Working electrode

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In electrochemistry, the working electrode is the electrode in an electrochemical system on which the reaction of interest is occurring. [1] [2] [3] The working electrode is often used in conjunction with an auxiliary electrode, and a reference electrode in a three-electrode system. Depending on whether the reaction on the electrode is a reduction or an oxidation, the working electrode is called cathodic or anodic, respectively. Common working electrodes can consist of materials ranging from inert metals such as gold or platinum, to inert carbon such as glassy carbon, boron-doped diamond [4] or pyrolytic carbon, and mercury drop and film electrodes. [5] Chemically modified electrodes are employed for the analysis of both organic and inorganic samples.

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<span class="mw-page-title-main">Conductive polymer</span> Organic polymers that conduct electricity

Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The main advantage of conductive polymers is that they are easy to process, mainly by dispersion. Conductive polymers are generally not thermoplastics, i.e., they are not thermoformable. But, like insulating polymers, they are organic materials. They can offer high electrical conductivity but do not show similar mechanical properties to other commercially available polymers. The electrical properties can be fine-tuned using the methods of organic synthesis and by advanced dispersion techniques.

<span class="mw-page-title-main">Cyclic voltammetry</span> Method of analyzing electrochemical reactions

In electrochemistry, cyclic voltammetry (CV) is a type of potentiodynamic measurement. In a cyclic voltammetry experiment, the working electrode potential is ramped linearly versus time. Unlike in linear sweep voltammetry, after the set potential is reached in a CV experiment, the working electrode's potential is ramped in the opposite direction to return to the initial potential. These cycles of ramps in potential may be repeated as many times as needed. The current at the working electrode is plotted versus the applied voltage to give the cyclic voltammogram trace. Cyclic voltammetry is generally used to study the electrochemical properties of an analyte in solution or of a molecule that is adsorbed onto the electrode.

<span class="mw-page-title-main">Reference electrode</span> Electrode with a stable and accurate electrode potential

A reference electrode is an electrode that has a stable and well-known electrode potential. The overall chemical reaction taking place in a cell is made up of two independent half-reactions, which describe chemical changes at the two electrodes. To focus on the reaction at the working electrode, the reference electrode is standardized with constant concentrations of each participant of the redox reaction.

<span class="mw-page-title-main">Glassy carbon</span> Allotrope of carbon

Glass-like carbon, often called glassy carbon or vitreous carbon, is a non-graphitizing, or nongraphitizable, carbon which combines glassy and ceramic properties with those of graphite. The most important properties are high thermal stability, high thermal conductivity, hardness (7 Mohs), low density, low electrical resistance, low friction, extreme resistance to chemical attack, and impermeability to gases and liquids. Glassy carbon is widely used as an electrode material in electrochemistry, for high-temperature crucibles, and as a component of some prosthetic devices. It can be fabricated in different shapes, sizes and sections.

<span class="mw-page-title-main">Voltammetry</span> Method of analyzing electrochemical reactions

Voltammetry is a category of electroanalytical methods used in analytical chemistry and various industrial processes. In voltammetry, information about an analyte is obtained by measuring the current as the potential is varied. The analytical data for a voltammetric experiment comes in the form of a voltammogram, which plots the current produced by the analyte versus the potential of the working electrode.

<span class="mw-page-title-main">Chronoamperometry</span> Analytical method in electrochemistry

In electrochemistry, chronoamperometry is an analytical technique in which the electric potential of the working electrode is stepped and the resulting current from faradaic processes occurring at the electrode is monitored as a function of time. The functional relationship between current response and time is measured after applying single or double potential step to the working electrode of the electrochemical system. Limited information about the identity of the electrolyzed species can be obtained from the ratio of the peak oxidation current versus the peak reduction current. However, as with all pulsed techniques, chronoamperometry generates high charging currents, which decay exponentially with time as any RC circuit. The Faradaic current - which is due to electron transfer events and is most often the current component of interest - decays as described in the Cottrell equation. In most electrochemical cells, this decay is much slower than the charging decay-cells with no supporting electrolyte are notable exceptions. Most commonly a three-electrode system is used. Since the current is integrated over relatively longer time intervals, chronoamperometry gives a better signal-to-noise ratio in comparison to other amperometric techniques.

<span class="mw-page-title-main">Polarography</span> Method of chemical analysis

Polarography is a type of voltammetry where the working electrode is a dropping mercury electrode (DME) or a static mercury drop electrode (SMDE), which are useful for their wide cathodic ranges and renewable surfaces. It was invented in 1922 by Czechoslovak chemist Jaroslav Heyrovský, for which he won the Nobel prize in 1959. The main advantages of mercury as electrode material are as follows: 1) a large voltage window: ca. from +0.2 V to -1.8 V vs reversible hydrogen electrode (RHE). Hg electrode is particularly well-suited for studying electroreduction reactions. 2) very reproducible electrode surface, since mercury is liquid. 3) very easy cleaning of the electrode surface by making a new drop of mercury from a large Hg pool connected by a glass capillary.

In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically-determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density is achieved.

In electrochemistry, electrosynthesis is the synthesis of chemical compounds in an electrochemical cell. Compared to ordinary redox reactions, electrosynthesis sometimes offers improved selectivity and yields. Electrosynthesis is actively studied as a science and also has industrial applications. Electrooxidation has potential for wastewater treatment as well.

Electroanalytical methods are a class of techniques in analytical chemistry which study an analyte by measuring the potential (volts) and/or current (amperes) in an electrochemical cell containing the analyte. These methods can be broken down into several categories depending on which aspects of the cell are controlled and which are measured. The four main categories are potentiometry, amperometry, coulometry, and voltammetry.

In electrochemistry, the auxiliary electrode, often also called the counter electrode, is an electrode used in a three-electrode electrochemical cell for voltammetric analysis or other reactions in which an electric current is expected to flow. The auxiliary electrode is distinct from the reference electrode, which establishes the electrical potential against which other potentials may be measured, and the working electrode, at which the cell reaction takes place.

In analytical chemistry, a rotating disk electrode (RDE) is a working electrode used in three-electrode systems for hydrodynamic voltammetry. The electrode rotates during experiments, inducing a flux of analyte to the electrode. These working electrodes are used in electrochemical studies when investigating reaction mechanisms related to redox chemistry, among other chemical phenomena. The more complex rotating ring-disk electrode can be used as a rotating disk electrode if the ring is left inactive during the experiment.

An ultramicroelectrode (UME) is a working electrode used in a voltammetry. The small size of UME give them large diffusion layers and small overall currents. These features allow UME to achieve useful steady-state conditions and very high scan rates (V/s) with limited distortion. UME were developed independently by Wightman and Fleischmann around 1980. Small current at UME enables electrochemical measurements in low conductive media, where voltage drop associated with high solution resistance makes these experiments difficult for conventional electrodes. Furthermore, small voltage drop at UME leads to a very small voltage distortion at the electrode-solution interface which allows using two-electrode setup in voltammetric experiment instead of conventional three-electrode setup.

<span class="mw-page-title-main">Marchywka effect</span>

The Marchywka effect refers to electrochemical cleaning of diamond using an electric field induced with remote electrodes.

<span class="mw-page-title-main">Electrocatalyst</span> Catalyst participating in electrochemical reactions

An electrocatalyst is a catalyst that participates in electrochemical reactions. Electrocatalysts are a specific form of catalysts that function at electrode surfaces or, most commonly, may be the electrode surface itself. An electrocatalyst can be heterogeneous such as a platinized electrode. Homogeneous electrocatalysts, which are soluble, assist in transferring electrons between the electrode and reactants, and/or facilitate an intermediate chemical transformation described by an overall half reaction. Major challenges in electrocatalysts focus on fuel cells.

Electrochemical engineering is the branch of chemical engineering dealing with the technological applications of electrochemical phenomena, such as electrosynthesis of chemicals, electrowinning and refining of metals, flow batteries and fuel cells, surface modification by electrodeposition, electrochemical separations and corrosion.

A liquid metal electrode is an electrode that uses a liquid metal, such as mercury, Galinstan, and NaK. They can be used in electrocapillarity, voltammetry, and impedance measurements.

<span class="mw-page-title-main">Electrochemical stripping analysis</span> Method of chemical analysis

Electrochemical stripping analysis is a set of analytical chemistry methods based on voltammetry or potentiometry that are used for quantitative determination of ions in solution. Stripping voltammetry have been employed for analysis of organic molecules as well as metal ions. Carbon paste, glassy carbon paste, and glassy carbon electrodes when modified are termed as chemically modified electrodes and have been employed for the analysis of organic and inorganic compounds.

Electro-oxidation(EO or EOx), also known as anodic oxidation or electrochemical oxidation (EC), is a technique used for wastewater treatment, mainly for industrial effluents, and is a type of advanced oxidation process (AOP). The most general layout comprises two electrodes, operating as anode and cathode, connected to a power source. When an energy input and sufficient supporting electrolyte are provided to the system, strong oxidizing species are formed, which interact with the contaminants and degrade them. The refractory compounds are thus converted into reaction intermediates and, ultimately, into water and CO2 by complete mineralization.

<span class="mw-page-title-main">Spectroelectrochemistry</span>

Spectroelectrochemistry (SEC) is a set of multi-response analytical techniques in which complementary chemical information is obtained in a single experiment. Spectroelectrochemistry provides a whole vision of the phenomena that take place in the electrode process. The first spectroelectrochemical experiment was carried out by Theodore Kuwana, PhD, in 1964.

References

  1. Kissinger, Peter; William R. Heineman (1996-01-23). Laboratory Techniques in Electroanalytical Chemistry, Second Edition, Revised and Expanded (2 ed.). CRC. ISBN   978-0-8247-9445-3.
  2. Bard, Allen J.; Larry R. Faulkner (2000-12-18). Electrochemical Methods: Fundamentals and Applications (2 ed.). Wiley. ISBN   978-0-471-04372-0.
  3. Zoski, Cynthia G. (2007). Handbook of Electrochemistry. Amsterdam: Elsevier. ISBN   978-0-444-51958-0.
  4. Irkham; Watanabe, T.; Fiorani, A.; Valenti, G.; Paolucci, F.; Einaga, Y. (2016). "Co-reactant-on-Demand ECL: Electrogenerated Chemiluminescence by the in Situ Production of S2O82− at Boron-Doped Diamond Electrodes". Faraday Discuss. 138 (48): 15636–15641. doi:10.1021/jacs.6b09020. hdl: 11585/591484 . PMID   27934028.
  5. Heard, D. M.; Lennox, A.J.J. (2020-07-06). "Electrode Materials in Modern Organic Electrochemistry". Angewandte Chemie International Edition. 59 (43): 18866–18884. doi: 10.1002/anie.202005745 . PMC   7589451 . PMID   32633073.