The role of atomic ensembles in the reactivity of bimetallic electrocatalysts

Bimetallic electrodes are used in a number of electrochemical processes, but the role of particular arrangements of surface metal atoms (ensembles) has not been studied directly. We have evaluated the electrochemical/catalytic properties of defined atomic ensembles in atomically flat PdAu(111) electrodes with variable surface stoichiometry that were prepared by controlled electrodeposition on Au(111). These properties are derived from infrared spectroscopic and voltammetric data obtained for electrode surfaces for which the concentration and distribution of the respective metal atoms are determined in situ by atomic resolution scanning tunneling microscopy with chemical contrast. Palladium monomers are identified as the smallest ensemble ("critical ensemble") for carbon monoxide adsorption and oxidation, whereas hydrogen adsorption requires at least palladium dimers.     

Electrochemical micromachining

The application of ultrashort voltage pulses between a tool electrode and a workpiece in an electrochemical environment allows the three-dimensional machining of conducting materials with submicrometer precision. The principle is based on the finite time constant for double-layer charging, which varies linearly with the local separation between the electrodes. During nanosecond pulses, the electrochemical reactions are confined to electrode regions in close proximity. This technique was used for local etching of copper and silicon as well as for local copper deposition.     

Spin-polarized light-emitting diode based on an organic bipolar spin valve

The spin-polarized organic light-emitting diode (spin-OLED) has been a long-sought device within the field of organic spintronics. We designed, fabricated, and studied a spin-OLED with ferromagnetic electrodes that acts as a bipolar organic spin valve (OSV), based on a deuterated derivative of poly(phenylene-vinylene) with small hyperfine interaction. In the double-injection limit, the device shows ~1% spin valve magneto-electroluminescence (MEL) response, which follows the ferromagnetic electrode coercive fields and originates from the bipolar spin-polarized space charge-limited current. In stark contrast to the response properties of homopolar OSV devices, the MEL response in the double-injection device is practically independent of bias voltage, and its temperature dependence follows that of the ferromagnetic electrode magnetization. Our findings provide a pathway for organic displays controlled by external magnetic fields.     

内场致发射电极在电解水中的电化学行为

内场致发射电极是根据内场致发射原理制备的一种电极。把它应用于电化学实验中是最近几年新兴起的一个学术研究领域。本文介绍了内场致发射电极的基本原理及在电解水中的应用，讨论了它在电解水中的电化学行为的规律，得出了内场致发射电子可以参加电化学反应的结论。     

Turing-type patterns on electrode surfaces

We report stationary, nonequilibrium potential and adsorbate patterns with an intrinsic wavelength that were observed in an electrochemical system with a specific type of current/electrode-potential (I-phi(DL)) characteristic. The patterns emerge owing to the interplay of a self-enhancing step in the reaction dynamics and a long-range inhibition by migration currents rather than by diffusion. Theoretical analysis revealed that this self-structuring of the electrode occurs in all electrochemical systems with an S-shaped I-phi(DL) characteristic in wide and well-accessible parameter ranges. This unusual pattern-forming instability in electrochemical systems has all the characteristics of the mechanism proposed by Turing in 1952 in the framework of an early theory of morphogenesis. Our finding might account for structure formation in certain biological systems that have gradients in the electric potential and may open new paths for fabricating patterned electrodes.     

多酸修饰电极对深色果蔬中维生素C的测定

【目的】制备磷钼酸复合膜修饰电极,并对其电化学性质和果蔬维生素C含量的测定进行相关探究,为深色果蔬中维生素C的测定提供理论依据。【方法】利用电化学沉积法在E=+0.26 V恒电位下制备磷钼酸复合膜修饰电极,并在不同条件下对其电化学性质进行检测,再以水果和蔬菜为研究对象,检验磷钼酸复合膜修饰电极对维生素C含量测定的效果。【结果】制备所得的磷钼酸具有稳定的Keggin结构;磷钼酸修饰后的电极在-0.4~+0.6 V内具备可逆的氧化还原峰;磷钼酸复合膜修饰电极的电催化能力与磷钼酸浓度呈正相关,且在高酸环境中电化学催化能力更强;该修饰电极对维生素C的氧化催化活性较明显,氧化催化活性随磷钼酸氧化程度和扫速的增加而提高,在连续增加维生素C浓度的过程中,修饰电极能快速响应维生素C,最短响应时间仅需3 s;以该电极为工作电极检测获得橙子、胡萝卜和青椒3种样品维生素C含量分别为45.32、71.16和96.99 mg/100 g,3次测定结果平均值的相对标准偏差（RSD）均未超过5.0%,且最低检测限为1.1×10-8 mol/L（S/N=3）。【结论】磷钼酸复合膜修饰电极的氧化催化活性良好,对深色果蔬维生素C的检测具有灵敏度高、检出限低和测定结果误差较小等特点。     

伏安型电子舌在食品检测中的研究进展

伏安型电子舌是一种基于电化学传感器阵列并结合多变量数据分析的方法对液体成分进行分析的检测系统。它一般由三电极构成,即工作电极、参考电极和辅助电极。本文简要介绍了电子舌的工作原理,重点阐述了伏安型电子舌在牛奶、食用油、茶叶和酒类等检测领域的应用状况,以及目前研究中伏安型电子舌存在的问题,并对其发展方向进行了展望。     

Capacitor electrode stimulates nerve or muscle without oxidation-reduction reactions

Porous tantalum disks, available as "slugs" from the capacitor industry, have large available surface area and a thin insulating coating of tantalum pentoxide. When implanted, they fill with extracellular fluid and operate as capacitor-stimulating electrodes having high capacitance per unit volume. Capable of stimulating excitable tissute without generating electrochemical by-products, these electrodes should provide a safer interface between neural prosthetic devices and human tissue.     

Chemical imaging of surfaces with the scanning electrochemical microscope

Scanning electrochemical microscopy is a scanning probe technique that is based on faradaic current changes as a small electrode is moved across the surface of a sample. The images obtained depend on the sample topography and surface reactivity. The response of the scanning electrochemical microscope is sensitive to the presence of conducting and electroactive species, which makes it useful for imaging heterogeneous surfaces. The principles and instrumentation used to obtain images and surface reaction-kinetic information are discussed, and examples of applications to the study of electrodes, minerals, and biological samples are given.     

Developments in electrochemical instrumentation

Commercial electrochemical instrumentation is in a state of mature development. Microprocessors are used mainly as devices for data handling, and there are no commercial computer-based instruments. Progress in the science and proliferation of applications depend on noninstrumental factors such as electrode materials.     

检测牛奶中结合珠蛋白的电流型免疫传感器的研制

为构建可定量检测牛奶中结合珠蛋白(Hp)含量的电流型免疫传感器,以三电极系统中的金电极为工作电极,采用层层自组装技术将L-半胱氨酸、纳米金颗粒和抗牛Hp抗体依次组装在工作电极上,制成免疫传感器。制成的免疫传感器对Hp的线性检测范围为15～100 mg.L-1,最低检测限为0.63 mg.L-1,并具有较好的重现性和稳定性。分别采用该传感器和ELISA检测试剂盒对隐性乳房炎患牛乳样中的Hp含量进行检测的结果表明,两种检测结果间无显著差异(P>0.05)。结论:制备的免疫传感器可定量检测牛奶中的结合珠蛋白(Hp)。     

三维电极体系工作机理探讨

反应器采用颗粒状活性炭为填料,中间位置添加隔膜,对极板和反应区电极电位的分布进行测定。结果表明:填料的隔膜处理使反应区电极电位分布规律明显,阴、阳极区靠近隔膜处的电极电位绝对值明显高于靠近两极处,且阴、阳极区电极电位绝对值都随外加电压的增大而增大;固定阳极板,改变阴极板材料,阴极板电极电位高低与极板材料性质密切相关;阴、阳极板电极电位的差值决定了阴、阳极反应区电极电位的变化方向。     

Surface-driven switching of liquid crystals using redox-active groups on electrodes

Electrochemical control of the oxidation state of ferrocene-decorated electrodes leads to surface-driven changes in the orientations of thermotropic liquid crystals. When the electrodes possess nanometer-scale topography, voltages of 0.0 to 0.3 volts (versus a counter electrode in a two-electrode cell) can drive changes in the orientation of the liquid crystals in the plane and/or out of the plane of the electrodes. Electrodes not supporting ferrocene do not lead to surface-driven orientational transitions. The in-plane transitions are driven by the reorganization of the monolayer of ferrocene upon oxidation of ferrocene to ferrocenium. The out-of-plane transition reflects a dielectric coupling between the liquid crystal and the diffuse part of an electrical double layer that evolves upon oxidation of ferrocene to ferrocenium. These results suggest new ways to couple the orientations of liquid crystals to chemical and electrical stimuli in electro-optical devices and chemical sensors.     

木质素高盐模板碳气凝胶制备及其电化学应用

目的以工业碱木质素和甲醛为原料，在盐的制孔和稳定作用下，水热反应后直接碳化制备多孔碳气凝胶，并检测其结构、理化性质和电化学性能，探究其在超级电容器电极材料中的运用。方法将2 g工业碱木质素分别与3种盐（ZnCl₂、NaCl、Na₂CO₃）混合均匀，各加入1.5 mL甲醛，搅拌成黏稠浆状，转移至反应釜中，160 ℃反应2 h，得到一系列的木质素碳气凝胶（LCA）前驱体，在通氮气保护的管式炉中，以3 ℃/min的升温速率升温至900 ℃，保温3 h进行碳化，自然冷却后取出并洗涤，得到LCA。通过比表面积测定（SSA）、扫描电镜（SEM）、X射线衍射（XRD）表征碳气凝胶的结构和理化性质，将其研磨粉碎后制成超级电容器电极，通过循环伏安测试、恒流充放电测试和开位电路阻抗测试进行电化学储能表征。结果以ZnCl₂为模板制备的LCA最高比表面积可达711 m2/g，在SEM下能观察到凝胶状结构，XRD表明LCA以无定形碳为主。在0.2 A/g的电流密度下，比电容达到124 F/g；在10 A/g的高电流密度下，比电容维持在60 F/g，电容保持率约为48%，拥有最佳的倍率性能。结论本实验以价格低廉的工业碱木质素为原料，在盐模板下经过水热和碳化过程直接制备LCA。在ZnCl₂盐模板下可以制备出高比表面积，以无定形碳为主的LCA，并拥有优良的电化学性能，可用于超级电容器电极材料。该方法绿色环保、操作简单、成本低，具有潜在的工业化利用前景。      

Phase-coherent transport in graphene quantum billiards

As an emergent electronic material and model system for condensed-matter physics, graphene and its electrical transport properties have become a subject of intense focus. By performing low-temperature transport spectroscopy on single-layer and bilayer graphene, we observe ballistic propagation and quantum interference of multiply reflected waves of charges from normal electrodes and multiple Andreev reflections from superconducting electrodes, thereby realizing quantum billiards in which scattering only occurs at the boundaries. In contrast to the conductivity of conventional two-dimensional materials, graphene's conductivity at the Dirac point is geometry-dependent because of conduction via evanescent modes, approaching the theoretical value 4e(2)/pih (where e is the electron charge and h is Planck's constant) only for short and wide devices. These distinctive transport properties have important implications for understanding chaotic quantum systems and implementing nanoelectronic devices, such as ballistic transistors.     

Nanofabrication of Small Copper Clusters on Gold(111) Electrodes by a Scanning Tunneling Microscope

The use of scanning tunneling microscopy in an electrochemical environment as a tool for the nanoscale modification of gold electrodes was demonstrated. Small copper clusters, typically two to four atomic layers in height, were precisely positioned on a gold(111) electrode by a process in which copper was first deposited onto the tip of the scanning tunneling microscope, which then acted as a reservoir from which copper could be transferred to the surface during an appropriate approach of the tip to the surface. Tip approach and position were controlled externally by a microprocessor unit, allowing the fabrication of various patterns, cluster arrays, and "conducting wires" in a very flexible and convenient manner.     

联荼冠醚修饰电极测定汞

Several special crown ethers have been used to prepare modified electrodes and their performances are compared. The electrode prepared from bi-dinaphthy1-22-crown-6 shows the best performance characteristics has been studied in detail, which has been appl     

Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes

The selection and assembly of materials are central issues in the development of smaller, more flexible batteries. Cobalt oxide has shown excellent electrochemical cycling properties and is thus under consideration as an electrode for advanced lithium batteries. We used viruses to synthesize and assemble nanowires of cobalt oxide at room temperature. By incorporating gold-binding peptides into the filament coat, we formed hybrid gold-cobalt oxide wires that improved battery capacity. Combining virus-templated synthesis at the peptide level and methods for controlling two-dimensional assembly of viruses on polyelectrolyte multilayers provides a systematic platform for integrating these nanomaterials to form thin, flexible lithium ion batteries.     

高压直流接地极对埋地管道的干扰监测及影响规律

为了掌握高压直流输电工程接地极对埋地管道杂散电流干扰的影响规律,在17个高压直流输电工程接地极附近的12条管道上安装了电位远程监测系统,对管道电位进行长时间连续监测。通过管道电位变化分析接地极的干扰频次和干扰时间,以及管道受干扰程度、影响范围。监测结果显示:通过对管道电位长时间连续监测能够准确判断出接地极对管道的干扰影响,2017年17个接地极的总干扰频次为201次,干扰总时长为657.31 h,较2016年略有下降;监测到1987 km管道受到接地极的干扰,其中华南地区接地极对管道的干扰较华东、华中及西北地区大。干扰电位分布规律分析结果表明,接地极与管道的垂直距离越短,靠近接地极端杂散电流流入流出的管段越短,其对远离接地极端的管道的干扰程度越大、干扰范围越广。     

Anomalous increase in carbon capacitance at pore sizes less than 1 nanometer

Carbon supercapacitors, which are energy storage devices that use ion adsorption on the surface of highly porous materials to store charge, have numerous advantages over other power-source technologies, but could realize further gains if their electrodes were properly optimized. Studying the effect of the pore size on capacitance could potentially improve performance by maximizing the electrode surface area accessible to electrolyte ions, but until recently, no studies had addressed the lower size limit of accessible pores. Using carbide-derived carbon, we generated pores with average sizes from 0.6 to 2.25 nanometer and studied double-layer capacitance in an organic electrolyte. The results challenge the long-held axiom that pores smaller than the size of solvated electrolyte ions are incapable of contributing to charge storage.