Highly ion conductive poly(ethylene oxide)-based solid polymer electrolytes from hydrogen bonding layer-by-layer assembly

We report the development of a solid polymer electrolyte film from hydrogen bonding layer-by-layer (LBL) assembly that outperforms previously reported LBL assembled films and approaches battery integration capability. Films were fabricated by alternating deposition of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) layers from aqueous solutions. Film quality benefits from increasing PEO molecular weight even into the 10(6) range due to the intrinsically low PEO/PAA cross-link density. Assembly is disrupted at pH near the PAA ionization onset, and a potential mechanism for modulating PEO:PAA ratio within assembled films by manipulating pH is discussed. Ionic conductivity of 5 x 10(-5) S/cm is achievable after short exposure to 100% relative humidity (RH) for plasticization. Adding free ions by exposing PEO/ PAA films to lithium salt solutions enhanced conductivity to greater than 10(-5) S/cm at only 52% RH and tentatively greater than 10(-4) S/cm at 100% RH. The excellent stability of PEO/PAA films even when exposed to 1.0 M salt solutions led to an exploration of LBL assembly with added electrolyte present in the adsorption step. Fortuitously, the modulation of PEO/PAA assembly by ionic strength is analogous to that of electrostatic LBL assembly and can be attributed to electrolyte interactions with PEO and PAA. Dry ionic conductivity was enhanced in films assembled in the presence of salt as compared to films that were merely exposed to salt after assembly, implying different morphologies. These results reveal clear directions for the evolution of these promising solid polymer electrolytes into elements appropriate for electrochemical power storage and generation applications.     

Kinetic and mechanistic studies of the thermal stabilization of polyacrylamide by metal ions

The kinetics of thermal decomposition of polyacrylamide under a nitrogen atmosphere are studied in the presence of adsorbed metal ions using rising temperature thermogravimetry. Results are analysed using the method of Coates and Redfern¹⁵ and indicate that all of the metal ions, except Tl(I), Hg(I) and Ni(II), stabilize the polymer against degradation. Attempts are made to correlate both initial and total activation energies for degradation with various parameters, including reciprocal ionic radii, ionization potentials, electronegativity and ligand field stabilization energy, to obtain a better understanding of the mechanism of stabilization. The best correlations are between the total activation energy and either reciprocal ionic radii, or the Kahwa-Mulokozi function involving covalent and ionic radii, and ionization potentials. It is suggested that both covalent and ionic interactions in the polymer-metal ion complexes may be important in the stabilization.     

特烯合成中金属子的模板效应

本文报道了以乙醇为溶剂, 呋喃与丙酮在浓盐酸催化下缩合生成2,2,7,7,12,12,17,17-八甲基-21,22,23,24-四氧 特烯, 采用固定反应时间, 比较产率的方法, 研究Sn^2^+, Sb^3^+, Al^3^+, Zn^2^+等金属离子对合成 特烯的模板效应的影响.     

离子质电比和相差异因子对离子半径的综合标度

根据万有引力势与电势的关系式和系统的质电比(单位电量的质量)Sr的物理意义, 研究了离子半径r与离子的Sr和相差异因子的关系. 对于阳离子, r与lgSr和相差异因子呈线性关系; 对于稳定构型阴离子, r与Sr和相差异因子也存在定量关系. 采用回归分析方法, 给出稳定构型和非稳定构型阳离子半径计算公式, 以及稳定构型阴离子半径计算公式. 从相关系数R和回归方程的显著性检验(F)都可说明r与Sr和相差异因子密切相关, 其中拟合的96种元素的138种阳离子半径数据与具有代表性参考值相比, 平均绝对误差为2.0 pm, 相对误差为2.5%. 并预测出较为合理的稀有气体等30种离子半径数据. 同时给出一条获取离子半径(包括复杂离子)数据的新途径.     

Phase and extraction equilibria in the antipirin-pyrocatechol-water system

Solubility isotherms of the antipirin-pyrocatechol-water ternary system at 25 and 50°C were constructed. A field where two liquid phases are present in equilibrium which results from the protolytic interaction between the components was revealed. The various-composition chemical compounds that formed were isolated preparatively. Interphase distribution of a series of metal ions was studied. The half-extraction pHs of rare-earth metals were found to be linearly related to their ionic radii.     

Approaches to hydration, old and new: Insights through Hofmeister effects

Hydration effects in colloidal interactions or problems involving electrolytes are usually taken care of by effective electrostatic potentials that subsume notions like hydrated ion size, Gurney potentials, soft and hard, chaotropic and cosmotropic ions, and inner and outer Helmholtz planes. Quantum fluctuation (dispersion) forces between ions and between ions and surfaces are missing from classical theories, at least not explicit in standard approaches to hydration. This paper outlines an evolving back-to-basics approach that allows these ion specific forces to be included in theories quantitatively. In this approach ab initio quantum mechanics is used to calculate dynamic polarisabilities of ions and to quantify bare ion radii. The ionic dispersion potentials between ions, and between ions and surfaces in water can then be given explicit analytic form from an extension of Lifshitz theory. They are included in the theory along with electrostatic potentials. In a first stage the primitive (continuum solvent) model provides a skeletal theory on which to build in hydration. Extension of the ab initio calculations to include “dressed” ions, i.e. water hydration shells for cosmotropic ions, quadrupolar and octupolar polarisability contributions and; for colloids, allowance for a surface hydration layer, permits quantification of Hofmeister effects and Gurney potentials. With these extensions, primary hydration forces (short range repulsion) arise due to an interplay between surface hydration layers and specific ion interactions. Apparent longer range “secondary hydration forces” are shown to be a consequence of ion-surface dispersion interactions and are not true “hydration forces”.     

A nearly complete system of average crystallographic ionic radii and its use for determining ionization potentials

Available systems of empirical (crystallographic) ionic radii are compared. All these systems turn out to be compatible if the O^2? radius is taken to be 0.140 nm. The choice of the oxygen ionic radius is dictated by the equality of the metal ion-oxygen ion distances in oxide crystals and the metal ion-oxygen atom distances in crystal hydrates and concentrated aqueous solutions. In all systems of empirical ionic radii under consideration, the uncertainty of determination of ionic radii is 0.002–0.005 nm. A new method of determination of the ionic radii of elements in unusual valence states is suggested: from the empirical dependence of the electron density at an atom in a given valence state on the atomic radius, a two-parameter equation relating the ionic radii of Period 4–7 elements in two valence states is derived, which allows one to calculate the ionic radius that cannot be determined by crystallography because of the lack of stable compounds in this valence state. Ionic radii are calculated for all Period 4–7 elements in all valence states. They constitute a nearly complete system of ionic radii. There is a linear relationship between the atomic nucleus charge and the inverse ionic radius. It is shown that the square root of the ionization potential is a linear function of the inverse ionic radius. The as yet experimentally unknown ionization potentials of 78 ions of different elements are estimated.     

Mass spectrometric studies on small open-chain piperazine-containing ligands and their transition metal complexes

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry was used to characterize the complexes formed between open-chain piperazine-containing ligands and transition metal salts (Cobalt, Copper, Zinc, and Cadmium as chlorides, nitrates, and acetates). Only single-charged complexes were observed, formed of one ligand (L) and mainly one metal ion (M). Since the net charge of the complexes was one, a counterion (X) was attached to some of the complexes, with formation of [L + M + X]+ complexes, and a proton was lost from others, as in [L - H + M]+ complexes. In most cases the composition of the complexes was more dependent on the ligand than the metal salt. Collision-induced dissociation measurements showed that complexes with related composition often differed in structure, or that interactions between the ligand and the metal ion were not alike. The metal ion influenced considerably the fragmentation pathways of the ligands, so that the fragmentation products could be used to deduce the binding sites of the metal. The variations observed in fragmentation behavior of complexes possessing the same ligand but different metal ions can mostly be explained by the ionic radius and electronic configuration of the metal ion. The results indicated a preference of the piperazine ring of the coordinated ligand for the boat conformation.     

Comparing π-complexation capabilities of ionic liquids containing silver(I) and copper(I) ions by headspace single drop microextraction in combination with high-performance liquid chromatography

Selective π-complexation capabilities of silver(I) and copper(I) ions can be effectively facilitated in ionic liquids. To understand the effects of environmental factors that influence the π-complexation of these metal ions with analytes, techniques that employ small volumes of ionic liquid that can be readily analyzed are desired. In this study, headspace single drop microextraction coupled with HPLC is used to investigate a diverse set of environmental factors on the metal ion-mediated complexation with aromatic compounds in ionic liquid media. Silver(I) and copper(I) bis[(trifluoromethyl)sulfonyl]imide salts were both studied by dissolving them in the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ionic liquid and employing the mixture as extraction media for aromatic compounds. Water and acetonitrile within the sample solution were observed to interfere with the complexation of silver(I) ions and aromatic compounds, while ethylene glycol and triethylene glycol did not. The temperature and extraction times were optimized to fully facilitate the π-complexation capabilities of metal ions in ionic liquid media. Partition coefficients between the sample headspace and metal ion were determined using a three-phase equilibria model. Although no discernable difference in analyte partitioning between the headspace and ionic liquid solvent was observed, analyte partition coefficients to silver(I) ion tended to be greater compared to copper(I) ion.     

离子半径的质量和电量综合因子的标度

根据作者曾建立的万有引力势与电势的关系式和系统的对比质电比(单位电量的质量)Sr的物理意义, 研究了离子半径r与Sr的关系: 对于相同电子构型的阳离子, 离子半径与lgSr呈线性关系; 对于相同电子构型的阴离子, 离子半径与Sr的关系满足Michealis-Menten 数学模型. 采用回归分析方法, 拟合出周期表中94种元素108种阳离子的半径和16种阴离子的半径. 从相关系数R和回归方程的显著性检验(F)都说明r与Sr密切相关, 其中102种阳离子半径数据与具有代表性的离子半径参考值相比平均绝对误差仅0.9 pm, 相对误差1.1%. 同时给出一条获取离子半径(包括复杂离子)数据的新途径.     

Gold glyconanoparticles for mimics and measurement of metal ion-mediated carbohydrate-carbohydrate interactions

To mimic and measure calcium ion-mediated carbohydrate-carbohydrate interactions, four lactose derivatives have been synthesized for assembly on gold nanoparticles. The series of lactose derivatives varied by the length of the thiolated ethylene glycol anchor chain [O(CH2CH2O)(m)CH2CH2SH; where m = 0, 1, 2, and 3] used to self-assemble the carbohydrates to the preformed gold nanoparticles of ca. 16 nm diameter. Upon addition of calcium ions to the lactose-stabilized nanoparticles, rapid carbohydrate-carbohydrate interactions were visualized and subsequently measured using UV-visible spectrometry and transmission electron microscopy (TEM). The nanoparticle aggregates formed via metal-mediated carbohydrate-carbohydrate interactions could be readily redispersed through the addition of EDTA. Multiple reaggregation and redispersion cycles were achieved, confirming that the aggregation process was due to metal ion-mediated carbohydrate interactions rather than calcium chelation by residual citrate ions on the particle surface. The essential involvement of the lactose moiety in Ca2+ complexation was shown by control measurements on related D-glucose-derivatized nanoparticles, where a significantly reduced aggregation response was obtained only at high ion concentrations. Other group 2 metal ions with radii larger than that of calcium, viz., barium and strontium, were also shown to mediate the aggregation of the lactose-stabilized nanoparticles. The induced aggregation of the lactose nanoparticles was determined to be quantitatively dependent upon the calcium ion concentration. Furthermore, the analytical sensitivity of the calcium-induced aggregation and the linear dynamic range were dependent on the length of the ethylene glycol anchor chain. The shortest ethylene glycol chain (m = 0) gave the most sensitive response with the optimum limit of detection (0.8 mM Ca2+), whereas the longest ethylene glycol chain (m = 3) provides a measurement of calcium ion concentration over the largest linear dynamic range (10-35 mM Ca2+). This work has shown that the self-assembled deposition of lactose derivatives on gold nanoparticles provides multivalent carbohydrate surfaces that can be used as mimics for the measurement of biologically relevant carbohydrate-carbohydrate interactions. Additionally, this study has highlighted the importance of the structure and length of the ligand that anchors the carbohydrate sugar to the gold particle surface to facilitate such carbohydrate interactions and for "tuning" the analytical characteristics of bioassays developed using metal nanoparticle technology.     

Molecular simulation of a concentrated aqueous KCl solution

A 1.0 M aqueous KCl solution was studied by molecular dynamics simulations at 293 K in order to study the influence of the ionic concentration on the hydration structure of the ions as well as the formation of ion clusters. The hydration structures of the ions are almost independent of the ionic concentration unless in respect to the perturbation that appears due to ionic clustering. Fractions equal to 31.9% of the anions and 37.8% of the cations are associated. Clusters constituted by two, three and four ions were detected. Their mean lifetimes are always affected by thermal effects, reorientational relaxation while the longest lifetimes are a consequence of ionic cloud relaxations. The pairs constituted by two anions or two cations are stabilized by water molecules belonging to the solvation shells of both ions. The neutral K⁺Cl⁻ pairs are formed under the influence of the electrostatic attraction that, however, is small due to the ionic radii of these ions. Consequently, this kind of pairs contains only 8.8% of the ions while the fraction of ions in the negative and positive pairs are equal to 29.2 and 39.3%, respectively, when the same ion can pertain to more than one pair.     

Treatment of heavy metal ions in wastewater using layered double hydroxides: A review

Heavy metal ions are toxic, and their toxicities change with different valence states, charges, and radii. Among the methods used for heavy metal ion removal, adsorption is widely employed due to its low cost and simple operation. As natural anionic clays, layered double hydroxides (LDHs) have drawn considerable attention for their use in the removal of anionic pollutants (such as heavy metal anions) due to their high removal efficiency and environmental friendliness. This article reviews the effects of the charge, type, and radius of the cations in the laminates of LDHs and the anions in the LDH interlayers, as well as the charge and radius of the heavy metals and the conditions (such as pH, coexisting ions, and temperature) on removing heavy metal ions with LDHs. The removal mechanisms have also been discussed. LDHs are hugely promising as an application for removing heavy metal ions that exist in different ionic forms by controlling the type and condition of LDHs.     

Thermal stability of ion-exchange Nafion N117CS membranes

The effect of exchanged ions on the thermal stability of Nafion N117CS membranes was investigated by X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and ion exchange capacity determinations. The ion exchange of alkaline metal ions was effective in improving the thermal stability of the Nafion N117CS membrane. Findings reveal that when Nafion was exchanged for cations with a larger ionic radius, the membrane attained superior thermal stability. On the other hand, we confirmed that the Na-exchange Nafion N117CS membrane possessed a distinctive degree of thermal stability among the alkaline ion-exchange Nafions, although the order of ionic radii is K > Na > Li. Thermal stability improved the most when the Nafion membrane was exchanged for alkaline ions, followed by divalent ions, then trivalent ions. As for the Nafion membrane when it was exchanged for divalent ions or trivalent ions, Nafion following the ion exchange had a thermal stability proportional to an increase in the ionic radius of the cation. This stability may be explained by the reduction of water content and a greater interaction between the sulfonate groups and the cations with larger ionic radii. Since the Al cations acted as a Lewis acid center, the decomposition of the ether bonds of the perfluoroalkylether pendant-chains of the Nafion membrane was observed for the Nafion N117CS membrane that had been exchanged for Al ions. The activation of molecular mobility in Nafion was observed between the decomposition stages of the loss of water and the loss of sulfonic groups. The temperature of activation of cation-exchange Nafion became much higher than that of Nafion in an acid form.     

Remarkably high asymmetric amplification in the chiral lanthanide complex-catalyzed hetero-Diels-Alder reaction: first example of the nonlinear effect in ML3 system

[reaction: see text] A remarkably high asymmetric amplification was realized in the Yb[(R)-BNP]3-catalyzed hetero-Diels-Alder reaction as the first example in the metal/chiral ligand 1:3 system. The mechanism may be explained by the autogenetic formation of the enantiopure complex as the most active catalyst. The enantiomer-discriminative formation of homochiral ML3 complexes is quite general within the lanthanide metal ions with similar ionic radii to that of the ytterbium ion.     

Modification of Surface Forces by Metal Ion Adsorption

Abstract

Sorption of ions may lead to variations in interparticle forces and, thus, changes in the stability of colloidal particles. Chemical interactions between metal ions and colloidal particles modify the molecular structure of the surface, the surface charge, and the electrical potential between colloidal particles. These modifications to the surface and to the electrical double layer due to metal ion sorption are reflected in the interaction force between a particle and another surface, which is measured in this study by atomic force microscopy (AFM). Specifically, AFM is used to investigate the sorption of copper ions from aqueous solutions by silica particles. The influence of metal ion concentration and solution ionic strength on surface forces is studied under transient conditions. Results show that as the metal ion concentration is decreased, charge reversal occurs and a longer period of time is required for the system to reach equilibrium. The ionic strength has no significant effect on sorption kinetics. Furthermore, neither metal concentration nor ionic strength exhibits any effect on sorption equilibria, indicating that for the experimental conditions used in this study, the surface sites of the silica particle are fully occupied by copper ions.     

基于过渡金属离子与三联吡啶的配位作用构筑全共轭层-层 自组装超薄功能膜

本文利用所合成的4'-（4''-重氮基）苯基-（2,2':6',2'）-三联吡啶氟硼酸盐（Diazo-tpy）在紫外光照射下的光分解反应特性,实现三联吡啶基团与基片之间形成共轭价键连接,这不仅提高了自组装膜的稳定性,而且降低了载流子在两者之间传输时的阻抗;在此基础上,通过两端含三联吡啶的直线型配体1,4-二-(2,2':6',2'-三联吡啶)基苯（Bi-tpy）与四种过渡金属离子（Mtn+：Pt4+、Ru3+、Rh3+、Pd2+）之间的配位作用,通过层－层自组装制备了全共轭金属－有机自组装超薄功能膜。由紫外-可见光谱跟踪自组装过程证明了自组装过程的成功实现,还分析了金属离子的种类对自组装的影响规律。光电转换测试表明Bi-tpy/Ru3+自组装膜要比Bi-tpy/ Pt4+具有更明显的光电转换性能;同时,由于缺陷与阻抗随层数的增加而增大的原因,在自组装6层时光电流达到最大值。这为我们设计新型光电转换器件提供参考依据。     

Preparation of transparent conductive multilayered films using active pentafluorophenyl ester modified multiwalled carbon nanotubes

A mutilayered film was prepared by layer-by-layer (LBL) assembly of active ester modified multiwalled carbon nanotubes (MWCNTs) and poly(allylamine hydrochloride) (PAH). For this purpose, carboxylic groups on the surface of the oxidized MWCNTs were converted to the acyl chlorides by their reaction with thionyl chloride. Subsequent reaction of the acyl chlorides with pentafluorophenol formed the active esters. These active ester modified MWCNTs (MWCNTs-COOC 6F 5) were air-stable and moisture resistant, but showed a high reactivity toward primary or secondary amines resulting in amide bonds. For the preparation of a multilayered film, the surface of a quartz slide was first activated and sacrificial double layers of PAH and poly(sodium 4-styrene sulfonate) (PSS) were deposited. Subsequently, LBL assembly of MWCNTs-COOC 6F 5 and PAH was then conducted on these double layers [(PAH/PSS) 2]. In the process of the assembly, a reaction occurred between the active ester on the surface of MWCNTs and the amine groups of polyallylamine yielding amide bonds, which resulted in a mechanically stable thin film. A free-standing film was obtained after dissolving the sacrificial layer [(PAH/PSS) 2] in a concentrated aqueous NaOH solution. The surface resistance of the multilayered film with 20 bilayers decreased to around 10 kOmega while remaining a reasonable transparency (70% at 500 nm).     

Two‐Dimensional Calix[4]arene‐based Metal–Organic Coordination Networks of Tunable Crystallinity

A flexible and versatile method to fabricate two‐dimensional metal–organic coordination networks (MOCNs) by bottom‐up self‐assembly is described. 2D crystalline layers were formed at the air–water interface, coordinated by ions from the liquid phase, and transferred onto a solid substrate with their crystallinity preserved. By using an inherently three‐dimensional amphiphile, namely 25,26,27,28‐tetrapropoxycalix[4]arene‐5,11,17,23‐tetracarboxylic acid, and a copper metal node, large and monocrystalline dendritic MOCN domains were formed. The method described allows for the fabrication of monolayers of tunable crystallinity on liquid and solid substrates. It can be applied to a large range of differently functionalized organic building blocks, also beyond macrocycles, which can be interconnected by diverse metal nodes.     

Binding of Cu(II) to poly(methacrylic acid)

The binding of Cu(II) ions to partly neutralized poly(methacrylic acid) (PMA) has been investigated by potentiometric titration and dialysis to determine the stoichiometry the Cu–PMA complexes formed. Partly ionized PMA was titrated with solutions of the metal ion to enable a large range of metal ion/polymer ratios to be studied. Combination of the results from these two techniques at ionic strength 0.1 indicates that at very low Cu(II)/polymer ratios, a 4:1 complex exists, but at higher ratios the complex breaks down to give a mainly 2:1 coordination with some 1:1 binding. Conductance titrations support these results. Viscometric titrations show strong interactions between the metal and polymer, preventing the full extension of the polyion at high degrees of ionization, and spectrophotometric titrations support the existence of at least two types of complexes in the solution.