High‐Temperature Electrochemistry: A Review

High‐temperature electrochemistry remains a relatively unexplored field of research, although in recent years significant developments have been made. This report details the main experimental methods and approaches to heating an electrochemical system under both isothermal and non‐isothermal conditions and gives an insight into the experimental and electroanalytical results obtainable under such conditions. It has been shown that the promotion of mass transport at high‐temperatures, through diffusion or convection, often results in increased current signals. This increase benefits electroanalytical measurements by lowering detection limits. High temperatures also usefully enhance the sensitivity of systems with sluggish kinetics.     

基于超微电极的原位电化学拉曼光谱

原位电化学拉曼光谱是一种重要的光谱电化学技术.基于超微电极的原位电化学拉曼光谱将拉曼光谱反映的结构信息与电极表面的电化学过程从实验上严格对应和关联,为深刻理解电化学反应机理提供依据.本文综述了采用超微电极作为工作电极的原位电化学拉曼光谱的研究方法和应用进展,总结了应用超微电极作为工作电极开展电化学拉曼光谱实验的方法和具有表面增强拉曼活性的超微电极制备方法,展示了如何利用在超微电极表面获得的拉曼光谱与界面电化学过程的严格关联研究单个锌颗粒电化学氧化过程、吡啶分子在Au电极表面的电化学吸附过程,以及如何利用该技术能以高的信噪比和灵敏度同时测量光电流与分子反应这一特性研究对巯基苯胺选择性光氧化反应.采用超微电极作为工作电极的原位电化学拉曼光谱技术极大拓展了拉曼光谱技术的研究范围,有望成为探索(光)电化学反应的有力工具.     

The review of advances in interfacial electrochemistry in Estonia: electrochemical double layer and adsorption studies for the development of electrochemical devices

The electrochemistry nowadays has many faces and challenges. Although the focus has shifted from fundamental electrochemistry to applied electrochemistry, one needs to acknowledge that it is impossible to develop and design novel green energy transition devices without a comprehensive understanding of the electrochemical processes at the electrode and electrolyte interface that define the performance mechanisms. The review gives an overview of the systematic research in the field of electrochemistry in Estonia which reflects on the excellent collaboration between fundamental and applied electrochemistry.

     

Advancing the Electrochemistry of the Hydrogen‐Evolution Reaction through Combining Experiment and Theory

The electrocatalytic hydrogen‐evolution reaction (HER), as the main step of water splitting and the cornerstone of exploring the mechanism of other multi‐electron transfer electrochemical processes, is the subject of extensive studies. A large number of high‐performance electrocatalysts have been developed for HER accompanied by recent significant advances in exploring its electrochemical nature. Herein we present a critical appraisal of both theoretical and experimental studies of HER electrocatalysts with special emphasis on the electronic structure, surface (electro)chemistry, and molecular design. It addresses the importance of correlating theoretical calculations and electrochemical measurements toward better understanding of HER electrocatalysis at the atomic level. Fundamental concepts in the computational quantum chemistry and its relation to experimental electrochemistry are also presented along with some featured examples.     

Carbon Nanotubes Heavy Metal Detection with Stripping Voltammetry: A Review Paper

The challenge of heavy metal detection for environmental, industrial and medical purposes has led to the development of many analytical techniques. Stripping voltammetry is a very sensitive electrochemical method and has been widely used for heavy metal detection. Carbon nanotubes, a well‐studied carbon material with physical and chemical properties suited for electrode material is commonly employed for sensitive and selective metal detection in electrochemistry. This article reviews the recent (2011–2016) applications of carbon nanotubes as an electrode or electrode surface modifier for heavy metals detection with stripping voltammetry.     

《碳纳米材料电化学》专辑序言 ——方兴未艾的电化学能量转换和存储先进材料和技术

可以预见,在相当一段时期内,能源和环境将是全球发展的两大主题. 其实,人类对能源的获取方式将对地球的生态环境和人类未来的生存状态和生活方式产生重要影响. 正因为如此,世界各国正在大力发展可再生能源和清洁能源. 电化学能源是将化学能高效转变为电能的一种能量转换方式,它历史悠久,但不断被改进和创新,尤其是近年来得到了较快的发展. 目前,电化学能源转换和存储器件主要包括一次电池（如锌锰电池等）、二次电池（如铅酸电池、镍氢电池、锂离子电池等）、燃料电池、金属-空气电池以及超级电容器等. 电化学能源和其它可再生能源相互补充、交叉利用将是未来清洁能源的主要发展方向.     

《界面电化学》专辑序言

界面电化学是以研究电极-电解液界面的结构和性质以及各种电极过程为特点的电化学科学的重要方向. 随着能源科学的迅猛发展,围绕各种复杂电化学界面、探讨其在能源电化学过程中的特殊作用显得十分重要,而发展和运用各种原位和非原位表征方法研究复杂界面的结构和性能关系也日益受到关注. 本专辑收录论文9篇,包括7篇研究论文和2篇综述,侧重于锂基电池、电催化和离子液体电化学体系中的界面问题,反映我国学者在电化学界面基础和应用研究方面所取得的最新进展,并评述有关能源电化学界面所存在的问题、挑战和解决策略.希望籍此促进我国电化学研究的进一步发展. 在此,谨对所有为本专辑撰稿的作者所给予的大力支持和贡献表示诚挚谢意！ 同时对审稿人及编辑部工作人员为本专缉的出版所付出的辛勤劳动表示衷心感谢！     

稀土对LaNi_(3.5)Co_(0.8)Mn_(O.4)Al_(0.3)合金电化学及储氢特性的影响

研究了以Ce,Nd和Pr部分替代LaNi(3．5)Co(0.8)Mn(0.4)Al(0.3)中的La后对合金电化学及储氢特性的影响。稀土含量的变化明显改变合金的电化学及储氢特性。Pr对合金的电化学性能影响小于Ce。Ce使合金的放电容量降低,并升高合金的氢分解压。随着Nd含量的增加,合金的放电容量降低。     

A Glassy Carbon Electrode Modified with LangmuirBlodgett Film Composed of DNA and Polyaniline for the Sensitive Determination of Salbutamol

A composite Langmuir? Blodgett film prepared from DNA and polyaniline was deposited on the surface of a glassy carbon electrode (GCE) to give a new voltammetric sensor for the β2‐agonist salbutamol (SAL). Cyclic voltammetry and electrochemical impedance spectroscopy were employed to study the characteristic of the modified electrode. The electrochemistry of SAL at the modified electrode was investigated at pH 6.8 by cyclic voltammetry and differential pulse anodic voltammetry. The oxidation of SAL at this electrode is an adsorption‐controlled irreversible process. A sensitive electroanalytical method for determination of SAL was worked out that displays high precision and good reproducibility. The method was applied to quantify SAL in tablets with satisfactory results.     

Coupling Electrochemistry with Probe Electrospray Ionization Mass Spectrometry

A new coupling of electrochemistry with mass spectrometry (MS) using probe electrospray ionization (PESI) is presented. Due to the high salt tolerance of PESI, the detection of electrochemical reaction products in room‐temperature ionic liquids (RTILs) is realized for the first time. Furthermore, PESI‐MS allows the analysis of electrochemical reaction products on different or multiple electrode surfaces. In addition, peptides and proteins fractionated through isoelectric focusing (IEF) in the presence of an external electric field can also be directly analyzed by using PESI‐MS, suggesting a new and rapid characterization means for the IEF technique. This study reveals the versatility of EC/PESI‐MS, which could have an impact in electrochemistry and bioanalysis fields.     

单体动态电化学

由于个体的差异性和异质性作用,整体平均测量掩盖了个体的本征性质和电化学性能之间的关联.单体碰撞电化学作为一种强大而方便的电化学方法,已被用于研究超微电极上自由扩散的单个个体随机碰撞过程中的电化学行为.然而,个体的动态行为与其电化学反应过程息息相关.因此,对于单体动态电化学行为的研究可实时获取单体在电极界面上的动态电化学...     

A Novel Electrochemical Method for the Analysis of Hydrogen Peroxide with the Use of a Glassy Carbon Electrode Modified by a Prussian Blue/Copper‐Gold Bimetallic Nanoparticles Hybrid Film

A novel Prussian blue/copper‐gold bimetallic nanoparticles hybrid film modified electrode was prepared by electrochemical deposition on a glassy carbon electrode (PB/Cu‐AuNPs/GCE). Morphology and electrochemistry of this electrode were studied by UV‐vis spectroscopy, scanning electron microscopy, X‐ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly better electrocatalytic activity for the reduction of hydrogen peroxide in comparison with the single PB/GCE and PB/AuNPs/GCE. This was attributed to the synergistic effect of PB and Cu‐Au bimetallic nanoparticles. Also, the sensor demonstrated an overall high level of performance for the analysis of H₂O₂ in the concentration range from 0.002 to 0.84 mM.     

Preparation of Nano‐bismuth with Different Particle Sizes and the Size Dependent Electrochemical Thermodynamics

Nano‐bismuth has excellent electrochemical properties. However, it is still unclear how the particle size of nano‐bismuth influences its electrochemical thermodynamic properties. In this paper, spherical bismuth nanoparticles with different particle sizes were prepared by solvothermal method; the electrode potentials, the temperature coefficients of the electrode potentials and the thermodynamic functions of reaction for nano‐bismuth electrodes with different particle sizes at different temperatures were determined; and the effects of particle size on the electrode potential, the temperature coefficient and the thermodynamic functions were discussed. The experimental results show that particle size of bismuth nanoparticles has a significant influences on the electrochemical thermodynamic properties. The standard electrode potential of the nano‐bismuth electrode with a diameter of 39.9 nm was 0.009 V lower than that of the ordinary standard electrode (0.308 V); the temperature coefficient of the electrode potential with a diameter of 39.9 nm was nearly double that of 85.9 nm. With the particle sizes decrease, the standard molar Gibbs energy of reaction, the standard molar enthalpy of reaction, the standard molar entropy of reaction, the molar reversible reaction heat and the temperature coefficient increase; and these quantities are linearly related to the reciprocal of the particle diameter.     

Electron transfer studies of redox probes in bovine milk

In this work, we show that milk can act as an electrolytic medium to study electrochemical processes in the absence of any supporting electrolyte. The electron transfer properties of three different redox systems in bovine homogenized whole milk, skimmed milk, and reconstituted milk powder have been studied by cyclic voltammetry and impedance spectroscopy using a three-electrode system with a gold disk working electrode, a platinum sheet counter electrode, and a standard calomel reference electrode. It has been shown that the milk incredibly sustains the redox reactions in the absence of any supporting electrolyte and the electrochemical responses are comparable to those obtained when the same reactions were carried out in standard solvent preparations containing supporting electrolytes. The study clearly demonstrates the potential of developing new innovative techniques based on the intricate concepts of electrochemistry to study various aspects of milk that may help in the development of analytical sensors for the diary industry.     

Electrochemistry in bicontinuous microemulsions based on control of dynamic solution structures on electrode surfaces

Bicontinuous microemulsions (BMEs, Winsor III), also called middle-phase microemulsions, are low-viscosity, isotropic, thermodynamically stable, and spontaneously formed mixtures of water, oil, and surfactants. They are unique solution media for electrochemistry. Here, we introduce the recent progress in the electrochemistry of BMEs from their fundamental aspects to their practical applications. Electrochemistry using BMEs has two irreplaceable properties: the coexistence of hydrophilic and lipophilic species with high self-diffusion coefficients; and the dynamic deformation of structures at an oil/water/electrode ternary interface, which is easily changed according to the property of the electrode surface. Electrochemical contact with the micro-saline and oil phases in a BME is alternately or simultaneously achieved by controlling the hydrophilicity and lipophilicity of the electrode surfaces. The selective electrochemical analysis of hydrophilic and lipophilic antioxidants in liquid foods without extraction demonstrated as the use of the unique ternary solution structures of BME on solid surfaces.     

Determination of Explosives Using Electrochemically Reduced Graphene

A graphene‐based electrochemical sensing platform for sensitive determination of explosive nitroaromatic compounds (NACs) was constructed by means of electrochemical reduction of graphene oxide (GO) on a glassy carbon electrode (GCE). The electrochemically reduced graphene (ER‐GO) adhered strongly onto the GCE surface with a wrinkled morphology that showed a large active surface area. 2,4‐Dinitrotoluene (2,4‐DNT), as a model analyte, was detected by using stripping voltammetry, which gave a low detection limit of 42 nmol L⁻¹ (signal‐to‐noise ratio=3) and a wide linear range from 5.49×10⁻⁷ to 1.1×10⁻⁵ M . Further characterizations by electrochemistry, IR, and Raman spectra confirmed that the greatly improved electrochemical reduction signal of DNT on the ER‐GO‐modified GC electrode could be ascribed to the excellent electrocatalytic activity and high surface‐area‐to‐volume ratio of graphene, and the strong π–π stacking interactions between 2,4‐DNT and the graphene surface. Other explosive nitroaromatic compounds including 1,3‐dinitrobenzene (1,3‐DNB), 2,4,6‐trinitrotoluene (TNT), and 1,3,5‐trinitrobenzene (TNB) could also be detected on the ER‐GO‐modified GC electrode at the nM level. Experimental results showed that electrochemical reduction of GO on the GC electrode was a fast, simple, and controllable method for the construction of a graphene‐modified electrode for sensing NACs and other sensing applications.     

The Zeolitic Imidazolate Framework ZIF‐4 under Low Hydrostatic Pressures

The zeolitic imidazolate framework ZIF‐4 has recently been shown to exhibit large structural flexibility as a response to hydrostatic pressures, going from an open pore phase ( ZIF ‐ 4 ( Zn )‐ op ) to a closed pore phase ( ZIF ‐ 4 ( Zn )‐ cp ). The use of diamond anvil cell (DAC) setups has so far restricted thorough experimental insight into the evolution of lattice parameters at pressures below p < 0.1 GPa. Here we revisit the high‐pressure properties of ZIF‐4(Zn) by applying a new high‐pressure powder X‐ray diffraction setup that allows for tracking the evolution of lattice parameters in pressure increments as small as Δp = 0.005 GPa in the pressure range p = ambient – 0.4 GPa; a pressure resolution that cannot be achieved by using traditional DACs. We find ZIF‐4(Zn) has a bulk modulus of K( ZIF ‐ 4 ( Zn )‐ op ) = 2.01 ± 0.05 GPa and K( ZIF ‐ 4 ( Zn )‐ cp ) = 4.39 ± 0.20 GPa, clarifying and confirming some ambiguous results that have been reported previously.     

Carbon Paste Electrodes in Facts,Numbers, and Notes: A Review on the Occasion of the 50‐Years Jubilee of Carbon Paste in Electrochemistry and Electroanalysis

This article reviews the electrochemistry and electroanalytical applications of carbon paste‐based electrodes, sensors, and detectors on the occasion of the half‐of‐century anniversary since the discovery of carbon paste. The review (with 333 references) has been prepared in the form of a retrospective compilation presenting the field by means of various facts, notes, data, surveys, and summaries, including numerous rarities or curiosities that illustrate the individual achievements and milestones. Carbon paste‐based electrodes are discussed in their entirety by covering all important areas of the field, starting from basic characterization of carbon paste as the electrode material, via its typical physicochemical and electrochemical properties or specific features, up to a representative documentation of their applicability in electrochemical and electroanalytical measurements.     

Reversible Electrochemistry of Cytochrome c on Recompressed,Binderless Exfoliated Graphite Electrodes

The direct electrochemistry of cytochrome c (cyt‐c) has been investigated on exfoliated graphite (EG) electrodes. The as‐polished and roughened (using SiC emery sheet) EG surfaces are inactive for the direct electron transfer. However, when the EG electrode was sonicated before the experiment, a pair of redox waves were obtained for freely diffusing cyt‐c in the solution phase. The formal potential was found to be 0.01 V (vs. SCE) in 0.1 M phosphate buffer at a pH of 7.1. The electrochemical response for the adsorbed cyt‐c on sonicated EG electrodes, which is shown to have carbonyl functional groups on its surface, shows nearly reversible voltammograms in the same electrolyte. However, the formal potential in the adsorbed state is more negative than that observed for the solution phase cyt‐c. A structure based on an open heme conformation proposed by Hildebrandt and Stockburger is probably present on the EG surface. It is suggested that the electrochemistry at the EG electrode is essentially governed by favourable electrostatic interactions.