Voltammetry behavior

Although cyclic voltammetry in a variety of electrolyte systems, and with a variety of doped polymers, has shown strong effects due to ion transport, it has provided little understanding. In fact, one of the important uses of ion transport data from the techniques discussed in the preceding subsections is that they help to provide an understanding of the cyclic voltammetry behavior of conducting polymer films. Their importance will... 

The cyclic voltammetry behavior of the Cu(II) rotaxane, 4(5)2+ (Fig. 14.8b), is very different from that of 4, t l +. The potential sweep for the measurement was started at - 0.9 V, a potential at which no electron transfer should occur, regardless of the nature of the surrounding of the central Cu(II) center (penta- or tetracoordinate). Curve i shows two cathodic peaks a very small one, located at + 0.53 V, followed by an intense one at —0.13V. Only one anodic peak at 0.59 V appears during the reverse sweep. If a second scan ii follows immediately the first one i, the intensity of the cathodic peak at 0.53 V increases noticeably. The main cathodic peak at —0.15 V is characteristic of pentacoordinate Cu(II). Thus, in 4(5)2+ prepared from the free rotaxane by metalation with Cu(II) ions, the central metal is coordinated to the terdentate terpyridine of the wheel and to the bidentate dpp of the axle. On the other hand, the irreversibility of this peak means that the pentacoordinate Cu(I) species formed in the diffusion layer when sweeping cathodically is transformed very rapidly and in any case before the electrode potential becomes again more anodic than the potential of the pentacoordinate Cu2 + /Cu+ redox system. The irreversible character of the wave at —0.15 V and the appearance of an anodic peak at the value of + 0.53 V indicate that the transient species, formed by reduction of 4(5)2 +, has undergone a complete reorganization, which leads to a tetracoordinate copper rotaxane. The second scan ii, which follows immediately the first one i, confirms this assertion. 

Different sehemes of eleetroehemieal pretreatments have been proposed. In general, they depend on the system under investigation. For instance, for the oxidation of dopamine, 18 cyeles between -1.00 V and 1.50 V at 1.0 V/s in a 0.050 M phosphate buffer pH 7.40 demonstrated to be the optimum pretreatment for obtaining the best voltammetrie behavior of dopamine [46]. However, for the oxidation of amitrole, 75 cyeles between -1.0 and 1.5 V at 1.0 V/s in 0.050 M phosphate buffer solution pH 7.4 were necessary to obtain the best analytical signal [47]. 

The cyclic voltammetry behavior of the Cu(II) rotaxane 13 (Fig. 12b), is very different from that of 13. The potential sweep for the measurement was started at +0.9 V, a potential at which no electron transfer should occur, whatever the surrounding of the central Cu(II) is (penta- or tetracoordinated). Curve (i) (first scan, recorded at 100 mV x s-1) shows two cathodic peaks a very small one, located at +0.53 V followed by an intense one at -0.15 V. Only one anodic peak at 0.59 V appears during the reverse sweep. If a second scan (ii) follows immediately after the first one (i), the intensity of the cathodic peak at 0.53 V increases noticeably. 

Impedance and Voltammetry Behavior of Brush Electrode Models of Porous Electrodes... 

Obradovic MD, Lessard J, Jerkiewicz G (2010) Cyclic-voltammetry behavior of Pt(l 11) in aqueous HCIO4 + CsHg influence of concentration, scan rate and temperature. J Electroanal Chem 649 248-256... 

Modestov A D, Zhou G-D, Ge FI-FI and Loo B FI 1995 A study by voltammetry and the photocurrent response method of copper electrode behavior in acidic and alkaline solutions containing chloride ions J. Electroanal. Chem. 380 63-8... 

Julid investigated the behavior of terfuran 22 and bis(thienyl)furan 23 by cyclic voltammetry as well as the EPR spectra of the radical cations derived from these two compounds. Condensation of the diketone 20 with sulfuric acid furnished furan 22 in 18% yield, while reaction of diketone 21 with hydrochloric acid produced 23 in 84% yield.In a related report, Luo prepared oligomeric bis(thienyl)furans via similar methodology. ... 

Cyclic voltammetry can also be used for evaluating die interfacial behavior of electro active compounds. Both the reactant and the product can be involved in an... 

The electrochemical behavior of heterometallic clusters has been reviewed clsewbcre."" The interest in examining clusters stems from their potential to act as "electron sinks " in principle, an aggregate of several metal atoms may be capable of multiple redox state changes. The incorporation of heterometals provides the opportunity to tune the electrochemical response, effects which should be maximized in very mixed"-metal clusters. Few very mixed -metal clusters have been subjected to detailed electrochemical studies the majority of reports deal with cyclic voltammetry only. Table XII contains a summary of electrochemical investigations of "very mixed"-metal clusters. 

The coordination of redox-active ligands such as 1,2-bis-dithiolates, to the M03Q7 cluster unit, results in oxidation-active complexes in sharp contrast with the electrochemical behavior found for the [Mo3S7Br6] di-anion for which no oxidation process is observed by cyclic voltammetry in acetonitrile within the allowed solvent window [38]. The oxidation potentials are easily accessible and this property can be used to obtain a new family of single-component molecular conductors as will be presented in the next section. Upon reduction, [M03S7 (dithiolate)3] type-11 complexes transform into [Mo3S4(dithiolate)3] type-I dianions, as represented in Eq. (7). 

The redox behavior in the silver-selenium-water system at ambient and higher (85 °C) temperatures was studied by Petrov and Belen kii [163]. According to their voltammetry results, and the presented Pourbaix diagram (Fig. 3.9), the stability... 

The qualitative voltammetric behavior of methanol oxidation on Pt is very similar to that of formic acid. The voltammetry for the oxidation of methanol on Pt single crystals shows a clear hysteresis between the positive- and negative-going scans due to the accumulation of the poisoning intermediate at low potentials and its oxidation above 0.7 V (vs. RHE) [Lamy et al., 1982]. Additionally, the reaction is also very sensitive to the surface stmcture. The order in the activity of the different low index planes of Pt follows the same order than that observed for formic acid. Thus, the Pt(l 11) electrode has the lowest catalytic activity and the smallest hysteresis, indicating that both paths of the reaction are slow, whereas the Pt( 100) electrode displays a much higher catalytic activity and a fast poisoning reaction. As before, the activity of the Pt(l 10) electrode depends on the pretreatment of the surface (Fig. 6.17). 

The voltammograms at the microhole-supported ITIES were analyzed using the Tomes criterion [34], which predicts ii3/4 — iii/4l = 56.4/n mV (where n is the number of electrons transferred and E- i and 1/4 refer to the three-quarter and one-quarter potentials, respectively) for a reversible ET reaction. An attempt was made to use the deviations from the reversible behavior to estimate kinetic parameters using the method previously developed for UMEs [21,27]. However, the shape of measured voltammograms was imperfect, and the slope of the semilogarithmic plot observed was much lower than expected from the theory. It was concluded that voltammetry at micro-ITIES is not suitable for ET kinetic measurements because of insufficient accuracy and repeatability [16]. Those experiments may have been affected by reactions involving the supporting electrolytes, ion transfers, and interfacial precipitation. It is also possible that the data was at variance with the Butler-Volmer model because the overall reaction rate was only weakly potential-dependent [35] and/or limited by the precursor complex formation at the interface [33b]. 

---