导电高分子薄膜修饰电极的研究I. 聚吡咯薄膜电极的电化学合成及行为

利用在水溶液中的电化学聚合制备了聚吡咯烷、薄膜修饰电极. 讨论了对电化聚合的影响因素及薄膜修饰电极在不同电解质中的伏安特性, 从X-射线光电子能谱推测, 在吡咯的电化聚合过程中氧的参加引起在聚吡咯烷膜的结构中有羰基和羟基的生成.     

聚吡咯/聚合物固体电解质双层复合膜研究

在聚合物固体电解质（聚乙二醇不饱和聚酯网络－LiClO4)中进行吡咯聚合原位制得了聚吡咯／聚合物固体电解质双层复合膜。用扫描电镜观察复合膜的界面结构,用循环伏安和交流阻抗法研究了复合膜的电化学杂脱掺杂性能。结果表明,聚吡咯／聚合物固体电解质双层复合膜具有相互穿插渗透的固／固密接界面结构,这种界面结构改善了聚吡咯和聚俣物固体电解质间的界面接触,提高了聚吡咯在聚俣物固体电解质中的电化学掺杂脱掺杂性能。     

聚吡咯纳米线的恒电位合成及形貌分析

采用恒电位法,直接在石墨电极表面快速合成聚吡咯纳米线,并重点研究了聚吡咯纳米线的生成过程及形貌变化规律。结果表明,聚吡咯纳米线的生成包括成核和生长过程,纳米线的形貌随聚合条件的不同而变化,直径随聚合电位、吡咯单体浓度、电解质浓度的升高而增大,这是由于不同聚合条件下聚吡咯的成核速率不同引起的。     

电解质溶液对聚吡咯电聚合中过氧化行为的影响

分别以硫酸/水和高氯酸锂/乙腈为电解质溶液, 采用循环伏安法在铂基底电极上电聚合制备了聚吡咯, 研究了电解质溶液对聚吡咯电聚合过程中过氧化行为的影响. 与硫酸/水溶液相比, 在高氯酸锂/乙腈溶液中电聚合制备的聚吡咯发生过氧化的峰电位正移了0.42 V. 采用原位傅里叶变换红外(in situ FTIR)光谱技术检测, 结果表明, 电聚合制备的聚吡咯在2种电解质溶液中均发生了过氧化反应, 其β-C经氧化生成C-OH或CO. 在硫酸/水溶液中, 部分聚吡咯发生电氧化降解生成CO₂, 致使其共轭结构被破坏, 电导率迅速下降. 而在高氯酸锂/乙腈溶液中, 在更高的电位范围内, 聚吡咯并没有氧化降解成CO₂.     

基于石墨/聚吡咯电极的葡萄糖生物传感器

采用电化学聚合技术,在掺杂的导电聚吡咯薄膜修饰过的铅笔芯电极上,吸附葡萄糖氧化酶制备葡萄糖生物传感器。首先在含有0.1 mol/L吡咯和0.01 mol/L HCl的溶液中,于0.7 V恒电位下吡咯单体氧化聚合,在铅笔芯电极表面形成聚吡咯薄膜;然后将葡萄糖氧化酶吸附在修饰过的电极上制备出葡萄糖氧化酶-聚吡咯-铅笔芯电极电流型生物传感器。实验考察了吡咯聚合时间、聚合温度、葡萄糖氧化酶吸附量、检测电压以及干扰物对传感器性能的影响。实验结果表明,在优化条件下,传感器的灵敏度为17.78μA/mmol/L,线性范围0.8 mmol/L,线性相关度R=0.9918,响应时间小于16 s,检测下限为18.75μmol/L,有较强的抗干扰能力。     

化学氧化法合成聚吡咯薄膜

通过界面氧化合成了聚吡咯薄膜。对使用的溶剂和氧化剂进行了讨论，并在不同的温度和浓度下观察聚吡咯薄膜生成的速度及生成膜的稳定性能。通过扫描电镜，红外光谱，电导测定，元素分析等实验，研究了聚合膜的组成和结构。     

天然氨基酸水溶液中聚吡咯的电化学合成及其表征

报道了各种天然α-氨基酸水溶液中电化学聚合吡咯获得氨基酸掺杂的聚吡咯.实验表明吡咯在酸性氨基酸电解质中的氧化聚合电位较低,速度较快;而在碱性氨基酸水溶液中几乎无法进行电化学聚合.在电化学聚合过程中,氨基酸既作为支持电解质,又作为对离子被掺杂到聚合物中.该聚吡咯的电导率被测定为0.3～1.0 S/cm,在酸性氨基酸溶液中得到的聚合物电导率明显高于酸性较弱的氨基酸溶液中得到的聚合物,同时聚合物还具有良好的电化学活性和电化学稳定性,在-0.5 V到+0.5 V区间有一对氧化还原峰,该氧化还原峰的形状和特性在100次循环后基本保持不变.通过扫描电镜和透射电镜照片可以看出,不同种氨基酸的掺杂对聚吡咯的形貌具有影响,由于氨基酸的软模板效应,在数种氨基酸水溶液中能制得具有纳米纤维结构的聚吡咯.     

聚吡咯薄膜中茜素红S的电化学特性

利用循环伏安法研究了聚合电位和聚合电量对茜素红S掺杂聚吡咯薄膜修饰玻碳电极性质的影响,考察了不同电位范围内修饰电极的电化学特性.发现在茜素红S的氧化还原过程中存在着茜素红S分子与聚吡咯链的相互作用,且这一相互作用敏感于扫描正电位限.基于实验结果,提出了可能的茜素红S在电极表面聚吡咯膜内的氧化还原机理.     

聚吡咯及包夹亚甲绿的聚吡咯修饰电极对血红蛋白电极过程的促进

用电化学聚合法制备的聚吡咯及包夹亚甲绿的聚吡咯薄膜修饰电极可以促进血红蛋白的非均相电子传递过程。用光透薄层光谱电化学技术测定了血红蛋白在包夹亚甲绿的聚吡咯修饰电极上的电子传递数(n),标准电极电位(E~(o'))和非均相电子传递速度常数(k_(εh)~o)。对血红蛋白在聚吡咯修饰电极上的电子传递反应机理进行了探讨。     

离子液体中吡咯的电化学聚合及性质研究

以1-丁基-3-甲基咪唑六氟磷酸盐离子液体作为溶剂和支持电解质,分别在铂电极和导电玻璃电极上电化学聚合得到了聚吡咯,聚合过程中发现,在离子液体中聚合的循环伏安图,其电流的变化和传统有机溶剂中的不同,通过交流阻抗技术研究了修饰电极的电化学性质,采用在线紫外、拉曼、红外谱对聚吡咯进行了光谱表征,得到了聚吡咯的特征峰,采用扫描电镜研究了聚合物的形貌。最后将修饰电极应用到了对对苯二酚的催化反应当中,显示了一定的催化作用。     

Synthesis and Conductivity of CaZr<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3–δ</Subscript> Electrolyte Films on Supporting Composite Electrodes

Conditions of the chemical solution deposition of CaZrO₃-based electrolyte films on supporting composite electrodes are studied. The films are formed on the composites of CaZrO3 with metal oxides СuO, Fe₂O₃, and NiO. The morphology and the phase and elemental composition of supports and films are studied as well as the gas permeability and conductivity of films. It is concluded that composites of calcium zirconate with nickel can be recommended as the supporting anodes for the proton-conducting CaZr_0.9Y_0.1O_3–δ film electrolyte.     

Improving the fabrication of all-polythiophene supercapacitors

The influence of the preparation method in the properties of poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes used to manufacture organic energy storage devices, as for example supercapacitors, have been examined by considering a reduction of both monomer and supporting electrolyte concentrations during the anodic polymerization reaction. Thus, the excellent electrochemical properties of PEDOT films prepared using quiescent solutions have been preserved by applying controlled agitation to the polymerization process, even though the concentration of monomer and supporting electrolyte were reduced 5 and 2 times, respectively. For example, the charge stored for reversible exchange in a redox process, the electrochemical stability and the current productivity of films achieved using quiescent solutions have been preserved using a dynamic reaction medium in which the concentrations of monomer and supporting electrolyte are several times lower. The excellent properties of PEDOT electrodes prepared using optimized dynamic conditions have also been proved by constructing a symmetric supercapacitor. This energy storage device, which has been used as power source for a LED bulb, is rechargeable and exhibits higher charge-discharge capacities than supercapacitors prepared with electrodes derived from quiescent solutions. In addition of bring an efficacious procedure for preparing cost-effective PEDOT films with excellent properties, the proposed dynamic conditions reduce the environmental hazards of depleted reaction media.     

Anion-excluding polypyrrole films

A new method for modifying polypyrrole films is described. It involves complete oxidation of the film. The film produced is electronically non-conductive but ionically conductive, and has ion-selective properties based on the exclusion of anionic species. The effective pH within the film can be controlled by the choice of supporting electrolyte used during the oxidative treatment, without loss of selectivity. Cyclic voltammetry is used to demonstrate the effect of film pH on the rate of dopamine oxidation in a neutral supporting electrolyte.     

Effect of supporting electrolyte concentration on one-step electrodeposited CuInS2 films for ZnS/CuInS2 solar cell applications

Journal of Solid State Electrochemistry - A one-step electrodeposition process was used to obtain CuInS2 (CIS) films on a molybdenum substrate by varying the supporting electrolyte (lithium...     

Formation of solid electrolyte films on porous supporting electrodes

In this work, the method of chemical deposition from the gas phase of organometallic compounds (CVDOM) was used to obtain thin electrolyte films of zirconia stabilized by yttria (YSZ) on a supporting electrode. Tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)zirconium and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium often termed as zirconium (IV) Zr(dpm)₄ and yttrium (III) Y(dpm)₃ dipivaloylmethanates were used as precursors for film deposition. Gas-tight electrolyte films were obtained on a supporting anode with a thickness of 4–10 μm at moderate deposition temperatures of 500–700°C. An electrochemical cell was prepared and tested using the obtained films. The cell allowed obtaining the power density values of 680, 360, and 175 mW/cm² at the temperatures of 800, 700, and 600°C, accordingly.     

在水溶液中电化学反应制备大面积聚吡咯膜

以不锈钢为电极,在吡咯水溶液中,经电化学聚合制备了大面积的聚吡咯薄膜。研究了反应电流密度、反应温度、对阴离子种类和浓度等因素对成膜性能及电导率的影响。选择合适的反应条件,可得到电导率为120Scm~(-1)、抗拉强度46MPA、模量为1.75GPA的聚吡咯膜。     

Electron self-exchange reaction of viologen and its derivatives in poly(ethylene glycol)

The electron self-exchange rates (k_ex) of viologen and its derivatives are estimated by using microelectrode voltammetry in poly(ethylene glycol) films. The dependences of supporting electrolyte concentration and sizes of viologen and its derivatives on k_ex and diffusion coefficients (D) are discussed. Results show that k_ex increases with the decrease of supporting electrolyte concentration and sizes of reactants.     

Potential shifts at electrodes coated with ion-exchange polymeric films

Voltammetry at electrodes modified with ion-exchange polymers, named "ion exchange voltammetry", has been recently developed for characterizing and determining quantitatively ionic electroactive analytes preconcentrated at the electrode surface. Like for other voltammetric techniques, characterization is based on the position of the response on the potential scale, but an appreciable difference is frequently observed between the formal half-wave potential for redox couples incorporated within ion-exchange polymeric films and those for the same redox couples in solution as measured at bare electrodes. Such a difference has been rationalized here by a generalized equation, inferred from a suitable elaboration of the Nernst equation, whose validity has been tested by a thorough investigation performed at glassy carbon electrodes modified with either cationic (Nafion) or anionic (Tosflex) polymeric films. With this purpose, the effect of both charge and concentration of the analyte and of the loading counterion, this last introduced as the cation or anion of the supporting electrolyte, of the ion-exchange selectivity coefficients of the redox partners and of their stoichiometric coefficients, as well as of the number of electrons involved in the charge transfer has been evaluated. The results obtained agree quite well with theoretical expectations and indicate that the potential shifts found are mainly conditioned by both charge and concentration of the counterion from the supporting electrolyte and by the ratio of the ion-exchange equilibrium constants for the two redox partners involved. Other parameters considered have no influence on the potential shift or lead to negligible effects, provided that the quantities of the redox partners incorporated within the ion-exchange coating represents less than 5% of the film capacity. Again in agreement with theoretical expectations, positive shifts are found for increasing supporting electrolyte concentrations when cationic redox species incorporated within cationic films are involved, while the opposite effect is found for anionic redox species incorporated within anionic films.     

Two-component polymer films of palladium and fullerene with covalently linked crown ether voids: effect of cation binding on the redox behavior

Redox active films have been generated via electrochemical reduction in a solution containing palladium(II) acetate and fulleropyrrolidine with covalently linked crown ethers, viz., benzo-15-crown-5 and benzo-18-crown-6. In these films, fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. Films show ability to coordinate alkali metal cations from the solution. Therefore, in solutions containing salts of alkali metal cations, benzo-15-crown-5-C₆₀/Pd and benzo-18-crown-6-C₆₀/Pd films are doped with cations coordinated by crown ether moiety and anions of supporting electrolyte which enter the film to balance positive charge. These films are electrochemically active in the negative potential range due to the reduction of the fullerene moiety. Reduction of the polymer is accompanied by the transport of supporting electrolyte ions between solution and solid phase. In solution containing alkali metal salts, the process of film reduction is accompanied by the transport of anions from the film to the solution. In the presence of tetra(alkyl)ammonium salts, transport of cations from the solution to the film takes place during the polymer reduction.     

The effect of electrolyte-controlled growth morphology on the charge transport properties of poly(3-methylthiophene)

Poly(3-methylthiophene) films were potentiostatically and galvanostatically synthesized on platinum electrodes in acetonitrile using lithium perchlorate, lithium tetrafluoroborate, tetra-n-butylammonium perchlorate, and tetra-n-butylammonium tetrafluoroborate as supporting electrolytes. Cyclic voltammetric analyses of the polymer films indicate the synthesis is polymerization process dependent. Constant potential syntheses, which resulted in a higher current density and were carried out at higher potentials, yielded polymer films with a higher charge capacity. Chronocoulometric results show that the charge transport rates of the films were electrolyte dependent and that tetra-n-butylammonium tetrafluoroborate yielded poly(3-methyl-thiophene) with the highest charge transport rate. The charge transport rate was found to be electric field dependent for all cases, suggesting that the films resemble a porous electrode. Scanning electron microscope analyses of the films, prepared under various conditions, indicate that the synthesis method used, and the nature of the electrolyte, strongly influence morphology and charge transport.