Plasma electrochemistry: potential measured at boron doped diamond and platinum in gaseous electrolyte

Premixed hydrogen/oxygen flame doped with ionisable alkali metals was considered as a dilute electrolyte. Two identical premixed flames which were in physical contact, served as a two compartment flame electrolyte cell. Five different electrochemical cells were studied, each containing a different combination of three alkali metals, Li, K and Cs. Pairs of boron doped diamond (BDD) and platinum electrodes were used to measure the overall zero current cell potential. The total potential measured across the cell was shown to be the sum of the mixed potential, dependent on the identity of ionised species present in the flame, and the diffusion potential originating at the junction between the two flames. Classical kinetic molecular theory and electrochemical theory of mixed potentials have been applied to account for the potential difference measured across these gas phase electrochemical cells. The relative merits of both models are discussed in the context of the experimental results obtained.     

Dynamic electrochemistry in flame plasma electrolyte

Chemistry in flames: Dynamic electrochemistry in the gas phase is described by considering the ionized medium of a flame as an electrolyte (see picture). This study opens up the possibility of accessing redox reactions that are outside the potential limits set by the solvent in conventional liquid-phase electrochemistry.     

Electrochemistry in solids prepared by sol-gel processes

Sol-gel chemistry provides a route to preparing inorganic polymers with ionically conducting properties by room temperature synthetic routes. The products, which are rigid solids, are well-suited as media for conventional electrochemical techniques such as cyclic voltammetry. This property, when combined with their ability to host a wide variety of species, has allowed development of a variety of devices of interest in electrochemistry and analytical chemistry. Examples include cathodes for fuels cells, electrochromic devices, biosensors, and amperometric sensors for analytes in the gas phase. In this review, the emphasis will be on reported applications to analytical chemistry; however, studies on the general properties of these materials and on their use in electrochemical science also will be summarized because they may provide the basis for further development of sensors.     

Electron-transfer reactions at the plasma-liquid interface

Electrochemical reactions are normally initiated in solution by metal electrodes such as Pt, which are expensive and limited in supply. In this Communication, we demonstrate that an atmospheric-pressure microplasma can act as a gaseous, metal-free electrode to mediate electron-transfer reactions in aqueous solutions. Ferricyanide is reduced to ferrocyanide by plasma electrons, and the reduction rate is found to depend on discharge current. The ability to initiate and control electrochemical reactions at the plasma-liquid interface opens a new direction for electrochemistry based on interactions between gas-phase electrons and ionic solutions.     

Electrochemical investigation of redox thermodynamics of immobilized myoglobin: ionic and ligation effects

In this study, we investigated redox thermodynamics of myoglobin as well as the ionic (phosphate ions) and ligation (imidazole) effects via a dynamic electrochemical approach. We employed a previously established system that features nonmediated, direct electrochemistry of myoglobin and myoglobin in an immobilized state (i.e., diffusionless electrochemistry). Thermodynamics parameters were obtained by measuring redox potential (E degrees ') of myoglobin at varied temperature (T), in the presence and in the absence of specific ions or axial ligands. As a step further, we evaluated contributions from allosteric effect and axial iron ligation by partitioning E degrees ' changes into entropic and enthalpic terms. Compensation phenomena between the entropic and enthalpic changes were observed in all these cases. On the basis of these studies, we also correlated these phenomena to possible structural variations.     

Electrochemical diffusion potential in the gas phase

Potentiometric based electrochemical measurement of diffusion potential at a junction between two flowing flame plasma gases is described. A flame electrochemical cell was constructed using a specially designed burner, which supports two individual flames, each fed by separate premixed methane/oxygen/nitrogen streams. The two flames were in intimate contact, creating a flowing fluid gaseous junction. By aspirating metal salt solutions into these premixed feed gases, the concentration gradient at the interface between the two flames may be controlled. A measurable electrochemical diffusion potential was formed at this junction, the magnitude of which was dependent on the concentration ratio of charged species with different mobilities. In our flame electrolyte, the dominant charged species were atomic or molecular cations and electrons, which have a difference in mobilities of approximately three orders of magnitude. A two-electrode system, in conjunction with a high impedance electrometer was used to measure the potential difference across the flame electrochemical cell. The measured potential difference was analysed using theory developed for the liquid junction potentials by the Henderson equation.     

Plasma electrochemistry: electroreduction in a flame

The manipulation of electron transfer reactions at surfaces forms the cornerstone of electrodeposition and processing of materials on substrates with precise control of stoichiometry and oxidation state. However, the utility of this technique, which is mainly carried out in liquid electrolytes, is ultimately limited by the electrolysis of the solvent which limits a potential window to at best 4.8 V in nonaqueous solutions (A. J. Bard and L. R. Faulkner, Electrochemical Methods: Fundamentals and Applications, Wiley, New York, NY, 2nd edn, 2001; ref. 1) and can be up to 6 V in ionic liquids (A. P. Abbott, K. J. McKenzie, Phys. Chem. Chem. Phys., 2006, 8, 4265-4279; ref. 2). A long-sought-after goal has been to develop a corresponding technique at the solid/gas interface in the absence of a solvent which will allow in principle a potential window in excess of 100 V (J. M. Goodings, J. Guo, A. N. Hayhurst and S. G. Taylor, Int. J. Mass Spectrom., 2001, 206, 137-151; ref. 3). This extended potential window will enable chemistry at the solid/gas interface that is not possible at the solid/liquid interface. Here we describe a new approach to gas-phase electrochemistry using a flame plasma as the electrolyte medium. We demonstrate the controlled electrochemical reduction of Cu(+) to Cu(0) at an electrode surface in a flame environment with resulting deposition of either Cu(2)O or Cu species on conducting diamond electrodes. This approach is novel in that it involves the application of an electrochemical potential difference to change the redox state of surface confined species, not the measurement of flame bore ions (as in flame ionisation detectors). This new technique will permit deposition of films and particles on surfaces with control over the oxidation state of the species. This will provide a valuable enhancement to the capabilities of materials preparation methods such as flame spray deposition.     

Ash removal from viscous media by supercritical gas extraction

The separation of solid μ-sized particles from viscous media sometimes raises difficulties because sedimentation is too slow, so that use of a centrifuge is required. In the centrifuge, however, the particles may act as an abrasive material. Examples are finely dispersed solid ingredients in shale oil, in oils from tar sand, in hydrogenation process (slurries) suspensions etc.

The media containing the finely dispersed particles are processed with a compressed gas at high density using an entrainer. The conditions are chosen so that the ternary (or pseudoternary) system composed of supercritical gas, entrainer and viscous substance (or mixture) is supercritical. In this way, high concentration of the viscous medium are obtained in the gas phase. As the viscosity of the supercritical gas phase is relatively low, the density of the gas phase can be adjusted by variation of pressure and temperature so that the difference between the solid and the gas phase is sufficiently high for rapid separation of the solid particles. The velocity of sedimentation at constant temperature and pressure depends on the concentration of the viscous substance in the gaseous phase. Even at concentrations of the viscous medium in the gaseous phase, of 30 to 35 % in weight the velocity of sedimentation is sufficiently rapid for the process to be of economical interest.     

Atomization efficiencies in halocarbon-loaded acetylene-air flames—I. Monochlorides of readily volatilized elements

Carbon tetrachloride vapour was introduced with a carrier air stream into the mixing chamber of an acetylene-air flame while nebulizing aqueous solutions of several metal salts. The atomic absorption signal was measured under increasing flow rate of the halocarbon vapour at constant fuel-to-oxidant ratio, and the latter parameter was also varied in separate experiments. By applying the theory developed by Sugden and Bulewicz, the exclusive formation of monochlorides in the gaseous phase (presented here, in Part I) and the additional formation of hydroxychlorides and dichlorides (presented in Part II) could be elucidated. From the decrease of the signal measured for the alkali elements of known monochloride dissociation constants and dissociation energies, the temperature and the chlorine concentration present in the observed flame zone could be calculated. It is inferred that only 19% of the total halogen introduced is converted to HCl and Cl species in a slightly fuel-rich flame. The signal depression is stronger in a fuel-lean flame of higher monoatomic chlorine concentration for those elements which have a relatively efficient atomization under these flame conditions. An increase of the electron concentration resulting from the introduction of the halocarbon in an alkali-containing flame was deduced from the experimental findings, in agreement with earlier observations.     

Electrochemistry of nanobubbles

Gas bubble formation is a common phenomenon in numerous electrochemical processes, such as water splitting, chloralkaline process, and fuel cells. Many efforts have been made to understand the behaviors of microsized or larger gas bubbles in electrochemical systems in the past few decades. It was not until recent years that the electrochemistry of nanosized gas bubbles (nanobubbles) has begun receiving attention. In this short review, we summarize recent advances in the field of electrochemistry of nanobubbles, ranging from new fundamental understandings of nanobubble behaviors to the development of novel bubble-based applications inspired by the basic research of nanobubble electrochemistry.     

Electrostatic and electrochemical nature of liquid-gated electric-double-layer transistors based on oxide semiconductors

The electric-double-layer (EDL) formed at liquid/solid interfaces provides a broad and interdisciplinary attraction in terms of electrochemistry, photochemistry, catalysts, energy storage, and electronics because of the large interfacial capacitance coupling and its ability for high-density charge accumulation. Much effort has recently been devoted to the fundamental understanding and practical applications of such highly charged EDL interfaces. However, the intrinsic nature of the EDL charging, whether it is electrostatics or electrochemistry, and how to distinguish them are far from clear. Here, by combining electrical transport measurements with electrochemical impedance spectroscopy (EIS), we studied the charging mechanisms of highly charged EDL interfaces between an ionic liquid and oxide semiconductor, ZnO. The direct measure for mobile carriers from the Hall effect agreed well with that from the capacitance-voltage integration at 1 Hz, implying that the pseudocapacitance does not contribute to carrier transport at EDL interfaces. The temperature-frequency mapping of EIS was further demonstrated as a "phase diagram" to distinguish the electrostatic or electrochemical nature of such highly charged EDL interfaces with densities of up to 8 × 10(14) cm(-2), providing a guideline for electric-field-induced electronic phenomena and a simple method for distinguishing electrostatic and electrochemical charging in EDLTs not only based on a specific oxide semiconductor, ZnO, but also commonly applicable to all types of EDL interfaces with extremely high-density carrier accumulation.     

Bubbles pinned on electrodes: Friends or foes of aqueous electrochemistry?

Electrochemists and engineers regard adherent gas bubbles as redox-inactive and therefore blocking entities. Adhesion of bubbles at electrodes generally carries an energy penalty. But this is not always the case: bubbles pinned on an electrode surface initiate the oxidation of water-soluble species under conditions where such reactions would normally be considered impossible. Here we critically review the recent literature that is beginning to unveil the novel concept of on-water electrochemistry. Harnessing electrochemical reactivity of the water–gas–electrode interface has the potential to become a game-changer in organic electrosynthesis, accelerating the transition toward a sustainable chemical industry by simplifying the direct integration of renewable electricity into the production of commodity chemicals.     

电化学基础研究的进展电化学高级研讨班讲座

电化学基础研究的进展电化学高级研讨班讲座田昭武,苏文煅（固体表面物理化学国家重点实验室,厦门大学化学系,厦门,３６１００５）电化学是研究电子导体（或半导体材料）／离子导体（通常为电解质溶液）和离子导体／离子导体的界面结构、界面现象及其变化过程与机理的...     

The Protoelectric Potential Map (PPM): An Absolute Two‐Dimensional Chemical Potential Scale for a Global Understanding of Chemistry

We introduce the protoelectric potential map (PPM) as a novel, two‐dimensional plot of the absolute reduction potential (pe_abs scale) combined with the absolute protochemical potential (Brønsted acidity: pH_abs scale). The validity of this thermodynamically derived PPM is solvent‐independent due to the scale zero points, which were chosen as the ideal electron gas and the ideal proton gas at standard conditions. To tie a chemical environment to these reference states, the standard Gibbs energies for the transfer of the gaseous electrons/protons to the medium are needed as anchor points. Thereby, the thermodynamics of any redox, acid–base or combined system in any medium can be related to any other, resulting in a predictability of reactions even over different media or phase boundaries. Instruction is given on how to construct the PPM from the anchor points derived and tabulated with this work. Since efforts to establish “absolute” reduction potential scales and also “absolute” pH scales already exist, a short review in this field is given and brought into relation to the PPM. Some comments on the electrochemical validation and realization conclude this concept article.     

Electrochemical potentials from first principles

The electrochemical potential is the fundamental parameter in the theory of electrochemistry. Not only does it determine the position of electrochemical equilibria but also it acts as the driving force for electron transfer reactions, diffusion-migration phenomena, and phase transformations of all kinds. In the present work, the electrochemical potential is defined as the total work done in transferring a single particle of a substance from a universal reference state to a specified location, at constant temperature and pressure. It is the sum of two scalar fields: the electrostatic potential energy and the chemical potential energy. The electrochemical potential is widely underutilized within the fields of solid-state science and electrochemical engineering. For historical reasons, many authors prefer to analyze driving forces in terms of electrode potentials, concentration gradients, or Gibbs free energies. In this paper, the author provides a short introduction to the electrochemical potential and then shows how some of the major branches of electrochemistry can benefit from using it. Topics examined include the Volta potential difference, the membrane potential difference, the scanning Kelvin probe microscope, the electromotive force, the proton motive force, and the activation of electron transfer.

     

Heterogeneous electrocatalysis: a core field of interfacial science

Heterogeneous electrocatalysis involves chemical reactions occurring in an electrochemical cell at the surface of an electrode, that is, at the electrochemical interface. The reaction rates are set by electrode surface structure, electrode potential, and can be adjusted by other variables specific to the field of electrochemistry. In contrast to reactions occurring at the solid/gas interface, electron transfer usually takes place at the electrochemical interface, which may lead to new product formation (in catalytic electrosynthesis), or allows one to harvest electrons in fuel cells. In the Opinion, papers describing catalytic materials used in a proton exchange membrane fuel cell are highlighted, and those related to recently developed research methodology of heterogeneous electrocatalysis receive a particular emphasis. Conclusions are made as to the future development of the field.     

Membrane electrochemistry

Electrochemistry and biomembranes are interface science in that both are concerned with the phenomena at, as well as across, the interfaces. Membrane electrochemistry may be defined as the application of electrochemistry to biomembrane studies. Additionally, transport processes within the membrane are involved in biomembranes. Since biomembranes are diverse and are usually not amenable to probing by electrochemicophysical techniques, model membrane systems have been developed for their investigation.

The introduction of experimental bilayer lipid membranes (BLM) technique and its modifications have been instrumental in the development and testing of membrane transport concepts (carriers vs channels) and electronic processes in membranes. Instead merely viewing a biomembrane as a physical barrier containing carriers or channels to carry out ionic processes, an ultrathin lipid or biological membrane can also be considered as a complete ‘electrochemical cell’ with one membrane/solution interface reducing (as a cathode) and the other membrane/solution interface oxidizing (as an anode). It is now possible to understand energy transduction (charge generation, separation, and redox reactions) in terms of ultrathin lipid membranes separating two aqueous solutions.

In this paper, we shall discuss the basic principles of electrochemistry as they are applied to membrane studies. Emphasis will be on experimental bilayer lipid membranes (BLM) which have been extensively investigated as models of biomembranes.     

Influence of phosphorus valency on thermal behaviour of flame retarded polyurethane foams

This paper reports decomposition/pyrolysis studies of polyurethane (PU) rigid foams containing phosphinate, phosphonate or phosphate as flame retardant in order to study the effect of phosphorus oxidation state on their gas and/or solid phase action. The flame retardants analyzed were aluminium phosphinate (IPA), dimethylpropanphosphonate (DMPP), triethylphosphate (TEP) and ammonium polyphosphate (APP), which differ in oxidation state and/or decomposition temperature. Gases evolved during TGA analyses as well as solid residues have been studied by means of MS and FTIR.The results show that phosphorus flame retardants which significantly lose weight at temperatures lower than those of neat PU foams act in the gas phase irrespective of their valency: indeed, they are completely volatilized before polymer decomposition starts and thus no interaction between flame retardant and polymer can be expected. The effect of phosphorus oxidation state becomes important when flame retardant decomposition takes place in the same temperatures range as neat polymer. In this case, it seems that at lower P oxidation state (+1) a combined gas and solid phase action takes place while at higher P oxidation state (+5) only solid phase action was observed.     

Simplified analysis of organic compounds in headspace and aqueous samples by high-capacity sample enrichment probe

A sample enrichment probe (SEP) consisting of a thin rod of an inert material and provided at one end with a short sleeve of polydimethylsilicone rubber was used for the high-capacity sample enrichment of analytes from gaseous and aqueous samples for analysis by gas chromatography (GC) and its hyphenated techniques. The silicone rubber was exposed to the analytical sample, after which the end of the rod carrying the silicone rubber was introduced into the injector and the analytes thermally desorbed and analysed by GC. This technique is similar to, but differs from, solid-phase microextraction (SPME) in that a much larger volume of the sorptive phase is employed, the sorptive phase is not introduced into the inlet of the GC via a needle and the injector is opened to the atmosphere for the introduction and removal of the SEP. In the determination of volatile and semi-volatile organic compounds in gaseous and aqueous media, the SEP technique gave results comparable with those obtained by the stir-bar-sorptive extraction (SBSE) and high-capacity sorption probe (HCSP) techniques. Implementation of the SEP technique requires only minor adaptations to the gas chromatograph and does not require any auxiliary thermal desorption and cryotrapping equipment.     

Gas phase electrochemical detection of single latex particles

In this study we describe zero current potentiometric measurements in a gaseous flame electrolyte, for the detection of single latex particles. Combustion of polystyrene latex particles when added to a premixed hydrogen/oxygen/nitrogen flame, results in an increase in charged species relative to the surrounding hydrogen flame. As a consequence of this increase in ionic concentration over background, short-lived potential difference transients were measured between two platinum indicator electrodes placed in a two-compartment flame electrochemical cell (described in Electrochem. Commun., 2001, 3, 675-681). The frequency of the transient events was dependent on the number density of latex particles in solution. It is proposed that each short-lived transient event corresponds to the combustion of single latex particles in a flame. A potential difference maximum of 0.56 V when 3.0 microm diameter particles were added to the flame was measured. Also it was shown that it is possible to detect 0.3 microm diameter latex particles using the same technique. It is postulated that the physical basis of the potential difference is due to the establishment of diffusion/junction potential due to the increase in ionisation from polystyrene combustion at the surface of one indicator electrode. This methodology may be applied to the detection of particulates composed of ionisable species (organic or inorganic) in gaseous environment such as bacteria, viruses, pollen grains and dust.