Phase Sensitive Alternating Current Polarography: A Chemometric Approach for the Selection of Phase Angles

A method based on the combined use of multivariate curve resolution by alternating least squares (MCR‐ALS) with phase sensitive alternating current polarography (ACP) is proposed to evaluate the phase angle where capacitive current is minimized in a much more accurate way than the visual inspection of ACP signals. The method allows, through the analysis of series of AC polarograms measured at different phase angles out the potential, to distinguish between faradaic and capacitive contributions. Then the angle at which the capacitive current is negligible can be shown and, in some cases, the influence of adsorption on measured currents minimized.     

Carbon Transition‐metal Oxide Electrodes: Understanding the Role of Surface Engineering for High Energy Density Supercapacitors

Supercapacitors store electrical energy by ion adsorption at the interface of the electrode‐electrolyte (electric double layer capacitance, EDLC) or through faradaic process involving direct transfer of electrons via oxidation/reduction reactions at one electrode to the other (pseudocapacitance). The present minireview describes the recent developments and progress of carbon‐transition metal oxides (C‐TMO) hybrid materials that show great promise as an efficient electrode towards supercapacitors among various material types. The review describes the synthetic methods and electrode preparation techniques along with the changes in the physical and chemical properties of each component in the hybrid materials. The critical factors in deriving both EDLC and pseudocapacitance storage mechanisms are also identified in the hope of pointing to the successful hybrid design principles. For example, a robust carbon‐metal oxide interaction was identified as most important in facilitating the charge transfer process and activating high energy storage mechanism, and thus methodologies to establish a strong carbon‐metal oxide contact are discussed. Finally, this article concludes with suggestions for the future development of the fabrication of high‐performance C‐TMO hybrid supercapacitor electrodes.     

Adsorption of urea on a polycrystalline copper electrode

The adsorption of urea on a polycrystalline copper electrode from 0.01 M NaClO₄ solution has been studied by impedance spectroscopy and radiometric method. The dependence of the surface concentration of urea on the electrode potential and the bulk concentration was determined. From radiometric data, it follows that the adsorption of urea on the copper electrode takes place in the entire range of studied potentials where no faradaic processes occur. In this range, the process of adsorption is practically reversible with respect to the potential and the bulk concentration of urea. The experimental data were described by the Langmuir and the virial isotherms and the Gibbs energy of adsorption were calculated. The data of the urea adsorption on different electrodes have been compared and the role of the kind of the metal on the adsorption process was discussed.     

Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels

Electrochemical reduction of carbon dioxide, if powered by renewable electricity, could serve as a sustainable technology for carbon recycling and energy storage. Among all the products, ethanol is an attractive liquid fuel. However, the maximum faradaic efficiency of ethanol is only ≈10 % on polycrystalline Cu. Here, CuZn bimetallic catalysts were synthesized by in situ electrochemical reduction of ZnO‐shell/CuO‐core bi‐metal‐oxide. Dynamic evolution of catalyst was revealed by STEM‐EDS mapping, showing the migration of Zn atom and blending between Cu and Zn. CuZn bimetallic catalysts showed preference towards ethanol formation, with the ratio of ethanol/ethylene increasing over five times regardless of applied potential. We achieved 41 % faradaic efficiency for C₂₊ liquids with this catalyst. Transitioning from H‐cell to an electrochemical flow cell, we achieved 48.6 % faradaic efficiency and ?97 mA cm^?2 partial current density for C₂₊ liquids at only ?0.68 V versus reversible hydrogen electrode in 1 m KOH. Operando Raman spectroscopy showed that CO binding on Cu sites was modified by Zn. Free CO and adsorbed *CH₃ are believed to combine and form *COCH₃ intermediate, which is exclusively reduced to ethanol.     

Electrochemical monitoring of the thermal decomposition of arenediazonium ions with time in acidic MeOH/H2O mixtures: dediazotization rate constant

The rate of the spontaneous decomposition of 4-methylbenzenediazonium tetrafluoroborate, 4MBD, was determined. The effects of solvent composition (MeOH/H2O) on its electrochemical processes and on those of the derivatized 2-naphthol-6-sulfonate-4-toluene (6S2NPT) azo dye were investigated by Differential Pulse Polarography (DPP). This electrochemical technique shows an effective sensitivity for detecting arenediazonium ions and derivatized azo dyes.     

Determination of complex formation constants by phase sensitive alternating current polarography: Cadmium-polymethacrylic acid and cadmium-polygalacturonic acid

The use of phase sensitive alternating current polarography (ACP) for the evaluation of complex formation constants of systems where electrodic adsorption is present has been proposed. The applicability of the technique implies the previous selection of the phase angle where contribution of capacitive current is minimized. This is made using Multivariate Curve Resolution by Alternating Least Squares (MCR-ALS) in the analysis of ACP measurements at different phase angles. The method is checked by the study of the complexation of Cd by polymethacrylic (PMA) and polygalacturonic (PGA) acids, and the optimal phase angles have been ca. −10° for Cd-PMA and ca. −15° for Cd-PGA systems. The goodness of phase sensitive ACP has been demonstrated comparing the determined complex formation constants with those obtained by reverse pulse polarography, a technique that minimizes the electrode adsorption effects on the measured currents.     

Specific features of the behavior of an electrochemical system in the case of the Hopf instability for a spherical electrode

Model approximations are developed that allow establishing a quantitative relationship between the geometrical parameters of a spherical electrode, the faradaic impedance, and instabilities of the electrochemical system for an electrode reaction under potentiostatic conditions for the adsorption of species preceding their discharge. It is shown that the control parameter ω_H in the Hopf bifurcation point depends on the electrode size. The effect of the Nernst diffusion layer is observed at low frequencies in the range of negative faradaic impedance values.     

Advantage of Fractional Calculus Based Hybrid‐Theoretical‐Computational‐Experimental Approach for Alternating Current Voltammetry

The dynamic electrochemical behavior of electroactive species is believed to be represented better by the fractional calculus, because it can consider the history of mass‐transfers of that species near the electrode surface. The elucidation of mathematical fundamentals of fractional calculus has been recently introduced for batteries, supercapacitors and a few voltammetry studies. The working equations for faradaic fundamental and second‐harmonic (SHac) components of alternating current (ac) for ac voltammetry of an electrochemically reversible redox reaction on an electrode of macroscopic diameter have been derived here by using generalized formulae of the fractional calculus. A computation code is written in Python language with a matrix based algorithm developed based on latest, accurate, efficient and stable Grunwald‐Letnikov‐Improved fractional‐order differentiation equation. That computational code is used to find the concealed faradaic fundamental, SHac components of the total current and other double‐layer parameters of experimentally recorded voltammograms of ruthenium(III/II) redox reaction on gold‐disc electrode by a common electrochemical workstation without having inbuilt Fourier transformation features. The amplitude of the computed faradaic current concealed in the experimental data gets enhanced through this hybrid theoretical‐computational‐experimental approach and thus it keeps scope of application and further improvement in electroanalysis.     

提高电容性电化学储能装置能量容量的一些尝试

本文从作者所在的课题组在超级电容器和超级电容电池方向的研究内容为基础,在电极材料和装置层面综述了电容性电化学储能装置的发展. 导电聚合物和过渡金属氧化物分别与碳纳米管复合后的复合物能显著提高前两者作为电容性法拉第储能电极的电容性能. 活性炭和碳黑等一类碳材料则可作为非法拉第储能的电极材料. 通过对超级电容器正负极电容做相应的匹配调整可以提高超级电容器的最大充电电压,从而提高超级电容器的能量容量. 此外,为了与实际设备相匹配,超级电容可以以双极板的方式串联堆积,满足高电压的需求. 超级电容电池作为新一代的电容性电化学储能装置,分别由具有电容性和法拉第电荷储存原理的电极组成,具有高比功率和高比能量的特点,也是近年来的研究热点.     

An immitance study of the mechanism of hydrogen reactions on a tungsten carbide electrode: Part I. Experiment and analysis in terms of a linear model

The ac admittance spectra of a smooth tungsten carbide (WC) electrode in a stirred H₂-saturated 0.5 M H₂SO₄ solution were measured at hydrogen overpotentials from −0.15 to +0.25 V in the frequency range from 0.1 to 900 Hz, at a temperature of 80°C.An extended analysis of immitance spectra in diagrams of various coordinates led to an interpretation of the system under study at any potential in terms of a linear model which took into account the constant phase element behaviour of the electrode double layer and the presence of two parallel, activation-controlled faradaic processes: the hydrogen ionization/evolution process and an additional electrochemical adsorption reaction passivating the electrode surface for the hydrogen process.Computerized fitting of a rational equivalent circuit to the immitance spectra for all the potentials gave the dependences of the equivalent circuit elements on the potential. The fits proved that the mechanism of the faradaic processes taking place on the electrode is probably the same in the entire range of potentials.     

Electrochemical monitoring of the thermal decomposition of arenediazonium ions with time in acidic MeOH/H2O mixtures: dediazotization rate constant

The rate of the spontaneous decomposition of 4-methylbenzenediazonium tetrafluoroborate, 4MBD, was determined. The effects of solvent composition (MeOH/ H₂O) on its electrochemical processes and on those of the derivatized 2-naphthol-6-sulfonate-4-toluene (6S2NPT) azo dye were investigated by Differential Pulse Polarography (DPP). This electrochemical technique shows an effective sensitivity for detecting arenediazonium ions and derivatized azo dyes. Received: 26 September 2000 / Revised: 12 December 2000 / Accepted: 13 December 2000     

Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small‐Angle Neutron Scattering

A molecular‐level understanding of transport and adsorption mechanisms of electrolyte ions in nanoporous electrodes under applied potentials is essential to control the performance of double‐layer capacitors. Here, in operando small‐angle neutron scattering (SANS) is used to directly detect ion movements into the nanopores of a conductive metal–organic framework (MOF) electrode under operating conditions. Neutron‐scattering data reveals that most of the void space within the MOF is accessible to the solvent. Upon the addition of the electrolyte sodium triflate (NaOTf), the ions are adsorbed on the outer surface of the protrusions to form a 30 Å layer instead of entering the ionophobic pores in the absence of an applied charging potential. The changes in scattering intensity when potentials are applied suggests the ion rearrangement in the micropores following different mechanisms depending on the electrode polarization. These observations shed insights on ion electrosorption in electrode materials.     

Quantitative determination of the non-entrapped chlorothiazide in the presence of liposomes using differential pulse polarography

Differential Pulse Polarography (DPP) was used for the quantitative determination of the free and adsorbed (non-entrapped) chlorothiazide (CHT) in the presence of liposomes. It was found that CHT polarographic signal depends both on the concentration of multilamelar (MLV) liposomes, due to its adsorption on the liposomal surface, and on their size. Calibration plots of CHT concentration versus current density, at pH 7.4, in the presence of different liposomes concentrations were constructed. Based on these curves the non-entrapped chlorothiazide was determined. Results were compared to those obtained from the application of conventional procedure i.e. chromatographic separation of CHT from liposomes followed by UV spectrophotometric determination. Both techniques were found to be comparable with respect to their accuracy, with a relative error of 0.47%. Determination of the drug using DPP was faster.     

Reversible adsorption change of 2‐amino‐4,5‐imidazoledicarbonitrile on Ag electrode surfaces by potential‐dependent surface‐enhanced Raman scattering

The potential‐induced adsorption change of 2‐amino‐4,5‐imidazoledicarbonitrile (AIDCN) on Ag electrode surfaces has been examined by surface‐enhanced Raman scattering (SERS) in an applied potential range between ?1.0 and 0.2 V. Upon adsorption, AIDCN has a substantial interaction with the Ag metal surfaces via its two nitrile groups. The CN stretching peaks at ～2200 cm^?1 appeared to be more intensified and redshifted at a negative potential. The deconvolution peak analysis of the CN bands at various voltages suggests that there should be a change in binding modes of AIDCN on Ag surfaces. This potential‐dependent orientation change appeared to be reversible. The density functional theory (DFT) calculation of AIDCN on Ag cluster atoms is used to explain its potential‐dependent adsorption. Copyright © 2010 John Wiley & Sons, Ltd.     

Integrated pulsed amperometry for the analysis of organic compounds

Integrated pulsed amperometric detection (IPAD) was applied for the detection of organic compounds for flow injection analysis. The pulse waveform used in the integrated pulsed amperometry consisted of three steps: detection potential, oxidation potential, and adsorption potential. The pulse waveform was applied to the working electrode as the analyte flowed through the electrochemical cell. Unlike ordinary pulsed amperometry, a faradaic current was integrated over the duration period of the detection potential in the IPAD. Therefore, the total charge was measured by integrating the current after the detection potential was applied. The current for the initial 10 ms, after applying the detection potential, was excluded from the integration due to a large charging current at the initial period. Compared with pulsed amperometry, integrated pulsed amperometry provides a better signal-to-noise ratio and a lower detection limit. This method was applied to the quantitative analysis of thiourea as a representative analyte of organosulfur compounds in a flow injection analysis.     

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.     

Multivariate curve resolution applied to the simultaneous analysis of electrochemical and spectroscopic data: study of the Cd(II)/glutathione-fragment system by voltammetry and circular dichroism spectroscopy

Multivariate curve resolution with alternating least squares (MCR-ALS) is applied for the first time to the simultaneous analysis of electrochemical and spectroscopic data. Then, a data analysis is done with augmented matrices constituted by Differential Pulse Polarography and Circular Dichroism data submatrices. The use of proper, and different for each submatrix, constrains in the iterative ALS optimization allows to obtain chemically meaningful results constituted by a common matrix containing the concentration profiles, and two matrices with the pure electrochemical and spectroscopic signals. MCR-ALS is applied to the study of the complexation of Cd by Cys-Gly, a glutathione-fragment of great interest for understanding metal-phytochelatins complexation.     

Co‐adsorption of Cations as the Cause of the Apparent pH Dependence of Hydrogen Adsorption on a Stepped Platinum Single‐Crystal Electrode

The successful deployment of advanced energy‐conversion systems depends critically on our understanding of the fundamental interactions of the key adsorbed intermediates (hydrogen *H and hydroxyl *OH) at electrified metal–aqueous electrolyte interfaces. The effect of alkali metal cations (Li⁺, Na⁺, K⁺, Cs⁺) on the non‐Nernstian pH shift of the step‐related voltammetric peak of the Pt(553) electrode is investigated over a wide pH window (1 to 13) by means of experimental and computational methods. The co‐adsorbed alkali cations along the step weaken the OH adsorption at the step sites, causing a positive shift of the potential of the step‐related peak on Pt(553). Density functional calculations explain the observations on the identity and concentration of alkali cations on the non‐Nernstian pH shift, and demonstrate that cation–hydroxyl co‐adsorption causes the apparent pH dependence of “hydrogen” adsorption in the step sites of platinum electrodes.     

Polarography��past, present, and future

Polarography was first developed as an automated method of voltage-controlled electrolysis with dropping mercury electrode. The spontaneously renewed pure electrode surface provided reproducible electrochemical results which enabled scientists to work out adequate theory and rich analytical applications. The original method was then instrumentally modified in various ways. Later, hanging mercury drop was added as an alternative indicator electrode??in this way, polarography turned formally into voltammetry with mercury drop electrodes. Beside, in potential-controlled electrolysis, the mercury drop electrodes have been also used in current-controlled electrolysis (chronopotentiometry)??there, it has provided new experimental effects. Polarography has thus gradually covered a wide field of electrolytic methods based on the use of mercury electrodes, in which it continues developing.     

Photoelectrochemical H2 Evolution with a Hydrogenase Immobilized on a TiO2‐Protected Silicon Electrode

The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron‐transfer processes at highly active and well‐defined catalytic sites on a light‐harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO₂‐coated p‐Si photocathode for the photo‐reduction of protons to H₂. The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO₂ layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p‐Si|TiO₂|hydrogenase photocathode displays visible‐light driven production of H₂ at an energy‐storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p‐type semiconductor photocathode through the engineering of the enzyme–materials interface.