Cyclic voltammetry adsorption

Cyclic voltammetry (adsorption, monolayers) Potentiodynamic polarisation (passivation, activation) Cathodic reduction (thickness) Frequency response analysis (electrical properties, heterogeneity) Chronopotentiometry (kinetics)... 

Cyclic voltammetry is the most widely used technique for acquiring qualitative information about electrochemical reactions. The power of cyclic voltammetry results from its ability to rapidly provide considerable information on the thermodynamics of redox processes, on the kinetics of heterogeneous electron-transfer reactions, and on coupled chemical reactions or adsorption processes. Cyclic voltammetry is often the first experiment performed in an electroanalytical study. In particular, it offers a rapid location of redox potentials of the electroactive species, and convenient evaluation of the effect of media upon the redox process. 

According to experimental data,208,209 the SNIFTIR technique can be used to probe the electrical properties of the electrical double layer even in more concentrated solutions where cyclic voltammetry (cv), impedance, chronocoulometry, and other techniques are not applicable. Iwasita and Xia210 have used FTIR reflection-adsorption spectra to identify the potential at which the orientation of water molecules changes from hydrogen down to oxygen down. 

Reconstruction of the Cu(l 11) close-packed surface at room temperature upon oxygen adsorption has been reported by Niehus.590 This result is in good agreement with data on cyclic voltammetry and second-harmonic generation591 it has been concluded that oxygen-containing spe-... 

Adsorption of formaldehyde on Pt (111) and Pt(lOO) electrodes cyclic voltammetry and scanning tunneling microscopy. Langmuir, 21, 4964—4970. 

Cyclic voltammetry is perhaps the most important and widely used technique within the field of analytical electrochemistry. With a theoretical standard hydrogen electrode at hand, one of the first interesting and challenging applications may be to try to use it to make theoretical cyclic voltammograms (CVs). In following, we set out to do this by attempting to calculate the CV for hydrogen adsorption on two different facets of platinum the (111) and the (100) facets. 

In this section, we will present and discuss cyclic voltammetry and potential-step DBMS data on the electro-oxidation ( stripping ) of pre-adsorbed residues formed upon adsorption of formic acid, formaldehyde, and methanol, and compare these data with the oxidative stripping of a CO adlayer formed upon exposure of a Pt/ Vulcan catalyst to a CO-containing (either CO- or CO/Ar-saturated) electrolyte as reference. We will identify adsorbed species from the ratio of the mass spectrometric and faradaic stripping charge, determine the adsorbate coverage relative to a saturated CO adlayer, and discuss mass spectrometric and faradaic current transients after adsorption at 0.16 V and a subsequent potential step to 0.6 V. 

Mai C-F, Shue C-H, Yang Y-C, Yang L-YO, Yau S-L, Itaya K. 2005. Adsorption of formaldehyde on Pt(lll) and Pt(lOO) electrodes Cyclic voltammetry and scaniung tinmeUng microscopy. Langmuir 21 4964-4970. 

Cyclic voltammetry studies of single-crystal platinum electrodes in acidic aqueous electrolytes showed that the two characteristic peaks of hydrogen adsorption/desorption on platinum (see Fig. 5.40) correspond in fact to reactions at two different crystal faces the peak at lower potential to Pt(100) and the other one to Pt(lll). 

The electronic adsorption spectra for the complexes [Ir(OH)6]", where n = 0-2, have been resolved and peak maxima locations, molar extinction coefficients, oscillator strengths, and band half-widths calculated.44 Bands have been assigned in the main part to be one-electron MLCT transitions. Spectrophotometrically determined rate constants for the OH reduction of the IrVI and Irv complexes at 25 °C in 3M NaOH are (2.59 0.09) x 10—3 s—1 and (1.53 0.05) x 10 4 s 1 respectively. The activation energy for the reduction, Irv—>IrIV, is nAkcalmoC1. Cyclic voltammetry and potentiostatic coulometry of [Ir(OEI )r,]2 in 3M NaOH on a Pt electrode show that during the electro-oxidation compounds of Irv and IrVI are formed.45... 

It is concluded that the occupation of the step and kink sites plays a crucial role in the promotion of the Pt catalyst. The cyclic voltammetry results can be used to explain the conversion trends observed in Figure 2. For unpromoted 5%Pt/C the Pt step and kink sites are unoccupied and available for adsorption of reactant and oxidant species. During reaction these sites facilitate premature catalyst deactivation due to poisoning by strongly adsorbed by-products (5) and (or) the formation of a surface oxide layer (6). The 5%Pt,0.5%Bi/C catalyst has a portion of these Pt step and kink sites occupied and the result is a partial reduction in the catalyst deactivation and a consequent increase in alcohol conversion. As the Bi level is increased to lwt.% almost all of the Pt step and kink sites are occupied and the result is a catalyst with high activity. As more Bi is introduced onto the catalyst surface a bulk Bi phase is formed. Since the catalyst activity is maintained it is speculated that the bulk Bi phase is not involved in the catalytic cycle. 

Electrochemical techniques have been utilized for many years to study metal corrosion. Two of these techniques, linear polarization (LP) and cyclic voltammetry (CV), complement each other, LP providing corrosion rates under conditions where the surface is minimally altered and CV furnishing information about the corrosion mechanism. With the advent of impedance spectroscopy (IS), both kinds of information can be gleaned simultaneously and more rapidly, while leaving the surface almost intact. In this paper, we discuss the application of IS to the study of rapid steel corrosion and describe a study we undertook to elucidate the roles played by adsorption and film formation in the inhibition mechanisms of the above-named compounds. For comparison, we also investigated two quaternary nitrogen salts, which appear to adsorb electrostatically and presumably do not form macroscopic films (8). 

Gao, G., A. S. Jeevarajan et al. (1996). Cyclic voltammetry and spectroelectrochemical studies of cation radical and dication adsorption behavior for 7,7 -diphenyl-7,7 -diapocarotene. J. Electroanal. Chem. 411 51-56. 

Kowal, A. and Domianowski, A., 1973. Cyclic voltammetry of ethyl xanthate on a natural copper sulphide electrode. Electrocnal Chem. Interf. Electrochem., 46 411 - 420 Laajalehto, K., Nowak P., Pomianowski, A., Suonien, E., 1991. Xanthate adsorption at the PbS/aqueous interface comparison of XPS, infiared and electrochemical results. Colloids Surf., 57 319-333... 

Figure 26. Comparison of the resonance scattering from H atoms or H+ obtained by fitting the Fano line shape in HCIO4 (open squares) and H2SO4 (closed squares) with the adsorbed hydrogen coverage (closed circles) and sulfate adsorption (open circles) obtained by cyclic voltammetry. (Reproduced with permission from ref 50. Copyright 2001 The Electrochemical Society, Inc.)...

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