Charge attachment–induced transport: toward new paradigms in solid state electrochemistry

Modern applications in solid state electrochemistry, e.g. in the field of energy storage and conversion, involve the transport of charge carriers through surfaces or interfaces as a key aspect. Many of the electrochemical concepts in fact originate from the field of liquid state electrochemistry. The transfer of concepts from the liquid to the solid state causes some problem which are addressed in this review. Topics covered include (i) electrode potentials and half-cell potentials, (ii) charge carrier blocking and dielectric breakdown, and (iii) activities versus particle densities. Many of these topics can be addressed by the charge attachment–induced transport technique developed in the authors group. The discussion involves modifying some of the paradigms we became acquainted to in the liquid state.     

Surface charging behaviors of electrocatalytic interfaces with partially charged chemisorbates

The surface charge is a key concept in electrochemistry. Mathematically, the surface charge is obtained from a spatial integration of the volume charge along a particular direction. Ambiguities thus arise in choosing the starting and ending points of the integration. As for electrocatalytic interfaces, the presence of chemisorbates further complicates the situation. In this minireview, I adopt a definition of the surface charge within a continuum picture of the electric double layer. I will introduce surface charging behaviors of firstly ordinary electrochemical interfaces and then electrocatalytic interfaces featuring partially charged chemisorbates. Particularly, the origin of nonmonotonic surface charging behaviors of electrocatalytic interfaces is explained using a primitive model. Finally, a brief account of previous studies on the nonmonotonic surface charging behavior is presented, as a subline of the spectacular history of electric double layer.     

Electrochemical behaviors of adrenaline at acetylene black electrode in the presence of sodium dodecyl sulfate

The electrochemical behaviors of adrenaline at the acetylene black electrode in the presence of sodium dodecyl sulfate (SDS) were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). The results indicated that the electrochemical responses of adrenaline were apparently improved by SDS, due to the enhanced accumulation of protonated adrenaline via electrostatic interaction with negatively charged SDS at the hydrophobic electrode surface. This was verified by the influences of different kinds of surfactants on the electrochemical signals of adrenaline. The electrochemical parameters of the adrenaline oxidation were explored by chronocoulometry. Under optimal working conditions, the oxidation peak current at 0.57 V was proportional to adrenaline concentration in the range of 5.0x10(-8) to 7.0x10(-6) mol/L, with a low detection limit of 1.0x10(-8)mol/L for 70s accumulation by differential pulse voltammetry (DPV). This method was applied to determine adrenaline in the hydrochloride injection sample. The results are satisfying compared with that by the standardized method of high performance liquid chromatography (HPLC).     

Impedance simulation of a solid oxide fuel cell anode in time domain

The purpose of the current study is to simulate the behavior of a solid oxide fuel cell (SOFC) anode under sinusoidal excitation. The obtained harmonic response is used as a base for electrochemical impedance spectra simulation. The electrochemical impedance spectroscopy (EIS) is a powerful non-destructive tool for SOFC researches. In order to evaluate the EIS experimental results, efforts are devoted to develop EIS numerical simulation tools. In this study, a planar SOFC is modeled, and the steady state behavior and frequency response, as well as the electrochemical spectra of the anode, are obtained. The developed model couples the electrochemical kinetics with mass transport. The Butler–Volmer equation is used for the anode electrochemistry, and the species equations are used for gas transport in the anode channel. In order to solve the system of the nonlinear equations, an in-house code based on finite difference method is developed and utilized. A parametric study is also carried out, and the results are discussed. The simulation results are in good agreement with published data. Results show a capacitive semicircle in the Nyquist plot, which is identical to the gas diffusion impedance as reported in literatures.     

Electrochemical Properties of Phospholipid Monolayers at Liquid–Liquid Interfaces

Biomembrane models built at the interface between two immiscible electrolytes (ITIES) are useful systems to study phenomena of biological relevance by means of their electrochemical processes. The unique properties of ITIES allow one either to control or measure the potential difference across the biomimetic membranes. Herein we focus on phospholipid monolayers adsorbed at liquid–liquid interfaces, and besides discussing recent developments on the subject, we describe electrochemical techniques that can be used to get insight on the interfacial processes and electrostatic properties of phospholipid membranes at the ITIES. In particular, we examine the electrochemical and physicochemical properties of (modified) phospholipid monolayers and their interaction with other biologically relevant compounds. The use of liquid–liquid electrochemistry as a powerful tool to characterize drug properties is outlined. Although this review is not a survey of all the work in the field, it provides a comprehensive referencing to current research.     

Solid–liquid interface analysis with in-situ Rutherford backscattering and electrochemical impedance spectroscopy

A novel Rutherford backscattering spectrometry (RBS) method is presented to investigate the interface between a solid surface and a surrounding liquid. The introduced measurement system allows to observe and quantify adsorption at the solid–liquid interface and the formation of the electrochemical double layer (EDL). BaCl₂ as a bicomponent electrolyte and a Si₃N₄ membrane surface are chosen as a model system to prove the capabilities of the setup. The results of these RBS measurements are combined with electrochemical impedance spectroscopy (EIS) to validate the findings for the solid–liquid interface under study. Complementary results and discrepancies regarding the formation of the EDL are discussed.     

Structural effects on metal ion migration across polymer inclusion membranes: Dependence of transport profiles on nature of active plasticizer

Structural modifications promoted by the nature of the plasticizer that affect metal ion migration in polymer inclusion membranes (PIMs) were evaluated using transport data, transmission infrared mapping microspectroscopy (TIMM) and electrochemical impedance spectroscopy (EIS). An analysis of the effects of different plasticizers on indium(III) transport across cellulose triacetate membranes with bis(2,4,4-trimethylpentyl)phosphinic acid (CYANEX 272) as carrier revealed differences in transport profiles that can be explained on the basis of the nature of plasticizer used. While a transport profile of the type carrier-diffusion was observed for tris(2-ethylhexyl)phosphate (TEHP), a transport profile of the type chained-carrier with reduced mobility was suggested by the presence of a percolation threshold for PIMs with tris(2-butoxyethyl)phosphate (TBEP), 2-nitrophenyloctylether (NPOE) and without plasticizer under the experimental conditions used in this work. Accordingly, diffusional equations and percolation theory were used to model permeation and to gain insight into the transport processes occurring in these systems. A correlation between the structural conformation of the PIMs and the transport profiles was successfully achieved using the aforementioned characterization techniques and theoretical frames. Values of the percolation parameters were rationalized considering the distribution of the membrane components observed by TIMM and PIM resistances evaluated by EIS. Membrane behavior for metal extraction was characterized by the determination of the equilibrium constants via solid–liquid extraction experiments. EIS measurements allowed correlating the equilibrium constants with membrane resistances as well.     

Electrochemistry of Diamond: A Review

Because of its extraordinary chemical stability, diamond is a perspective electrode material to be used in electrochemistry and electrochemical engineering. In this review-article, the results of basic studies in the synthetic-diamond electrochemistry are summarized: the electrochemical kinetics, photoelectrochemistry, electrochemical impedance spectroscopy. Relations between the semiconductor nature and crystal structure of diamond and its electrochemical behavior are revealed. Prospects for using diamond electrodes in the electroanalysis, electrosynthesis, and environmentally-oriented industry are outlined.     

Scanning electrochemical microscopy for direct imaging of reaction rates

Not only in electrochemistry but also in biology and in membrane transport, localized processes at solid-liquid or liquid-liquid interfaces play an important role at defect sites, pores, or individual cells, but are difficult to characterize by integral investigation. Scanning electrochemical microscopy is suitable for such investigations. After two decades of development, this method is based on a solid theoretical foundation and a large number of demonstrated applications. It offers the possibility of directly imaging heterogeneous reaction rates and locally modifying substrates by electrochemically generated reagents. The applications range from classical electrochemical problems, such as the investigation of localized corrosion and electrocatalytic reactions in fuel cells, sensor surfaces, biochips, and microstructured analysis systems, to mass transport through synthetic membranes, skin and tissue, as well as intercellular communication processes. Moreover, processes can be studied that occur at liquid surfaces and liquid-liquid interfaces.     

An ITO Based Disposable Biosensor for Ultrasensitive Analysis of Retinol Binding Protein

A highly sensitive electrochemical biosensor based on anti‐RBP biorecognition capable to analyze concentrations of retinol binding protein (RBP) was developed. The construction of the biosensor interfaces was carefully characterized by techniques such as electrochemistry, EIS, and scanning electron microscopy. In order to characterize impedance data, Kramers‐Kronig Transform was performed on the experimental impedance data. Besides, for an immunosensor system the Single Frequency Impedance technique was firstly used for the characterization of the interaction between RBP and anti‐RBP. Finally, artificial serum samples spiked with RBP were analyzed by the proposed ITO based immunosensor to investigate the usefulness of the biosensor for early biomarker diagnosis.     

Effects of applied voltage on water at a gold electrode interface from ab initio molecular dynamics

Electrode–water interfaces under voltage bias demonstrate anomalous electrostatic and structural properties that are influential in their catalytic and technological applications. Mean-field and empirical models of the electrical double layer (EDL) that forms in response to an applied potential do not capture the heterogeneity that polarizable, liquid-phase water molecules engender. To illustrate the inhomogeneous nature of the electrochemical interface, Born–Oppenheimer ab initio molecular dynamics calculations of electrified Au(111) slabs interfaced with liquid water were performed using a combined explicit–implicit solvent approach. The excess charges localized on the model electrode were held constant and the electrode potentials were computed at frequent simulation times. The electrode potential in each trajectory fluctuated with changes in the atomic structure, and the trajectory-averaged potentials converged and yielded a physically reasonable differential capacitance for the system. The effects of the average applied voltages, both positive and negative, on the structural, hydrogen bonding, dynamical, and vibrational properties of water were characterized and compared to literature where applicable. Controlled-potential simulations of the interfacial solvent dynamics provide a framework for further investigation of more complex or reactive species in the EDL and broadly for understanding electrochemical interfaces in situ.

Ab initio molecular dynamics of an aqueous electrode interface reveal the electrostatic, structural, and dynamic effects of quantifiable voltage biases on water.     

Photophysics and electrochemistry relevant to photocatalytic water splitting involved at solid–electrolyte interfaces

Direct photon to chemical energy conversion using semiconductor–electrocatalyst–electrolyte interfaces has been extensively investigated for more than a half century. Many studies have focused on screening materials for efficient photocatalysis. Photocatalytic efficiency has been improved during this period but is not sufficient for industrial commercialization. Detailed elucidation on the photocatalytic water splitting process leads to consecutive six reaction steps with the fundamental parameters involved: The photocatalysis is initiated involving photophysics derived from various semiconductor properties(1: photon absorption, 2: exciton separation). The generated charge carriers need to be transferred to surfaces effectively utilizing the interfaces(3: carrier diffusion, 4: carrier transport). Consequently, electrocatalysis finishes the process by producing products on the surface(5: catalytic efficiency, 6: mass transfer of reactants and products). Successful photocatalytic water splitting requires the enhancement of efficiency at each stage. Most critically, a fundamental understanding of the interfacial phenomena is highly desired for establishing "photocatalysis by design" concepts, where the kinetic bottleneck within a process is identified by further improving the specific properties of photocatalytic materials as opposed to blind material screening. Theoretical modeling using the identified quantitative parameters can effectively predict the theoretically attainable photon-conversion yields. This article provides an overview of the state-of-the-art theoretical understanding of interfacial problems mainly developed in our laboratory.Photocatalytic water splitting(especially hydrogen evolution on metal surfaces) was selected as a topic,and the photophysical and electrochemical processes that occur at semiconductor–metal, semiconductor–electrolyte and metal–electrolyte interfaces are discussed.     

Anisotropic structure and transport in self-assembled layered polymer-clay nanocomposites

Using the layer-by-layer (LbL) assembly technique, we create a polymer-clay structure from a unique combination of LbL materials: poly(ethylene imine), Laponite clay, and poly(ethylene oxide). This trilayer LbL structure is assembled using a combination of hydrogen bonding and electrostatic interactions. The films were characterized using ellipsometry, profilometry, X-ray photon spectroscopy, atomic force microscopy, scanning electron microscopy, wide-angle X-ray diffraction, grazing-incidence small-angle X-ray scattering, and electrochemical impedance spectroscopy (EIS). We observe a layered, anisotropic structure, which resulted in in-plane ion transport 100 times faster than cross-plane at 0% relative humidity. This study represents a first application of EIS in determining anisotropic ion transport in LbL assemblies and its correlation to structural anisotropy.     

Investigation of the effect of finite-sized ions on the nanowire field-effect transistor in electrolyte concentration using a modified Poisson–Boltzmann model

One-dimensional (1D) nanowire field-effect transistors (FETs) have recently played a major role in sensing applications. Due to charging of the surface functional chemical groups with protonation and deprotonation, the transport properties of these nanowire transistors affect the aqueous environment, altering the electrical double layer (EDL) potential drops and charge distributions in the electrolyte concentration. In this work, we have implemented the simple modified Poisson–Boltzmann (MPB) theory in a 1D silicon nanowire FET, and the effect of the various finite sizes of ions in z:z symmetric electrolyte concentration was investigated. For a given ionic concentration and surface charge, the EDL potential drop, accumulation of charges and the charge distributions of NaCl and CsCl ions were studied. From the MPB model results with the nanowire FET, it was observed that the potential drop of the EDL depends on the size of the ions in the electrolyte. The study of various electrostatic investigations of finite-sized ions was successfully done by implementing the MPB model on a silicon nanowire FET. It can be used in both chemical and biological sensors.     

Direct electron transfer of horseradish peroxidase and its electrocatalysis based on carbon nanotube/thionine/gold composites

Horseradish peroxidase (HRP) was incorporated into multiwalled carbon nanotube/thionine/Au (MTAu) composite film by electrostatic interactions between positively charged HRP and negatively charged MTAu composite. The results of electrochemical impedance spectroscopy (EIS) confirmed adsorption of HRP on the surface of MTAu modified GC electrode. Moreover, the electrochemical results showed that HRP retained its bioactivity and bioelectrocatalytical activity, and also showed good direct electron transfer behavior on such a composite film.     

Structure and dynamics of nanoscale electrical double layer

Electrical double layer (EDL) at substrate–solution interface plays essential roles in basic electrochemistry, energy conversion, desalination and separation, stochastic single-entity sensing, and other applications. The EDL structure generally refers to the inhomogeneous distribution of solution ions at the interfacial region. Dynamic changes in the EDL structure due to the transport of charges at the nanometer scale are the physicochemical origin of recently resolved novel nanotransport phenomena. High surface area materials and devices are potentially advantageous for better applications by providing more accessible interfaces. It is of high importance to emphasize that interfacial structures are indications of capacity, while the efficiency is often related to dynamics. This review discusses emerging transport phenomena under steady-state conditions and the transient deviations in prototype channel-type nanopores as unit elements for porous electrodes/membranes. The fundamental governing mechanism and structure–function correlations will be discussed in the context of energy harvesting and storage, desalination and phase transition, and resistive pulse sensing at the nanometer scale toward single-event/entity resolutions.     

Electrochemistry at micro- and nanoscopic liquid/liquid interfaces

In this tutorial review, we will briefly introduce the history and basic concepts of micro- and nanoscopic liquid/liquid interfaces (size from nm to μm) in electrochemical studies of charge (electron and ion) transfer reactions at soft molecular interfaces. Their advantages and problems are usually compared with those of conventional liquid/liquid interfaces (size from mm to cm); and with solid/electrolyte interfaces. Three methods of fabrication of micro-liquid/liquid interfaces and one approach to support a nano-liquid/liquid interface are surveyed. The experimental and theoretical aspects are discussed along with possible approaches to characterize these micro- and nanoscopic liquid/liquid interfaces, and the methods to modify them with new functionality. Unique examples of applications of electrochemistry at micro- and nanoscopic liquid/liquid interfaces are provided. Some novel and potential research interests in the future in this field are discussed.     

锂离子电池多孔电极理论的回顾与新思考

本文总结了Newman多孔电极理论的基本内容,提出若干改进思路. 提出基于离子-空穴耦合传输机制描述浓电解质中的离子输运过程,在此基础上引入离子-电子耦合转移反应的思想处理电极材料中的离子传输问题,并通过计算嵌锂材料的离子扩散系数验证其合理性. 总结了描述多孔电极多尺度结构的相关理论和技术,表明均质化方法和基于结构重建的介观模拟方法均能给出比较合理的有效输运参数,从而提高多孔电极理论模拟结果的准确性.