微盘电极应用-聚在乙二醇离子导体中的伏安分析

在聚乙二醇离子导体中, 研究了二茂铁在其中的伏安性质, 结果表明如果电活性物质与聚合物溶剂不发生相互反应, 那么电活性物质在聚合物溶剂中的扩散仍然遵循Fick扩散方程, 其伏安结果可以定量描述。提出了在聚合物离子导体中不需要知道电活性物质的摩尔浓度就可估算扩散系数的伏安方法, 探索了在聚合物离子导体中电活性物质的扩散规律。     

微盘电极应用在乙二醇离子导体中的伏安分析

在聚乙二醇离子导体中,研究了二茂铁在其中的伏安性质,结果表明如果电活性物质与聚合物溶剂不发生相互反应,那么电活性物质在聚合物溶剂中的扩散仍然遵循Fick扩散方程,其伏安结果可以定量描述.提出了在聚合物离子导体中不需要知道电活性物质的摩尔浓度就可估算扩散系数的伏安方法,探索了在聚合物离子导体中电活性物质的扩散规律.     

化学修饰电极的研究ⅩⅢ. 聚乙烯二茂铁(PVFc)薄膜电极和电催化效应

本文研究了影响PVFc薄膜电极伏安性质的各种因素, 讨论了聚合物薄膜电极的电荷传递过程。溶液平衡离子的水合半径大小、离子强度、溶剂对薄膜的溶胀性质以及聚合物薄膜的厚度是影响聚合物薄膜电极伏安性质的主要因素。研究了PVFc薄膜电极对亚铁氰化钾、左旋多巴和儿茶酚的电催化作用, 用旋转园盘电极研究了催化过程动力学。抗坏血酸和儿茶酚的混合物在PVFc薄膜电极上呈现分开的氧化还原峰, 有应用于生物化学分析的意义。     

聚合物电解质(PEG/LiClO4)中L-抗坏血酸氧化的现场显微红外光谱电化学研究

L-抗坏血酸(H2A)由于在生物介质氧化还原过程中的重要作用,其分子及其衍生物已有广泛研究[1～5].聚合物电解质由于能溶解电活性物质和具有离子导电性而成为一种新的溶剂,可用于研究一些物质的电化学行为[6].H2A在聚合物电解质中的电化学及光谱电化学行为还未见报道.     

Schiff碱基过渡金属镍络合物的电化学聚合:阳极电聚合中扫描速率的影响(英文)

采用线性电位扫描法制备了水杨醛-Schiff碱基过渡金属镍络合物的聚合物poly[Ni(salen)],扫描速率为5-150 mV.s-1.采用场发射显微镜观察了聚合物poly[Ni(salen)]的表面形貌.研究了电聚合中扫描速率对聚合物生长的影响,电聚合速率(dГ/dm)与扫描速率(v)呈指数衰退关系,通过库仑电量分析指出电聚合扫描速率在20mV.s-1时聚合产物中含有最多的氧化还原活性点.扫描速率提高时单体的扩散步骤限制了聚合物的生长,所以氧化还原活性点总量随着扫描速率的提高而开始下降.利用循环伏安法分析了聚合物poly[Ni(salen)]的扩散动力学,结果表明在20 mV.s-1时制备的聚合物具有较大的电荷扩散系数.     

循环伏安法制聚(1,5-萘二胺)膜及其对紫外可见光吸收的研究

利用循环伏安法合成了1,5-萘二胺(1,5DAN)聚合物膜.从反应的介质、膜的厚度以及掺杂酸的种类等方面,讨论了制备电活性聚1,5-萘二胺(P1,5DAN)膜的影响,结果发现,在酸性水溶液中,初始的电活性比较高,但是,随着循环的继续,聚合物膜的电量损耗比较大,而在乙腈溶液中电量损耗较小;同时还发现,P1,5DAN电活性膜的厚度并不随总电量的增加而增厚;活性聚合物膜是受扩散控制,扩散系数(D)与酸根离子有关.最后,结合电化学,讨论了不同掺杂状态下的紫外可见吸收光谱(UV-Vis),并用FT-IR对所合成的聚合物作了结构表征.     

离子强度对P(HEMA-co-MMA)水凝胶溶胀性能及水的状态的影响

对甲基丙烯酸-β-羟乙酯(HEMA)与甲基丙烯酸甲酯(MMA)共聚水凝胶扩散行为、聚合物-溶剂相互作用及水的状态进行了研究。考察了不同NaCl离子强度下水凝胶平衡含水率、扩散系数及聚合物-溶剂相互作用参数的变化关系。研究结果表明,随着NaCl离子强度增大,平衡含水率降低,扩散系数下降,聚合物-溶剂相互作用参数升高。通过DSC测定了水凝胶中冻结水和非冻结水的组成。     

离子液体聚合物的研究进展

离子液体聚合物是一类高分子链上至少含有一个离子中心,重复单元与常见离子液体结构类似,具有特殊性能的高分子,应用于诸多领域。本文综述了离子液体聚合物在离子导体、吸附及分离、稳定剂以及催化剂等方面应用的最新研究进展,重点介绍了离子液体聚合物作为离子导体在锂离子电池和染料敏化太阳电池中应用的研究现状,最后展望了离子液体聚合物的发展前景。     

掺杂电活性离子聚吡咯膜内的电荷传输

用循环伏安法和计时库仑法研究了掺杂亚铁氰化钾离子的聚哟咯膜内的电荷传输问题。实验结果表明，聚吡咯膜内的电荷传递可以处理成电子在膜内的扩散模型，电荷传递速度可以 用电子表观扩散系数（Ｄａｐｐ）来表征。Ｄａｐｐ的大小由聚合物膜的结构、电活怀离子之间的过及对离了在膜中的运动决定。     

快离子导体与固体化学

固态离子学是一门新兴的学科。它的产生,是由于发现了一类具有高电导率的离子导电的固体(称为快离子导体、超离子导体或固体电解质)。这类导体和电子导体不同,在传递电荷的同时还伴随有物质迁移。这种特性赋予它们多方面应用的可能性。例如,作为各种燃料电     

Swelling ratio driven changes of probe concentration in pH- and ionic strength-sensitive poly(acrylic acid) hydrogels

Poly(acrylic acid) gels are known to swell to different extent (measured by the swelling ratio) depending on pH and ionic strength of the solution. The experimental method employed by us to monitor the concentration and diffusion coefficient of the probes allows the simultaneous determination of their concentration and diffusion coefficient for any value of the ionic strength and pH of the solution trapped in the polymeric network. Two different electroactive probe systems, 1,1′-ferrocenedimethanol and 2,2,6,6-tetramethylpiperidine 1-oxyl, were selected for the examination. Small values of the swelling ratio, obtained either by application of a high ionic strength or a low pH, result in an unexpected high concentration of both probes in the gel samples. Correspondingly, the probes diffusion coefficients were much smaller compared to their values in the swollen gels.     

Describing the unsuspected advantage of redox ionic liquids applied to electrochemical energy storage

Ionic liquids are a class of solvents widely studied in the literature for various applications. As a subclass of ionic liquids, redox ionic liquids can endow charge exchange properties (electrons transfer) to these electrolytes for electrochemical energy storage. In this review article, we propose to study this family of ionic liquids and suggest a chronological classification. We introduce five generations of redox ionic liquids with different basic compounds such as polyethylene glycol, ferrocene, different linker lengths, TFSI anion, and biredox ionic liquids. The versatility of the redox ionic liquids synthesis will be discussed as well as the fundamental and applied aspects of their use as electrolytes, which have high charge densities. The impact of the redox ionic liquids on the electrochemical mechanisms will be described. We also present how the redox shuttle effect, detrimental to supercapacitors, can be prevented while it can be used to improve lithium-ion batteries.     

Electrooxidation of undiluted organic liquids swelling<Emphasis Type="Italic"> N</Emphasis>-isopropylacrylamide-based copolymers

Polyacrylate gels such as: N-isopropylacrylamide (NIPA), ionic copolymer NIPA-co-sodium acrylate (NIPA-co-SA) and ionic copolymer NIPA-co-[2-(acryloyloxy)ethyl]trimethylammonium chloride (NIPA-co-XCl) were swollen by methanol, ethanol and N,N-dimethylformamide. These solvents were oxidized voltammetrically in the gels at platinum microelectrodes. The blocking coefficients, defined as the ratio of the currents observed in the presence and absence of the polymeric chains, were different for the solvents in the charged and uncharged polymers and did not differ for the electroactive probe, ferrocene, present in the solvents at millimolar level. This may mean that the micro ionic layer that is formed at microelectrodes at the plateau of the voltammetric solvent waves leads to a kind of collapse/phase transition of the polymer in the depletion layer. For methanol, the gel structure was found to prevent occasionally the formation of large gas bubbles at the potentials positive versus the first wave and then three one-electron waves could be obtained. Experiments done with a capillary cell and an optical microscope indicated that before formation of large bubbles at the Pt microelectrode a very dynamic, dense stream of microbubbles leaves the electrode surface.Dedicated to Zbigniew Galus on the occasion of his 70th birthday     

聚电解质中电活性物质氧化还原反应机理的现场显微红外光谱电化学研究

用现场显微红外光谱电化学方法研究了几种电活性物质,包括无机盐、有机物、无机聚合物微粒在聚电解质中的氧化还原反应及其机理。     

Synthesis and characterization of protic ionic liquids containing cyclic amine cations and tetrafluoroborate anion

Several ionic liquids containing pyrrolidinium-, oxopyrrolidinium-, piperidinium-, morpholinium- and trialkylammonium-based cation are synthesized and their thermal property, refractive index, polarity, electrochemical property, and temperature dependency of dynamic viscosity, density and ionic conductivity are characterized. All tetrafluoroborate-based room temperature ionic liquids studied here have a high ionic conductivity (up to 31.4 mS cm^?1). These ILs were successfully used as suitable electrolytes for the diffusion coefficient measurement of ferrocene. Absorbance solvatochromic probes Nile red is used to investigate the relative polarity of these ionic liquids and compared them with several organic solvents. The relation of fluidity to conductance is considered in terms of a Walden plot that is shown to provide a useful basis for organizing the applications of solvent media for ??green?? synthetic reactions.     

Redox-active electrolyte supercapacitors using electroactive ionic liquids

Here we present redox ionic liquid supercapacitors (RILSCs) which use electrolytes made from ionic liquids modified with an electroactive function to increase the energy density of activated carbon electrodes via faradaic reactions. More specifically, two different ionic liquids were made by modifying either the imidazolium cation or the bis(trifluoromethanesulfonyl)imide anion with ferrocene in order to determine the importance of the electroactive ion's polarity. The functionalization of an ionic liquid with ferrocene led to high concentrations of redox moieties in the electrolyte (2.4 M) and a large maximum operating voltage (2.5 V). An energy density of up to 13.2 Wh per kg (both electrodes) was obtained which represents an 83% increase vs. the unmodified ionic liquid. When the ionic liquid's anion is modified with ferrocene, the self-discharge at the positive electrode is fully suppressed due to the deposition of a film on the electrode. The results presented herein demonstrate that electroactive ionic liquids constitute a promising alternative to conventional solute in solvent electrolytes found in energy storage devices, and are particularly well-suited for redox-active electrolyte supercapacitors.     

Influence of the reticular polymeric gel—electrolyte structure on ionic and molecular mobility of an electrolyte system salt—ionic liquid: LiBF4—1-ethyl-3-methylimidazolium tetrafluoroborate

Russian Chemical Bulletin - Peculiarities of the formation of a reticular polymeric gel—electrolyte matrix based on polyethylene glycol diacrylate in a medium of ionic liquid...     

A mechanism of photo-oxidative destruction for polythylene polymers in the presence of ferrocene derivative additives

The effect of ferrocene additive concentrations on the stability of polythylene polymers under atmospheric ageing and ultraviolet irradiation is reported. At concentrations under ca 5 × 10^?3 mol kg^?1 polymer the ferrocene compound is shown to diminish polymer resistance to light, whereas above this concentration such a compound stabilizes the polymeric matrix. Another purpose of the work is to look into the photo-oxidative destruction of polyethylene doped with ferrocene compound by using an EPR technique. A mechanism of photo-oxidative destruction of polyethylene polymers in the presence of ferrocene compounds is proposed.     

Electrochemistry in deep eutectic solvents

We report the cyclic voltammetry, chronoamperometry, and scanning electrochemical microscopy of ferrocene dissolved in deep eutectic solvents (DES), consisting of choline chloride (ChCl) and either trifluoroacetamide (TFA) or malonic acid as the hydrogen-bond donor. Despite the use of ultramicroelectrodes, which were required due to the modest conductivities of the DES employed, linear diffusion behavior was observed in cyclic voltammetric experiments. The high viscosity of 1:2 ChCl/TFA relative to non-aqueous electrochemical solvents leads to a low diffusion coefficient, 2.7 x 10(-8) cm2 s(-1) for ferrocene in this medium. Because of the difficulties in achieving steady-state conditions, SECM approach curves were tip velocity dependent. Under certain conditions, SECM approach curves to an insulating substrate displayed a positive-feedback response. Satisfactory simulation of this unexpected behavior was obtained by including convection terms into the mass transport equations typically used for SECM theory. The observance of positive-feedback behavior at an insulating substrate can be described in terms of a dimensionless parameter, the Peclet number, which is the ratio of the convective and diffusive timescales. Fitting insulator approach curves of ferrocene in 1:2 ChCl/TFA shows an apparent increase in the diffusion coefficient with increasing tip velocity, which can be explained by DES behaving as a shear thinning non-Newtonian fluid.     

Functionalized mesoporous silica films as a matrix for anchoring electrochemically active guests

Mesoporous silica thin films were shown to be an appropriate matrix for immobilization of discrete electroactive moieties, yielding uniform transparent thin film electrodes with defined texture and enhanced electrochemical activity. The mesoporous silica films prepared on conducting FTO-coated glass substrate were postsynthetically functionalized. Alkoxysilanes were used as precursors for subsequent grafting via ionic or covalent bonds of representative electroactive species, such as polyoxometalate PMo12O(40)3-, hexacyanoferrate(III), and ferrocene. The electrochemically active concentration within the silica-based composite electrodes achieves 90, 260, and 60 micromol cm(-3) for polyoxometalate, hexacyanoferrate(III), and ferrocene, respectively. The amount of molecules involved in the charge-transfer sequence is proportional to the film thickness and comparable to the total amount of embedded guests. Thus, eventually the whole bulk volume of the modified silica films is electrochemically accessible. Immobilization in the chemically modified silica matrix alters the redox potential of the electroactive molecules. Electron exchange between the adjacent redox centers (electron hopping) is proposed as a possible charge propagation pathway through the insulating silica matrix, which is supported by the fact that the high charge uptake is observed also for the hybrid electrodes with the covalently anchored redox guests.