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4.2.4 Anthraquinones 4.2.4.1 DHAQ DHAQ was investigated as another reproduction of literature results [29]. CV resulted in near-reversible voltammetry with a peak split of 83 mV and redox potential of −0.670 V vs. SHE, although with rather broad peaks (see Figure 4.2 (d), yellow line). Simulation work done by Lin et al. suggested that the DHAQ electrochemistry is best described by two successive one-electron processes [29], which would explain the broad peaks. The diffusion coefficients were determined with a Randles-Ševčík analysis of cyclic voltam- mograms recorded between 50 mV s−1 and 500 mV s−1. The voltammograms and peak current densities are shown in Figure 4.20 and diffusion coefficients of 1.15 × 10−6 cm2 s−1 and 1.55 × 10−6 cm2 s−1 were calculated for the oxidised and reduced species, respectively. The peak potentials change only slightly with scan rate and the regressions almost inter- sect at (0,0) and display a fair degree of linearity, suggesting that the electrochemistry of this system is near-reversible. The diffusion coefficients are around 4 times lower than the 4.8 × 10−6 cm2 s−1 determined by RDE measurements reported in literature [29], which follows the trend from other experiments that the Randles-Ševčík method results in lower estimates of the diffusion coefficient than the Levich method. Figure 4.20: (a) Cyclic voltammograms of 2mM DHAQ in 1M KOH recorded on a GC WE at various scan rates, initially in the cathodic direction. The dashed grey line represents a background recorded in blank solution. (b) Randles-Ševčík plot of the anodic and cathodic peak current densities. The dashed red and blue lines are an extension of the linear regression lines to x = 0. 4.2.4.2 PSAQ PSAQ was one of the anthraquinone structures developed and synthesised in-house. The ether-linked propylsulfonate functional groups were primarily added to increase the aqueous solubility and stability, as was later shown possible with similar functional groups [24, 25]. The cyclic voltammogram recorded in 1M H2SO4 is presented in Figure 4.2 (d) (green line) and shows near-reversibility with a peak split of 66mV and redox potential 4.2. Results and Discussion 63PDF Image | Organic Redox Flow Batteries 2023
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