Cyclic voltammetry

Cyclic voltammetry (CV) is a type of potentiodynamic electrochemical 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 (that is, the working electrode's potential) to give the cyclic voltammogram trace. Cyclic voltammetry is generally used to study the electrochemical properties of an analyte in solution[1][2][3][4] or of a molecule that is adsorbed onto the electrode.

Figure 1. Typical cyclic voltammogram where and show the peak cathodic and anodic current respectively for a reversible reaction.

Experimental method
Figure 2. Cyclic voltammetry waveform.

In cyclic voltammetry (CV), the electrode potential ramps linearly versus time in cyclical phases (Figure 2). The rate of voltage change over time during each of these phases is known as the experiment's scan rate (V/s). The potential is measured between the working electrode and the reference electrode, while the current is measured between the working electrode and the counter electrode. These data are plotted as current (i) versus applied potential (E, often referred to as just 'potential'). In Figure 2, during the initial forward scan (from t0 to t1) an increasingly reducing potential is applied; thus the cathodic current will, at least initially, increase over this time period assuming that there are reducible analytes in the system. At some point after the reduction potential of the analyte is reached, the cathodic current will decrease as the concentration of reducible analyte is depleted. If the redox couple is reversible then during the reverse scan (from t1 to t2) the reduced analyte will start to be re-oxidized, giving rise to a current of reverse polarity (anodic current) to before. The more reversible the redox couple is, the more similar the oxidation peak will be in shape to the reduction peak. Hence, CV data can provide information about redox potentials and electrochemical reaction rates.

For instance, if the electron transfer at the working electrode surface is fast and the current is limited by the diffusion of analyte species to the electrode surface, then the peak current will be proportional to the square root of the scan rate. This relationship is described by the Randles–Sevcik equation. In this situation, the CV experiment only samples a small portion of the solution, i.e., the diffusion layer at the electrode surface.

Characterization

The utility of cyclic voltammetry is highly dependent on the analyte being studied. The analyte has to be redox active within the potential window to be scanned.

Reversible couples
Potential against time, current against time and voltammogram (current against potential) for a one-electron, reversible redox couple diffusing freely in solution. The current density is normalised by 0.446 F C sqrt(D F nu / R T). Reductive current counted as negative.

Often the analyte displays a reversible CV wave (such as that depicted in Figure 1), which is observed when all of the initial analyte can be recovered after a forward and reverse scan cycle. Although such reversible couples are simpler to analyze, they contain less information than more complex waveforms.

The waveform of even reversible couples is complex owing to the combined effects of polarization and diffusion. The difference between the two peak potentials (Ep), ΔEp, is of particular interest.

ΔEp = Epa - Epc > 0

This difference mainly results from the effects of analyte diffusion rates. In the ideal case of a reversible 1e- couple, ΔEp is 57 mV and the full-width half-max of the forward scan peak is 59 mV. Typical values observed experimentally are greater, often approaching 70 or 80 mV. The waveform is also affected by the rate of electron transfer, usually discussed as the activation barrier for electron transfer. A theoretical description of polarization overpotential is in part described by the Butler–Volmer equation and Cottrell equation equations. In an ideal system the relationships reduces to for an n electron process.[2]

Focusing on current, reversible couples are characterized by ipa/ipc = 1.

When a reversible peak is observed, thermodynamic information in the form of a half cell potential E01/2 can be determined. When waves are semi-reversible (ipa/ipc is close but not equal to 1), it may be possible to determine even more specific information (see electrochemical reaction mechanism).

Nonreversible couples

Many redox processes observed by CV are quasi-reversible or non-reversible. In such cases the thermodynamic potential E01/2 is often deduced by simulation. The irreversibility is indicated by ipa/ipc ≠ 1. Deviations from unity are attributable to a subsequent chemical reaction that is triggered by the electron transfer. Such EC processes can be complex, involving isomerization, dissociation, association, etc.[5][6]

The analyte is adsorbed onto the electrode surface

Adsorbed species give simple voltammetric responses: ideally, at slow scan rates, there is no peak separation, the peak width is 90mV for a one-electron redox couple, and the peak current and peak area are proportional to scan rate (observing that the peak current is proportional to scan rate proves that the redox species that gives the peak is actually immobilised).[1] The effect of increasing the scan rate can be used to measure the rate of interfacial electron transfer and/or the rates of reactions that are coupltransfer. This technique has been useful to study redox proteins, some of which readily adsorb on various electrode materials, but the theory for biological and non-biological redox molecules is the same (see the page about protein film voltammetry).

Experimental setup

CV experiments are conducted on a solution in a cell fitted with electrodes. The solution consists of the solvent, in which is dissolved electrolyte and the species to be studied.[7]

The cell

A standard CV experiment employs a cell fitted with three electrodes: reference electrode, working electrode, and counter electrode. This combination is sometimes referred to as a three-electrode setup. Electrolyte is usually added to the sample solution to ensure sufficient conductivity. The solvent, electrolyte, and material composition of the working electrode will determine the potential range that can be accessed during the experiment.

The electrodes are immobile and sit in unstirred solutions during cyclic voltammetry. This "still" solution method gives rise to cyclic voltammetry's characteristic diffusion-controlled peaks. This method also allows a portion of the analyte to remain after reduction or oxidation so that it may display further redox activity. Stirring the solution between cyclic voltammetry traces is important in order to supply the electrode surface with fresh analyte for each new experiment. The solubility of an analyte can change drastically with its overall charge; as such it is common for reduced or oxidized analyte species to precipitate out onto the electrode. This layering of analyte can insulate the electrode surface, display its own redox activity in subsequent scans, or otherwise alter the electrode surface in a way that affects the CV measurements. For this reason it is often necessary to clean the electrodes between scans.

Common materials for the working electrode include glassy carbon, platinum, and gold. These electrodes are generally encased in a rod of inert insulator with a disk exposed at one end. A regular working electrode has a radius within an order of magnitude of 1 mm. Having a controlled surface area with a well-defined shape is necessary for being able to interpret cyclic voltammetry results.

To run cyclic voltammetry experiments at very high scan rates a regular working electrode is insufficient. High scan rates create peaks with large currents and increased resistances, which result in distortions. Ultramicroelectrodes can be used to minimize the current and resistance.

The counter electrode, also known as the auxiliary or second electrode, can be any material that conducts current easily, will not react with the bulk solution, and has a surface area much larger than the working electrode. Common choices are platinum and graphite. Reactions occurring at the counter electrode surface are unimportant as long as it continues to conduct current well. To maintain the observed current the counter electrode will often oxidize or reduce the solvent or bulk electrolyte.

Solvents

CV can be conducted using a variety of solutions. Solvent choice for cyclic voltammetry takes into account several requirements.[4] The solvent must dissolve the analyte and high concentrations of the supporting electrolyte. It must also be stable in the potential window of the experiment with respect to the working electrode. It must not react with either the analyte or the supporting electrolyte. It must be pure to prevent interference.

Electrolyte

The electrolyte ensures good electrical conductivity and minimizes iR drop such that the recorded potentials correspond to actual potentials. For aqueous solutions, many electrolytes are available, but typical ones are alkali metal salts of perchlorate and nitrate. In nonaqueous solvents, the range of electrolytes is more limited, and a popular choice is tetrabutylammonium hexafluorophosphate.[8]

Potentiodynamic techniques also exist that add low-amplitude AC perturbations to a potential ramp and measure variable response in a single frequency (AC voltammetry) or in many frequencies simultaneously (potentiodynamic electrochemical impedance spectroscopy).[9] The response in alternating current is two-dimensional, characterized by both amplitude and phase. These data can be analyzed to determine information about different chemical processes (charge transfer, diffusion, double layer charging, etc.). Frequency response analysis enables simultaneous monitoring of the various processes that contribute to the potentiodynamic AC response of an electrochemical system.

Whereas cyclic voltammetry is not hydrodynamic voltammetry, useful electrochemical methods are. In such cases, flow is achieved at the electrode surface by stirring the solution, pumping the solution, or rotating the electrode as is the case with rotating disk electrodes and rotating ring-disk electrodes. Such techniques target steady state conditions and produce waveforms that appear the same when scanned in either the positive or negative directions, thus limiting them to linear sweep voltammetry.

Applications

Cyclic voltammetry (CV) has become an important and widely used electroanalytical technique in many areas of chemistry. It is often used to study a variety of redox processes, to determine the stability of reaction products, the presence of intermediates in redox reactions,[10] electron transfer kinetics,[11] and the reversibility of a reaction.[12] CV can also be used to determine the electron stoichiometry of a system, the diffusion coefficient of an analyte, and the formal reduction potential of an analyte, which can be used as an identification tool. In addition, because concentration is proportional to current in a reversible, Nernstian system, the concentration of an unknown solution can be determined by generating a calibration curve of current vs. concentration.[13]

In cellular biology it is used to measure the concentrations in living organisms.[14] In organometallic chemistry, it is used to evaluate redox mechanisms.[15]

Measuring antioxidant capacity

Cyclical voltammetry can be used to determine the antioxidant capacity in food and even skin.[16][17] Low molecular weight antioxidants, molecules that prevent other molecules from being oxidized by acting as reducing agents, are important in living cells because they inhibit cell damage or death caused by oxidation reactions that produce radicals.[18] Examples of antioxidants include flavonoids, whose antioxidant activity is greatly increased with more hydroxyl groups.[19] Because traditional methods to determine antioxidant capacity involve tedious steps, techniques to increase the rate of the experiment are continually being researched. One such technique involves cyclic voltammetry because it can measure the antioxidant capacity by quickly measuring the redox behavior over a complex system without the need to measure each component's antioxidant capacity.[20][21] Furthermore, antioxidants are quickly oxidized at inert electrodes, so the half-wave potential can be utilized to determine antioxidant capacity.[22] It is important to note that whenever cyclic voltammetry is utilized, it is usually compared to spectrophotometry or high-performance liquid chromatography (HPLC).[23] Applications of the technique extend to food chemistry, where it is used to determine the antioxidant activity of red wine, chocolate, and hops. Additionally, it even has uses in the world of medicine in that it can determine antioxidants in the skin.

Evaluation of a technique

The technique being evaluated uses voltammetric sensors combined in an electronic tongue (ET) to observe the antioxidant capacity in red wines. These electronic tongues (ETs) consist of multiple sensing units like voltammetric sensors, which will have unique responses to certain compounds. This approach is optimal to use since samples of high complexity can be analyzed with high cross-selectivity. Thus, the sensors can be sensitive to pH and antioxidants. As usual, the voltage in the cell was monitored using a working electrode and a reference electrode (silver/silver chloride electrode).[24] Furthermore, a platinum counter electrode allows the current to continue to flow during the experiment. The Carbon Paste Electrodes sensor (CPE) and the Graphite-Epoxy Composite (GEC) electrode are tested in a saline solution before the scanning of the wine so that a reference signal can be obtained. The wines are then ready to be scanned, once with CPE and once with GEC. While cyclic voltammetry was successfully used to generate currents using the wine samples, the signals were complex and needed an additional extraction stage.[24] It was found that the ET method could successfully analyze wine's antioxidant capacity as it agreed with traditional methods like TEAC, Folin-Ciocalteu, and I280 indexes.[24] Additionally, the time was reduced, the sample did not have to be pretreated, and other reagents were unnecessary, all of which diminished the popularity of traditional methods.[25] Thus, cyclic voltammetry successfully determines the antioxidant capacity and even improves previous results.

Antioxidant capacity of chocolate and hops

The phenolic antioxidants for cocoa powder, dark chocolate, and milk chocolate can also be determined via cyclic voltammetry. In order to achieve this, the anodic peaks are calculated and analyzed with the knowledge that the first and third anodic peaks can be assigned to the first and second oxidation of flavonoids, while the second anodic peak represents phenolic acids.[21] Using the graph produced by cyclic voltammetry, the total phenolic and flavonoid content can be deduced in each of the three samples. It was observed that cocoa powder and dark chocolate had the highest antioxidant capacity since they had high total phenolic and flavonoid content.[21] Milk chocolate had the lowest capacity as it had the lowest phenolic and flavonoid content.[21] While the antioxidant content was given using the cyclic voltammetry anodic peaks, HPLC must then be used to determine the purity of catechins and procyanidin in cocoa powder, dark chocolate, and milk chocolate.

Hops, the flowers used in making beer, contain antioxidant properties due to the presence of flavonoids and other polyphenolic compounds.[22] In this cyclic voltammetry experiment, the working electrode voltage was determined using a ferricinium/ferrocene reference electrode. By comparing different hop extract samples, it was observed that the sample containing polyphenols that were oxidized at less positive potentials proved to have better antioxidant capacity.[22]

See also

References
  1. Bard, Allen J.; Larry R. Faulkner (2000-12-18). Electrochemical Methods: Fundamentals and Applications (2 ed.). Wiley. ISBN 978-0-471-04372-0.
  2. Nicholson, R. S.; Irving. Shain (1964-04-01). "Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems". Analytical Chemistry. 36 (4): 706–723. doi:10.1021/ac60210a007.
  3. Heinze, Jurgen (1984). "Cyclic Voltammetry-"Electrochemical Spectroscopy". New Analytical Methods (25)". Angewandte Chemie International Edition in English. 23 (11): 831–847. doi:10.1002/anie.198408313.
  4. Elgrishi, Noémie; Rountree, Kelley J.; McCarthy, Brian D.; Rountree, Eric S.; Eisenhart, Thomas T.; Dempsey, Jillian L. (3 November 2017). "A Practical Beginner's Guide to Cyclic Voltammetry". Journal of Chemical Education. 95 (2): 197. Bibcode:2018JChEd..95..197E. doi:10.1021/acs.jchemed.7b00361.
  5. http://www.currentseparations.com/issues/18-1/cs18-1b.pdf
  6. Savéant, Jean-Michel (2006), Elements of Molecular and Biomolecular Electrochemistry: An Electrochemical Approach to Electron Transfer Chemistry, John Wiley & Sons, p. 455, doi:10.1002/0471758078, ISBN 978-0-471-44573-9
  7. Faulkner, L. R., "Understanding electrochemistry: Some distinctive concepts", Journal of Chemical Education 1983, 60, 262. doi:10.1021/ed060p262
  8. Geiger, W. E.; Barriere, F., "Organometallic Electrochemistry Based on Electrolytes Containing Weakly-Coordinating Fluoroarylborate Anions", Accounts of Chemical Research 2010, volume 43, pp. 1030-1039. doi:10.1021/ar1000023
  9. "Potentiodynamic Electrochemical Impedance Spectroscopy".
  10. Nicholson, R.S. (1965). "Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics". Anal. Chem. 37 (11): 1351–1355. doi:10.1021/ac60230a016.
  11. DuVall, Stacy DuVall; McCreery,Richard (1999). "Control of Catechol and Hydroquinone Electron-Transfer Kinetics on Native and Modified Glassy Carbon Electrodes". Anal. Chem. 71 (20): 4594–4602. doi:10.1021/ac990399d.
  12. Bond, Alan M.; Feldberg,Stephen (1998). "Analysis of Simulated Reversible Cyclic Voltammetric Responses for a Charged Redox Species in the Absence of Added Electrolyte". J. Phys. Chem. 102 (49): 9966–9974. doi:10.1021/jp9828437.
  13. Carriedo, Gabino (1988). "The use of cyclic voltammetry in the study of the chemistry of metal carbonyls". J. Chem. Educ. 65 (11): 1020. Bibcode:1988JChEd..65.1020C. doi:10.1021/ed065p1020.
  14. Wightman, R. Mark (2006). "Probing Cellular Chemistry in Biological Systems with Microelectrodes". Science. 311 (5767): 1570–1574. Bibcode:2006Sci...311.1570W. doi:10.1126/science.1120027. PMID 16543451.
  15. Geiger, W. E., "Reflections on Future Directions in Organometallic Electrochemistry", Organometallics 2011, volume 30, pp. 28-31. doi:10.1021/om1010758
  16. Kohen, Ron, et.al. Overall low molecular weight antioxidant activity of biological fluids and tissues by cyclic voltammetry.Methods Enzymol. 1999;300:285-96.
  17. Chevion, Shlomit, and Mordechai Chevion. "Antioxidant status and human health: Use of cyclic voltammetry for the evaluation of the antioxidant capacity of plasma and of edible plants." Annals of the New York Academy of Sciences 899.1 (2000): 308-325.
  18. Sochor, Jiri, et al. "Electrochemistry as a tool for studying antioxidant properties." Int. J. Electrochem. Sci 8 (2013): 8464-8489.
  19. Firuzi, Omidreza, et al. "Evaluation of the antioxidant activity of flavonoids by “ferric reducing antioxidant power” assay and cyclic voltammetry." Biochimica et Biophysica Acta (BBA) - General Subjects 1721.1 (2005): 174-184.
  20. Kohen, R. Vellaichamy E, Hrbac J, Gati I, Tirosh O.Quantification of the overall reactive oxygen species scavenging capacity of biological fluids and tissues. Free Radic Biol Med. 2000 Mar 15;28(6):871-9.
  21. Brcanovic, Jelena M., et al. "Cyclic Voltammetric Determination of Antioxidant Capacity of Cocoa Powder, Dark Chocolate and Milk Chocolate Samples: Correlation with Spectrophotometric Assays and Individual Phenolic Compounds." Food Technology and Biotechnology 51.4 (2013): 460-470.
  22. Masek, Anna, et al. "Characteristics of compounds in hops using cyclic voltammetry, UV–VIS, FTIR and GC–MS analysis." Food chemistry 156 (2014): 353-361.
  23. Martinez, Sanja, et al. "Cyclic voltammetry study of plasma antioxidant capacity–Comparison with the DPPH and TAS spectrophotometric methods."Journal of Electroanalytical Chemistry 588.1 (2006): 68-73.
  24. Cetó, Xavi, et al. "Evaluation of red wines antioxidant capacity by means of a voltammetric e-tongue with an optimized sensor array." Electrochimica Acta120 (2014): 180-186.
  25. Arteaga, Jesús F., et al. "Comparison of the simple cyclic voltammetry (CV) and DPPH assays for the determination of antioxidant capacity of active principles." Molecules 17.5 (2012): 5126-5138.

Further reading
  • Bard, Allen J.; Larry R. Faulkner (2000-12-18). Electrochemical Methods: Fundamentals and Applications (2 ed.). Wiley. ISBN 978-0-471-04372-0.
  • Zoski, Cynthia G. (2007-02-07). Handbook of Electrochemistry. Elsevier Science. ISBN 978-0-444-51958-0.
  • 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.
  • Gosser, David K. (1993-09-20). Cyclic Voltammetry Simulation and Analysis of Reaction Mechanisms. VCH. ISBN 978-1-56081-026-1.
  • Compton, Richard D.; Craig E. Banks (2010-11-15). Understanding Voltammetry (2 ed.). Imperial College Press. ISBN 978-1848165854.
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