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Chapter 4. Molecular Electrochemistry of Quinones Figure 4.22: RDE experiment of 5 mM PPAQ(H) in 1 M KOH recorded on a GC WE. (a) Linear sweep voltammograms recorded at 5 mV s−1 in the cathodic direction at rotation rates from 300–2500 rpm. The areas shaded in blue and red show where the Levich and Koutecký-Levich currents were determined. (b) Levich plot. (c) Koutecký–Levich plot. (d) Tafel plot. The dashed lines in subplots (b)–(d) are extensions of the linear regression lines to x = 0. to the other investigated quinones. It is therefore possible that the electrode kinetics of DBEAQ on GC are too facile to allow reliable estimation of the transfer coefficient with the RDE method. An RRDE experiment was carried out simultaneously by recording the current on a gold ring WE at a constant potential of −0.275 V vs. SHE. The voltammograms are presented in Figure C.5 in Appendix C and show a ring-to-disk current ratio close to the theoretical value of 38.3 % for all rotation rates. This suggests that DBEAQ is chemically stable at pH 12, at least on short time scales. Lastly, the RDE experiment was repeated on a gold WE (see Figure C.4 in Appendix C) and resulted in an almost identical value for the diffusion coefficient (2.61 × 10−6 cm2 s−1) and lower values for the standard rate constant (2.50 × 10−2 cm s−1) and transfer coef- ficient (0.098). The calculated transfer coefficient is unlikely to be a good estimate, as symmetric oxidation and reduction peaks of DBEAQ were also observed on a gold WE during CV (see Figure 4.2 (d), dashed black line). 66PDF Image | Organic Redox Flow Batteries 2023
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