Doping cyclic voltammetry studies

Cyclic-voltammetry studies of the SmClj-doped glassy carbon in the presence and absence of cyclohexane suggested that a hydroperoxy radical generated on Sm was directly or indirectly responsible for oxygenation of cyclohexane. 

Pt or ITO electrodes dipped in a nitrobenzene solution containing tetrabutylammonium hexafluorophosphate or tetrabutylammonium tetrafluoroborate. Cyclic voltammetry study of the polymers grafted on to Pt revealed on electroactive material which exhibits an electrochromic behaviour (blue in the doped state, red in the reduced state) similar to that reported for poly(3-methylthiophene) (Figure 14.27). It is interesting to note that the Ep (monomer), the fpa (polymer) and the Ep -Epc values are larger than those reported for poly(3-methylthiophene) (Table 14.13). 

Wangfuengkanagul and Chailapakul [9] described the electroanalysis of ( -penicillamine at a boron-doped diamond thin film (BDD) electrode using cyclic voltammetry. The BDD electrode exhibited a well-resolved and irreversible oxidation voltammogram, and provided a linear dynamic range from 0.5 to 10 mM with a detection limit of 25 pM in voltammetric measurement. In addition, penicillamine has been studied by hydrodynamic voltammetry and flow injection analysis with amperometric detection using the BDD electrode. 

The first reports on direct electrochemistry of a redox active protein were published in 1977 by Hill [49] and Kuwana [50], They independently reported that cytochrome c (cyt c) exhibited virtually reversible electrochemistry on gold and tin doped indium oxide (ITO) electrodes as revealed by cyclic voltammetry, respectively. Unlike using specific promoters to realize direct electrochemistry of protein in the earlier studies, recently a novel approach that only employed specific modifications of the electrode surface without promoters was developed. From then on, achieving reversible, direct electron transfer between redox proteins and electrodes without using any mediators and promoters had made great accomplishments. 

These studies have been mainly carried out using cyclic voltammetry and frequency response analysis as experimental tools. As a typical example. Fig. 9.12 illustrates the voltammogram related to the p-doping process of a polypyrrole film electrode in the LiClQ -propylene carbonate electrolyte, i.e. the reaction already indicated by (9.16). 

Deposition of mercury at boron-doped diamond (BDD) and platinum electrodes has also been studied [33]. Deposition and oxidation of mercury was performed by cyclic voltammetry from the solution of 1 mM Hg2 ( 104)2 in 1 M Na l04. In order to learn more about this deposition, it was carried out also under chronoamperometric conditions. The results obtained are shown in Fig. 2 in the form of dimensionless current-time transients. Experimental curves obtained at two different overpotentials were compared with the theoretical curves calculated for instantaneous and progressive nucleation. A good agreement of experimental plots with the instantaneous nucleation mechanism was... 

The electrochemical behavior of poly(ferrocenylsilanes) has been studied at three levels—in solution by cyclic voltammetry, as films deposited on electrodes, and in the solid state via iodine doping. Solution cyclic voltammetric oxidation and reduction has shown that the polymer, where R/R is Me/Me, reversibly oxidizes in methylene chloride in two stages, apparently with the first oxidation being on alternating iron atoms along the chain.29 Films cast on electrodes behave in a similar way and also show an electrochromic response to oxidation and reduction.30... 

Among the large variety of in situ experiments that have been described one can distinguish (1) those whose purpose is investigation of the electrochemical doping process itself cyclic voltammetry, quartz balance [17], mirage effect [18], and ellipsometry [19], and (2) those developed for studies of the properties of the CP UV-near-IR spectroscopy [20], IR [21], ESR [22], conductivity [23], impedence [24], and so on. 

The storage and reactivity of electroactive molecules in polymerized diacetylene vesicles was the subject of studies reported by Stanish, Singh, and coworkers [109, 110], They entrapped ferricyanide in large unilamellar vesicles of photopolymerized PCg PC (1 - palmitoyl - 2 - (tricosa - 10,12-diynoyl)-OT-glycero-3-phosphocholine). Cyclic voltammetry was used to demonstrate that the ferricyanide was electrochem-ically isolated by the poly(lipid) bilayer [110]. At pH7 and 25°C, an anomalously long half-life of 2.4 weeks was calculated for Fe (CN)g- retention in polymerized vesicles. In a subsequent study [109], vesicles with entrapped ferricyanide were prepared from 2-bis(10,12-tricosadiynoyl)-OT-glycero-3-phosphatidylcholine (DCs.gPC) doped with a disulfide-capped lipid (Af-3-(pyridyl-2-dithio)propionyl-2-... 

Y.C. Liu, BJ. Hwang, W.J. Jian, and R. Santhanan, In situ cyclic voltammetry-surface-enhanced Raman spectroscopy studies on the doping-undoping of polypyrrole film. Thin Solid Films, 374, 85-91 (2000). 

M.D Levi, C. Lopez, E. Vieil, and M.A. Vorotyntsev, Influence of ionic size on the mechanism of electrochemical doping of polypyrrole films studied hy cyclic voltammetry, Electrochim. 

In further studies, the self-doping mechanism of these polymers was verified by cyclic voltammetry, pH measurements and atomic absorption spectroscopy [17,20]. The cyclic voltammograms of the sodium salt and acid forms of poly(3-thiophene butanesulfonate) cast films are shown in... 

---