Cyclic voltammogram, oxidation

Figure 6.2-3 Cyclic voltammogram of acid [BMIM] CI /AICl3 on Au(m) Au oxidation begins...

The unusual cyclic voltammograms and responses to large-amplitude potential steps of a variety of conducting polymer films have prompted a number of groups to develop nucleation models for their oxidation. The key features that they have sought to explain are the peaks observed in anodic chronoamperometry (see Fig. 14), and the dependence of the anodic peak position on scan rate207 and the time spent in the undoped state.20 ... 

If the film is nonconductive, the ion must diffuse to the electrode surface before it can be oxidized or reduced, or electrons must diffuse (hop) through the film by self-exchange, as in regular ionomer-modified electrodes.9 Cyclic voltammograms have the characteristic shape for diffusion control, and peak currents are proportional to the square root of the scan speed, as seen for species in solution. This is illustrated in Fig. 21 (A) for [Fe(CN)6]3 /4 in polypyrrole with a pyridinium substituent at the 1-position.243 This N-substituted polypyrrole does not become conductive until potentials significantly above the formal potential of the [Fe(CN)6]3"/4 couple. In contrast, a similar polymer with a pyridinium substituent at the 3-position is conductive at this potential. The polymer can therefore mediate electron transport to and from the immobilized ions, and their voltammetry becomes characteristic of thin-layer electrochemistry [Fig. 21(B)], with sharp symmetrical peaks that increase linearly with increasing scan speed. 

Polyanaline, a cyclic voltammogram of its oxidation, 563 Polymer film conducting Doblehofer, 587 Pickup, 549 of electrodes, 382... 

Figure 5.2. NEMCA and its origin on Pt/YSZ catalyst electrodes. Transient effect of the application of a constant current (a, b) or constant potential UWR (c) on (a) the rate, r, of C2H4 oxidation on Pt/YSZ (also showing the corresponding UWR transient)3 (b) the 02 TPD spectrum on Pt/YSZ4,7 after current (1=15 pA) application for various times t. (c) the cyclic voltammogram of Pt/YSZ4,7 after holding the potential at UWR = 0.8 V for various times t.

Fig. 7. Cyclic voltammograms for the oxidation of polyacetylene (PA), polypyrrole (PPy) and polyqnaterthienyl (PQTh)...

Fig. 17. Cyclic voltammogram of the water-soluble Rieske fragment from the bci complex of Paracoccus denitrificans (ISFpd) at the nitric acid modified glassy carbon electrode. Protein concentration, 1 mg/ml in 50 mM NaCl, 10 mM MOPS, 5 mM EPPS, pH 7.3 T, 25°C scan rate, 10 mV/s. The cathodic (reducing branch, 7 < 0) and anodic (oxidizing branch, 7 > 0) peak potentisds Emd the resulting midpoint potential are indicated. SHE, standEU d hydrogen electrode.

FIG. 26 Cyclic voltammograms of 40 monolayers of Langmuir-Schaefer films of cytochrome P450SCC on indium-tin oxide glass plate (ITO) in 10 mM phosphate buffer at a scan rate of 20 mV/s between 0.4 and —0.4 V vs. Ag/AgCl. LS films on ITO worked as the working electrode, platinum as the counter, and Ag/AgCl as the reference electrode. Cholesterol dissolved in X-triton 100 was added 50 p.1 at a time (1) with cholesterol, (2) 50 p.1 of cholesterol, (3) 100 p.1 cholesterol, and (4) 150 p.1 of cholesterol. 

Fig. 4. Cyclic voltammograms of various tungsten oxides (a) WOyxHjO, (b) WOj-xHjO, and (c) Nao. WOyxHjO.

Fig. 7. TGA plot of Fig. 8. Cyclic voltammograms of rfienium oxides as-prepared Re03-xH20 (a) amorphous ReOj-1.4H2O in ION H2SO4,...

Figure 6. Simulated cyclic voltammogram for the oxidation of ascorbic acid without Inclusion of ec catalysis by the surface qulnone functionalities. Filled circles represent the simulated data and an experimental curve Is shown with a line for comparison. A scan rate of 100 mV s was assumed for experimental and simulated data.

Figure 12. Cyclic voltammograms of direct methanol oxidation catalyzed by the porous Pt nanoparticle membrane and as-made Pt nanoparticles. The reaction solution was made of an aqueous mixture containing O.IMHCIO4 and 0.125 M methanol. (Reprinted with permission from Ref [31], 2005, Wiley-VCH.)...

Figure 13. (a) Cyclic voltammograms, (b) chronoamperometric curves for oxidation of methanol catalyzed by the Pt-porous nano-... 

Figure 5.9 Schematic cyclic voltammogram showing the electro-oxidation of the electrode (dashed box). The curve was generated from measurements by Jerkiewicz et al. [2004] of Pt in 0.5 M H2SO4 with a reversible hydrogen reference electrode (RHE). For each separable potential range, an atomistic model of the electrode structure is shown above.

Figure 6.22 (a) Cyclic voltammograms of the oxidation of 0.1 M acetaldehyde on Pt single-... 

Figure 8.9 Polarization curves for a PtSn/C catalyst recorded by a rotating disk electrode in 0.5 M H2SO4 saturated with either pure hydrogen, a H2/2% CO mixture, and pure CO (the arrow points to the onset of CO oxidation) at 60 °C with 1 mV/s and 2500 rev/min the dashed curve is the cyclic voltammogram (in arbitrary units) in an argon-purged solution at 60 °C with 50 mV/s. (Reprinted with permission from Aienz etal. [2005]. Copyright 2005. Elsevier.)...

Figure 11.18 Linear cyclic voltammograms of a FePc/C disk electrode and corresponding oxidation current of a Pt ring electrode maintained at 1.2 V vs. RHE, recorded at 2500 rev min in an 02-saturated 0.5 M H2SO4 electrolyte (temperature 20 °C, sweep rate 5 mV s ).

Figure 17.12 Direct electrocatal3ftic oxidation of D-fnictose at a glassy carbon electrode painted with a paste of Ketjen black particles modified with D-fructose dehydrogenase from a Gluconobacter species. The enzyme incorporates an additional heme center allowing direct electron transfer from the electrode to the flavin active site. Cyclic voltammograms were recorded at a scan rate of 20 mV s and at 25 + 2 °C and pH 5.0. Reproduced by permission of the PCCP Owner Societies, from Kamitaka et al., 2007.

Electrochemically active compounds can be evaluated using a potentiometer to generate a cyclic voltammogram for the analyte. Cyclic voltammetry will allow the analyst to determine whether the compound can be oxidized or reduced, to choose the appropriate potential to use in the electrochemical detector, and to establish whether oxidation or reduction is irreversible. Irreversible oxidation or reduction of the analyte could be predictive of problems with electrode poisoning and reduced sensitivity of the electrochemical detector over time. Turberg et al. used EC detection at an applied potential of -1-600 mV to analyze for ractopamine. 

FIG. 1 (a) Cyclic voltammogram of the heterogeneous oxidation of ferrocene by the hexacyano-... 

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