li(C₆H₁₆N₃O₃)(C₆H₁₅N₃O₃)]I₂·2H₂O or [Li(Htaci)(taci)]I₂·2H₂O (taci is 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol), (I), bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)sodium(I) iodide, [Na(C₆H₁₅N₃O₃)₂]I or [Na(taci)₂]I, (II), and bis(1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol‐κ³O²,O⁴,O⁶)potassium(I) iodide, [K(C₆H₁₅N₃O₃)₂]I or [K(taci)₂]I, (III), were grown by diffusion of MeOH into aqueous solutions of the complexes. The structures of the Na and K complexes are isotypic. In all three complexes, the taci ligands adopt a chair conformation with axial hydroxy groups, and the metal cations exhibit exclusive O‐atom coordination. The six O atoms of the resulting MO₆ unit define a centrosymmetric trigonal antiprism with approximate D_3d symmetry. The interligand O...O distances increase significantly in the order Li < Na < K. The structure of (I) exhibits a complex three‐dimensional network of R—NH₂—H...NH₂—R, R—O—H...NH₂—R and R—O—H...O(H)—H...NH₂—R hydrogen bonds. The structures of the Na and K complexes consist of a stack of layers, in which each taci ligand is bonded to three neighbours via pairwise O—H...NH₂ interactions between vicinal HO—CH—CH—NH₂ groups.     

Electron‐Driven Self‐Assembly of Salt Nanocrystals in Liquid Helium

The self‐assembly of salt nanocrystals from chemical reactions inside liquid helium is reported for the first time. Reaction is initiated by an electron impacting a helium nanodroplet containing sodium atoms and SF₆ molecules, leading to preferential production of energetically favorable structures based on the unit cell of crystalline NaF. These favorable structures are observed as magic number ions (anomalously intense peaks) in mass spectra and are seen in both cationic and anionic channels in mass spectra, for example, (NaF)_nNa⁺ and (NaF)_nF^?. In the case of anions the self‐assembly is not directly initiated by electrons: the dominant process involves resonant electron‐induced production of metastable electronically excited He^? anions, which then initiate anionic chemistry by electron transfer.     

Effects of Sodium Salts Organic Acids Modification on the Microstructure and Dispersion Behavior of Palygorskite Nano-Powder via High-Pressure Homogenization Process

High-pressure homogenization could disaggregate the crystal bundles of palygorskite and favor the adsorption of electrolyte ions onto its surface through the produced cavitation, shear, and turbulence forces, and has evident influences on the micromorphologies and properties of clay. In this work, a series of palygorskite samples modified with sodium citrate, sodium benzoate, sodium lactate, sodium acetate, and sodium propionate were obtained under the condition of high-pressure homogenization. The effects of type and concentration of sodium salts organic acids on the microstructure, morphology, surface charge, and physicochemical property of palygorskite were studied through x-ray diffraction (XRD), N₂ adsorption–desorption isotherm, field emission scanning electron microscopy, zeta potential, rotational viscosity, and rheological measurements. XRD results confirmed that the crystal structure of homogenized palygorskite was not changed after introduction of sodium salts organic acids, but the aggregates were effectively disaggregated. Modification of palygorskite with sodium citrate made the surface more negatively charged, and the samples exhibited higher specific surface area and rheological properties. This work provided a method to improve the rheological properties of palygorskite suspension through dispersion of clay in sodium citrate solution followed by homogenization at 30 MPa.      

Functionalized carbon dots as sensors for gold nanoparticles in spiked samples: Formation of nanohybrids

This paper reports the synthesis, passivation and functionalization of luminescent carbon dots (CDs) possessing surface thiol ending groups. A simple procedure involving amidation of passivated carbon dots (p-CDs) with cysteamine boosts their photoluminescent properties and enables their use as easily controlled fluorescent nanosensors for determining citrate–gold nanoparticles (AuNPs). The mechanism behind the quenching phenomenon was established from fluorescence measurements at high temperatures and lifetime tests, and found to involve static quenching leading to the formation of CD–AuNP nanohybrids. A method for determining AuNPs in complex matrices was developed and validated by application to spiked drinking water and mussel tissues. The limits of detection and quantitation for AuNPs thus obtained were 0.20 and 0.66 nmol L^–1, respectively.     

Copper‐Catalyzed Tandem Synthesis of Functionalized Sulfonyl‐yn‐imines from Sodium Arylsulfinates,Trichloroacetonitrile, and Terminal Alkynes

A one‐pot synthesis of functionalized sulfonyl‐yn‐imines via a Cu‐catalyzed tandem reaction of sodium arylsulfinates, trichloroacetonitrile, and terminal alkynes has been developed.     

ChemInform Abstract: Crystal Structure of Potassium Sodium Heptahydrogen Hexamolybdocobaltate(III) Octahydrate: An Extra‐Protonated B‐Series Anderson‐Type Heteropolyoxidometalate.

KNa[Co^III(OH)₇{Mo₆O₁₇}] ·8H₂O is obtained by ion‐exchange from a solution of K₃ [Co(μ₃‐OH)₆Mo₆O₁₈] ·7H₂O at ≈pH 1.4 using Amberlite IR120 ion exchange resin followed by concentrating the solution in a hot water bath.     

新型绿色有机合成反应设计:Pd/β-环糊精催化的纯水相铃木-宫浦偶联反应*

以环境友好的β-环糊精代替毒性膦配体、纯水代替有机溶剂,设计了4-溴苯乙酮和苯硼酸的绿色铃木-宫浦偶联反应。通过单因素实验,探讨了氯钯酸钠用量、氯钯酸钠/β-环糊精配比、苯硼酸用量、反应温度以及反应时间等对产率的影响。通过引导学生对β-环糊精结构的认识和机理探讨,让学生深刻感受到了绿色化学在有机合成中的重要性,并激发了他们对科学研究的兴趣。该实验环境友好,反应条件温和,反应时间短,产率高,重复性好,适宜于本科实验教学。     

乙醛与新制氢氧化铜反应的条件分析及产物成分探究*

借助手持技术通过电化学方法测定乙醛与新制氢氧化铜反应的电压变化情况,揭示了该反应的本质,通过控制变量的思想探究了NaOH在该反应中所起的作用,并结合相关文献知识和实验对比进一步探究了乙醛与新制氢氧化铜反应产物的成分。