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。     

Urea Biosensors Based on PVC Membrane Ion-Selective Electrodes

Abstract

This paper presents a general method of enzyme immobilization at the surface of ion selective membranes. Covalent binding of enzymes directly on the electrode surface is a very effective method that results in stable enzymatic membranes. As an example the construction of enzymatic sensors for urea determination based on ammonium and hydrogen carbonate ion selective electrodes is presented. The optimum working conditions for these biosensors were found. Bioelectrodes based on an ammonium sensor show very good analytical parameters: dynamic stability - over 2 months without decrease of sensitivity, response time - shorter then 20 s. high sensitivity, determination range from 0.3 to 70 mM. In the contrast to the ammonium ion based biosensors, those constructed on the basis of anion selective electrodes have worse analytical parameters. It is mainly due to poor selectivity and instability of an applied ion selective electrode. In spite of this, both types of urea biosensors were used for measurements in the differential potentiometry mode. The application of such system increased the sensitivity of urea determination.     

Highly Selective Sodium Ion Responsive Glass Electrode

Abstract

A highly selective electrode glass for the measurement of sodium ion activity is described. The corresponding glass electrodes shew a selectivity for sodium over hydrogen ions of about 10 and for sodium over potassium ions of about 10,000.     

Structure of Sol-Gel-Derived Sodium Dititanate Glass

The sodium dititanate, Na₂O·2TiO₂ glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti⁴⁺ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti⁴⁺ ions are rather in five-fold coordination state, forming TiO₅ pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass.     

Selective Electrochemical Detection of Explosives with Nanomaterial Based Electrodes

Explosive detection technologies play a critical role in maintaining national security, remain an active research field with many devices and analytical/electroanalytical techniques. Analytical chemistry needs for homeland defense against terrorism make it clear that real-time and on-site detection of explosives and chemical warfare agents (CWAs) are in urgent demand. Thus, current detection techniques for explosives have to be improved in terms of sensitivity and selectivity, opening the way to electrochemical devices suitable to obtain the targeted analytical information in a simpler, cheaper and faster way. For the electrochemical determination of energetic substances, a large number of sensor electrodes have been presented in literature using different modification materials, especially displaying higher selectivity with molecularly imprinted polymers (MIPs). MIPs have already been utilized for the detection of hazardous materials due to their mechanical strength, flexibility, long-time storage and low cost. The sensitivity of MIP-based electrosensors can be enhanced by coupling with nanomaterials such as graphene oxide (GOx), carbon nanotubes (CNTs), or nanoparticles (NPs). Specific characteristics of involved nanomaterials, their modification, detection mechanism, and other analytical aspects are discussed in detail. Non-MIP electrosensors are generally functionalized with materials capable of charge transfer, H-bonding or electrostatic interactions with analytes for pre-concentration and electrocatalysis on their surface, whereas nanobio-electrosensors use analyte-selective aptamers having specific sequences of DNA, peptides or proteins to change the potential or current. This review intends to provide a combination of information related to MIPs and nanomaterial-based electrochemical sensors, limited to the most significant and illustrative work recently published.     

Sulfonamides as Ionophores for Ise. III. Guanidinium Ion-Selective Electrodes Based on Lipophilic Bis-Sulfonamide Podands

Abstract

PVC membrane ion-selective electrodes based on bis-sulfonamide podands and DOS (Bis(2-ethylhexyl)-sebacate) as plasticizer are described. They were found to behave as guanidinium ion sensors, exhibiting high selectivity for guanidinium ions over potassium ions.     

Determination of Inorganic and Organic Thiophosphates with Ion-Selective Membrane Electrodes

Abstract

The conditions for the determination of sodium thiophosphate and sodium S-(2-amino-ethyl)-thiophos-phate in the presence of phosphate ion using ion-selective membrane electrodes are described. Both thiophosphates (inorganic and organic) are hydrolyzed in acidic medium. The phosphate ion is determined with Pb(II) using a Pb²⁺ – selective membrane electrode.

Cysteamine is determined by potentiometric titration with Hg(I1) using a Ag⁺/S^2? – crystal membrane electrode or by direct potentiometry with a Cu²⁺ selective membrane electrode. The results were verified by the iodination method.     

1,3,4-Trisubstituted-2-azetidinone Derivatives as Novel Receptors for Bismuth(III) Ion-Selective Electrodes: Application in Pharmaceutical and Glass Samples

Abstract

Polymeric membrane electrodes (PMEs) and coated graphite electrodes (CGEs) containing 1,3,4-trisubstituted-2-azetidinone derivatives as ion carriers are reported here for bismuth(III) ion selectivity. These electrodes exhibited Nernstian response for Bi³⁺ ions over a wide concentration range (5.0 × 10^?7 M to 1.0 × 10^?1 M for CGE) with a lower detection limit of 3.98 × 10^?7 M (for CGE) and wide pH range (1.3–5.0). Compared to polymeric membrane electrode, the coated graphite electrode has shown better selectivity for Bi³⁺ ions with respect to common metal ions. Proposed electrodes have been used for the estimation of Bi³⁺ ions in pharmaceutical and glass samples.     

掺锡三氧化二铟导电玻璃双工作电极薄层光透电化学池的设计

本文报道了ITO导电玻璃双工作电极薄层光透电化学池的设计。这种薄层池具有操作简便,成本低廉的特点,其突出优点在于工作电极的边际效应因采用辅助工作电极而得以明显消除。以Fe(CN)_6~(3-)/(4-)~考察了该池的电化学和光谱吸收响应特性。     

Peptide Modified Electrodes as Electrochemical Metal Ion Sensors

Sensors for the detection of metal ions are of considerable importance for enabling the monitoring of environmental samples for metal ion contamination directly in the field. This review outlines the use of peptides and amino acids as the recognition element of electrochemical sensors for metal ion detection. Initially the complexation of metals by peptides is discussed followed by the immobilization of peptides on electrode surfaces. Subsequently, the application of peptide modified electrodes for detecting metals is reviewed and finally challenges and future prospects are outlined.     

Coulometric Response of H+-Selective Solid-Contact Ion-Selective Electrodes and Its Application in Flexible Sensors†

The analytical performance of H⁺-selective solid-contact ion-selective electrodes (SCISEs) based on solid contact polyaniline doped with chloride (PANI(Cl)) and poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT(PSS)) was characterized by a developed coulometric signal transduction method. PEDOT(PSS) solid contact is covered by PVC based H⁺-selective membrane. The obtained coulometric signal demonstrates that the cumulated charge can be amplified by increasing the capacitance of solid contact. SCISEs covered with spin-coated membrane behave faster amperometric response than electrodes with drop-cast membrane. In contrast to earlier works, the amperometric response and impedance spectrum demonstrates H⁺ transfer through SCISEs is independent from the thickness of membrane. The exceptional behavior of PANI(Cl) H⁺-SCISEs shows that the capacitance estimated from impedance spectrum at low frequency 10 mHz and coulometric signal of PANI(Cl) based SCISEs is influenced by the applied potentials, whereas PEDOT(PSS) solid contact is independent from the chosen applied potentials. Furthermore, preliminary investigations of coulometric signal transduction on flexible pH sensor implies its potential applications in wearable sensors for sweat ion concentration detection.      

Sodium Ion Selective Electrodes Based on Lipophilic 16-Crown-5 Derivatives

Abstract

Six kinds of lipopholic 16-crown-5 derivatives possessing double side-chains were synthesized. The Na⁺-selectivities were examined with poly(vinyl chloride) (PVC) matrix-membrane electrodes using these crown compounds. It is an effective way for obtaining high Na⁺-selectivity by introducing a bulky side-chain such as a benzyloxymethyl group into the 16-crown-5. The electrodes based on 16-crown-5 derivatives having both a methyl or ethyl group and a benzyloxymethyl group at the pivot carbon (C-15) (3 or 4, see Figure 1) exhibited excellent Na⁺-selectivity over K⁺ (log k _Na.x = -2.65 and -2.75 for 3 and 4, respectively).     

Use of a Conditioning Buffer to Regenerate Gas Sensing Ion Selective Electrodes

Abstract

In the course of working with geothermal-geopressured brines we have developed a slight modification to the general procedure for the use of gas sensing ion selective electrodes which reduces the time between successive samples to about 10 minutes, as well as improving the precision and in the case of the ammonia electrode an improvement in the lower detection limit (to 0.1 ppm) was obtained. We have found that the modified procedure works equally well for both the Orion ammonia (Model 95–10) and the Orion carbon dioxide (Model 95–02) electrodes.     

Fabrication of Sensitive Membrane Electrodes and their Application in Electrochemical Quantification of Ibandronate in Dosage Form

A new, highly selective, simple and accurate method was adopted and validated for the direct quantification of ibandronate sodium monohydrate (IBN) in tablets using sensitive polyvinyl chloride membrane electrodes. Three membranes were fabricated using dibutyl sebacate, nitrophenyl octyl ether and dioctyl phthalate. The fabricated electrodes showed fast response, capability of application in wide pH range and direct determination of IBN in turbid solutions. The most important advantage of the proposed analytical method is that it successfully allows direct determination of IBN in dosage form. The proposed analytical methodology can be applied for the direct quantification of IBN in pharmaceutical formulations.     

Quantitation of Metal Ions in Archaeological Glass by Abrasive Stripping Square‐Wave Voltammetry Using Graphite/Polyester Composite Electrodes

A method for identifying Co, Cu, Sb, Sn, Fe, Zn, and Zr pigments in glasses using square‐wave voltammetry as the detection mode is described. It is based on the abrasive attachment of glass microsamples to graphite/polyester composite electrodes. Sample amounts less than 1 μg are used allowing for the study of archaeological samples. In all cases well‐defined anodic stripping peaks corresponding to the oxidation of metal deposits generated at potentials ranging from ?0.6 to ?1.6 V (vs. SCE) are obtained. This response is in agreement with that displayed by the corresponding metal oxides. Quantitative estimates of the relative population of metal ions in glasses are obtained from peak area measurements with an accuracy comparable to that obtained with SEM/EDX.     

钠离子电池钴酸钠正极材料研究进展

钠离子电池凭借分布广泛和低成本的钠资源在大规模电化学能量存储领域受到广泛关注. 层状过渡金属氧化物作为一种重要的钠离子电池正极材料, 具有比容量高、电化学可逆性相对较好和化学组成丰富且可调的特征, 得到广泛关注. 其中钴酸钠是一种典型层状过渡金属氧化物, 自20世纪80年代就得到大量研究. 由于钴酸钠含有丰富的电化学信息, 基于其充放电过程进行的机理研究对理解钠离子电池层状氧化物体系具有重要意义. 因此在介绍钴酸钠的常见结构类型与合成相图的基础上, 本文着重综述了不同结构钴酸钠在充放电过程中结构变化和电荷补偿机理的研究进展, 同时讨论了上述机制对电化学性能的影响. 本综述旨在为深入研究并建立层状过渡金属氧化物正极材料电化学过程中的构效关系提供支持.     

Structural Selectivity of Calix[m]pyrroles[n]furans (m + n = 4) as Ionophores in Ag(I) Ion-Selective Electrodes

A series of octamethylcalix[m]pyrroles[n]furans (m + n = 4), such astrans-octamethylcalix[2]pyrroles[2]furans L ₁ ),cis-octamethylcalix[2]pyrroles[2]furans (L ₂ ) and octamethylcalix[1]pyrrole[3]furans (L ₃ ) have been studied as sensors in liquid membrane ion-selective electrodes for Ag(I) ion. The electrode based on L ₁ , trans-N₂O₂ porphyrinogen, gave the best results with a wide working concentration range of 1.0 × 10^-1 - 1.0 × 10^5.6 M and a Nernstian slope of 57.0 mV/decade. This electrode exhibited a fast response time of 30 s and high selectivity over a number of mono-, di- and tri-valent cations, with only Tl(I) and Hg(II) ion interferences. The effect of anion excluders on the performance of the membrane electrodes has been also studied. The electrode based on L ₁ showed no significant potential changes in the range 2.5 < pH < 7.5. The crystalstructure of L ₃ , NO₃ porphyrinogen, was determined by single crystal X-ray analysis. The crystallographic analysis of L ₃ reveals that its structure is a saddle-shaped 1,3-alternate conformation with enough space to accommodate Ag(I) in the three dimensional cavity.     

基于精细结构对二元钠硅酸盐玻璃核磁共振波谱的研究

利用精细结构表征系列(Q_i^{\mathit{jklm}})对二元钠硅酸盐玻璃的核磁共振波谱进行解析, 并结合量子化学模拟了多种精细结构. 研究结果表明, 精细结构的 ²⁹Si化学位移与桥氧键角呈线性相关; 实验所得Q_i^{\mathit{jklm}}结构的化学位移不随玻璃成分的改变而波动, 且Q_i^{\mathit{jklm}}结构的高斯峰更窄, 说明精细结构表征是二元钠硅酸盐玻璃基本特征结构的表达, 导致初级微结构的 ²⁹Si化学位移变化的本质是精细结构含量的变化. 核磁共振波谱表征的是近邻结构的空间信息, 采用Q_i^{\mathit{jklm}}结构表征能更精确地描述硅酸盐的微结构信息.     

Voltammetry of Osmium End‐Labeled Oligodeoxynucleotides at Carbon,Mercury, and Gold Electrodes

Voltammetric behavior of oligodeoxynucleotide (ODN) 5′‐T₄₀ (GAA)₇–3′ end‐labeled with osmium tetroxide,2,2‐bipyridine [Os(VIII)bipy] was compared with Os(VIII)bipy‐base‐ and with Os(VI)bipy‐sugar‐modified thymine ribosides. Cyclic voltammograms of Os(VIII)bipy‐modified ODN at mercury and carbon electrodes were similar but not identical to those of Os(VIII)bipy‐modified thymine riboside. Treatment of the ODN with Os(VI)bipy did not result in the ODN modification, in agreement with the known specificity of the reagent to the sugar cis‐diols. We show that in addition to mercury and carbon electrodes, the gold electrode can be used to detect Os(VIII)bipy‐labeled ODN. Comparison of voltammetric behavior of end‐labeled ODN using three types of electrodes most frequently used in DNA analysis may help to optimize electrochemical DNA sensors.     

离子色谱法测定硝酸钠晶体中微量亚硝酸根的方法研究

为保持大尺寸硝酸钠单晶的优良性能,要求控制其微量杂质NO2^-的含量在极低的浓度水平。因此亟需提供具有高实用性和强操作性的NO2^-的测定方法。研究并提出了梯度淋洗^-离子色谱法(A法)和阀切换^-离子色谱法(B法)两种分离模式。取样品0.2000g溶于水中,定容至100.0mL,经0.22μm滤膜过滤,取滤液进行离子色谱分析。梯度淋洗中,在9min以内用8mmol·L^-1KOH溶液将NO2^-从AS11^-HC阴离子交换柱上洗脱,并用电导检测。随后用30mmol·L^-1KOH溶液将交换柱上由样品而来的大量NO3^-在较短时间内洗脱,从而避免其对下一样品分析的干扰。在阀切换中,利用仪器的六通阀与加装的十通阀之间的切换实现NO2^-与其基体的高浓度NO3^-之间的分离。方法采用峰面积积分方式计算测试结果。上述两种方法的线性范围均在0.10~2.00mg·L^-1之间,检出限(3S/N)为8×10^-4%(A法)和5×10^-4%(B法)。另取同一样品分别按两种方法进行6次平行测定,测定值的相对标准偏差(n=6)依次为4.2%,3.2%。另分别在6份样品的基础上加入NO2^-标准溶液,按上述两种方法操作进行回收试验,测得回收率分别为92.5%~108%(A法)和95.5%~104%(B法),结果表明两种方法各有优缺点。