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In this paper, the electrochemical phase isolation (EPI) is discussed as a process at higher current densities in which the desirable enrichment of precipitated phase particles leads to a blocking of the surface. This effect impedes the matrix dissolution rate. Under galvanostatic conditions, a higher current causes a heat build-up within the porous layer and accelerates the kinetics up to the moment when the saturation concentration is reached in the pores. Under this aspect, experiments for iron carbide isolation from a steel matrix are described. 相似文献
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Polyaniline (PA) film was chemically deposited onto the surface of activated carbon (AC) uniformly. Chemical deposition was carried out in 0.1 mol/L aniline plus 0.5 mol/L H2SO4 solution adopting V2O5·nH2O coated on the surface of activated carbon as oxidant. The surface morphologies and structures of the composite materials were characterized by scanning electron microscopy and FT-IR spectra. The electrochemical properties of the composite material electrodes were studied by cyclic voltammetry and constant current charge/discharge tests in 1 molFL H2SO4 solutions. The specific capacitance of composite materials was exhibited as high as 237.5 F/g at a current density of 1.0 A/g compared with a value of 120 F/g for pure carbon electrode. Good power characteristic and good stability of composite electrodes were also demonstrated. 相似文献
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Xiaoquan Lu Limin Zhang Minrui Li Xiaoqiang Wang Yan Zhang Xiuhui Liu Guofang Zuo 《Chemphyschem》2006,7(4):854-862
Herein, the scanning electrochemical microscopy (SECM) approach is applied to study the formation of thiol-porphyrin self-assembled monolayer (SAMs). Using cyclic voltammetry (CV), the formation process is characterized adopting different probe molecules. The observed phenomena indicate that the formation process is affected by solution properties and the molecular structure of the probe molecules. In K(3)Fe(CN)(6) , the SAMs show a strong electron-transfer (ET) blocking effect on a pure porphyrin-modified electrode. However, addition of metal ions to the porphyrin molecules leads to ET. A consistent tendency is observed throughout the modification process using CV and SECM methods. Furthermore, k(eff) values, the apparent heterogeneous rate constants, obtained for different modification periods affirm the validity of these results. SECM images are used to collect surface information in the course of the modification process when the substrate potential is 0.5 V versus Ag/AgCl. The effect of the substrate potential indicates that the oxidation of the porphyrin molecules is supported by more positive potentials because of the similar bimolecular reaction of the porphyrin ring with positive charge and the probe molecules with negative charge. 相似文献
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胞外电子传递(EET)是指氧化还原反应所产生的电子在微生物细胞内和细胞外的电子受体/电子供体之间互相转移的过程,这一过程伴随着能量和物质的转化。阐明EET机制是提高微生物能量和物质转化效率的基础,为元素的生物地球化学循环、金属防腐以及生物电化学系统的应用等提供理论支撑。电化学技术作为研究电极/溶液界面电子转移的简便、有效方法,在研究微生物的直接电子传递和间接电子传递机制中发挥了重要的作用,也促进了EET机制的研究从宏观层面到微观层面不断深入。本文综述了研究微生物EET机制所涉及的电化学联用技术(包括微电极、扫描电化学显微镜、电化学联用光学显微镜和光谱电化学等);详细介绍了这些电化学联用技术的功能和优势;重点阐述了这些电化学联用技术如何推动着EET机制的研究,从宏观的生物膜层面到微观的单个微生物细胞、蛋白和分子层面不断深入;展望了新的电化学联用技术在EET研究领域的应用前景。 相似文献
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尝试对共沉淀法进行改进, 利用自制的加料装置合成了橄榄石型LiFePO4/C复合正极材料. 应用X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)、循环伏安(CV)以及恒电流充放电测试等方法对目标材料进行了结构表征和电化学性能测试. 实验结果表明采用该法得到的样品具有单一的橄榄石结构, 样品形貌规则, 粒径细小均匀. 改性后的材料具有较高的首放容量及良好的循环稳定性能. 0.1C倍率下充放电测试表明, 其首次放电比容量超过145 mAh•g-1, 50次循环后, 容量没有明显衰减. 0.2C和0.5C倍率下的平均放电容量分别为130及120 mAh•g-1, 循环过程中样品表现出较好的循环稳定性. 相似文献
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Karachevtseva L. A. Litvinenko O. A. Stronskaya E. I. 《Theoretical and Experimental Chemistry》2003,39(6):385-388
The process of formation of macropores in silicon with stationary irradiation and a constant current density during the electrochemical process in dependence on the initial bias on the silicon anode, U
0, has been studied. Stable formation of macropores began when the bias reached U
c, corresponding to a critical concentration of holes p
c at the silicon–electrolyte interface. The process of macropore formation is unstable with U
0 > U
c. 相似文献
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The electrochemical generation of stable carbocations, among other heterocyclic products, by a unique electrochemical process involving the anodic oxidation of aryl-substituted ketene imines is described. The electrochemical oxidation undergoes an unusual multiannulation process to form these types of products by intermolecular cyclization. The X-ray crystal structures of two carbocation tetrafluoroborate salts,4c and4d, of which the latter is solvated by CH2Cl2, are presented. We have observed that one of the B-F bonds in4c is relatively long with respect to the other three similar in length B-F bonds, while in the solvated salt (4d·CH2Cl2), one of the B-F bonds is particularly short relative to its congeners. In both cases, the exceptional B-F bonds are oriented toward the positive center of the carbocation. These phenomena are compared with other known X-ray structures of organic tetrafluoroborate salts and discussed. 相似文献
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将MAX相陶瓷通过液相刻蚀等方法移除A原子层可得到与石墨烯(Graphene)类似二维结构的过渡金属碳或氮化物(MXene),是近年来二维材料领域出现的新成员。独特的二维结构与丰富可调的组分使得MXene具有优异的导电与机械性能、高亲水表面与离子传输性能,受到越来越广泛的关注。目前已成功制备出的MXene材料有20余种,研究发现MXene应用于锂离子、非锂离子(如Na+、K+、Mg2+、Ca2+和Al3+)二次电池和电化学超级电容器均表现出优异的性能,是一种很有潜力的电极材料。本文总结对比了MXene材料制备方法,简要概述了MXene材料的电子、电磁与机械性能,重点介绍了MXene在电化学电池与超级电容器储能方面的应用,最后对MXene材料目前存在的主要问题及未来研究与应用前景进行了展望。 相似文献
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食品中残留的痕量有毒物质严重威胁人体健康,对其进行分析十分必要。然而,食品中有毒物质种类多、量少、基质复杂,需选择适当的样品预处理技术进行提取和净化。磁固相萃取(MSPE)因具有操作简单、省时快速、无需离心过滤、环境友好等优点,被认为是一种高效的样品预处理技术并应用于食品分析中。MSPE中使用的磁性吸附剂的吸附容量和选择性是影响MSPE萃取效率和选择性高低的关键,对所建立分析方法的准确度起着关键作用。碳基磁性材料是具有价格低廉、来源丰富、比表面积大、化学稳定性好、吸附容量高、绿色环保等优点的一类新型功能性磁性材料,可以富集不同性质的有机、无机分析物,在环境分析、生物检测、污染治理等多个领域取得了较大进展。近年来,基于碳基磁性材料的MSPE技术在食品分析预处理领域逐渐得到应用,但尚处于起步阶段,存在巨大的应用潜力。该文以碳基类别(碳纳米管、石墨烯、金属有机骨架衍生碳、活性炭等)为主线,综述了采用MSPE技术,以碳基磁性材料为吸附剂,对食品样品中酯类、真菌毒素、多环芳烃、抗生素、生物碱、酚类、维生素、抗菌药等物质进行萃取,进而采用液相色谱法等进行分析的应用实例,同时阐述了该技术存在的问题,并对其发展方向做出了展望。该综述将为基于碳基磁性材料的MSPE技术在食品分析中的广泛应用提供理论依据和技术支撑。 相似文献
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在三电极体系中,以硝酸锌水溶液作为电解液,采用阴极还原电沉积法成功实现了一维纳米结构ZnO阵列在TiO2纳米粒子/ITO导电玻璃薄膜基底上的沉积,并通过XRD、SEM、EDS和PL光谱等方法对样品进行了表征.重点研究了薄膜基底、电解液浓度、沉积时间、六次亚甲基四胺(HMT)的引入对ZnO沉积及其发光性质的影响.结果显示:与ITO玻璃基底相比,ZnO更易于在TiO2纳米粒子薄膜上实现电化学沉积.ZnO属于六方晶系的铅锌矿结构,并且沿着c-轴方向表现出明显的择优化生长,以形成垂直于基底的ZnO纳米棒阵列.延长沉积时间、增加电解液浓度和引入一定量的HMT等均对ZnO的生长有促进作用,进而使其纳米棒的结晶度和取向程度提高,进而解释了所得的薄膜分别约在375和520nm处表现出ZnO的强而窄的带边紫外光发射峰和弱而宽的表面态绿光发射带. 相似文献
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铬(Ⅵ)与谷胱甘肽作用及其中间态配合物形成的电化学表征 总被引:2,自引:0,他引:2
本文采用电化学方法,对谷胱甘肽(GSH)与重铬酸钾的相互作用及其中间态配合物的形成过程进行研究。结果表明:在pH=5.6的HAc-NaAc缓冲溶液中,GSH浓度为Cr(Ⅵ)浓度5倍以上时,Cr(Ⅵ)与GSH作用完全并形成一新的中间态配合物,该中间态配合物于+0.21 V和+0.36 V(vs SCE)处产生一对新的氧化还原峰,UV-Vis的吸收光谱进一步证明了中间态配合物的形成。该配合物不稳定,在一定时间内缓慢分解,其电化学与UV-Vis光谱动力学信息同步。进一步探讨了GSH与Cr(Ⅵ)作用的电极反应机理。当Zn(Ⅱ)存在于该体系时,Zn(Ⅱ)对中间态配合物的生成和分解过程起着双向催化作用。 相似文献
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肼及其衍生物在固体电极上的直接电化学行为研究 总被引:1,自引:1,他引:0
肼及其衍生物被广泛应用于医药,化工,军事,航天等领域,并被用作推进剂,水处理剂,农药,医药,燃料电池,光稳定剂以及化工生产助剂等诸多方面。因此对肼及其衍生物的研究和开发有着极其重要的理论意义和应用价值。本文研究了肼(Hydrzdine,DH),苯肼(Phenylhydrazine,PH),对硝基苯肼(p-Nitrophenykhzille,PNPH)和2,4-二硝基苯肼(2,4-DinitrophenyIhydrazine,DPH)在固体玻碳电极和铂电极上的不可逆电化学氧化行为, 相似文献
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P. Trippel W. Maasfeld A. Kettrup 《International journal of environmental analytical chemistry》2013,93(1-2):97-110
Abstract A HPLC method has been developed for trace analysis of chlorophenols in the 0.2–2 ppb range from spiked water samples. Simple liquid-liquid extraction followed by on-line preconcentration of total mono- and dichlorophenols has been performed using a divinylbenzene-styrene copolymeric sorbent (PRP1) as packing material for the precolumn. The chlorophenols have been eluted from the precolumn on an analytical column (5μm LiChrosorb RP-18, 12.5 cm × 4 mm) by use of a switching valve system followed by separation. Detection was carried out with an electrochemical detector. The linearity of the detector response has been proved over two orders of magnitude. The detection limit of chlorophenols by means of the electrochemical method is in the lower picogram range. The recoveries of the isomeric chlorophenols from spiked river water samples having initial concentrations of 2ppb are usually 70–90%. The procedure has been applied to drinking water and river water. 相似文献