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species (Figure S1).a Finally good reversibility and stability for both redox species of C+ were observed by CV in acetonitrile (Figure 2b).39 Differential pulse voltammetry (DPV) showed that the redox events occurs at E1/2red = -1.14 V process and E1/2ox = + 0.98 V in acetonitrile (Figure 2c).39 The measured OCV between these processes was found to be 2.12 V, which supports its potential application as a high-voltage and symmetric ORFB (Figure 2c). Figure 2: a) Scheme of redox processes for C+. b) CV at scan rate of 100 mV s–1 and c) DPV of a 1.2 mM solution of C+ in 0.1 M TBAPF6/acetonitrile (ACN). d) D and k0 were determined by studying CVs at different scan rates from 10 to 500 mV/s. The reversibility of the redox events of C+ was further investigated by acquisition of CV at different scan rates (Figure S3). The measured intensity (ip) reported as a function of the square root of the scan rate exhibits a linear relation (Figure S4), indicating analyte diffusion from the electrodes and reversibility of the redox processes at each scan rate. Based on these plots, the a To facilitate comparison, all electrochemical measurements are presented in V vs the reference AgNO3/Ag couple (ERef). Through-out this paper, the numbers reported in parentheses indicate the standard deviation in the last reported digit. 5 3 1 -1 -3 -5 C● C+ C●++ D (cm2/s) k0 (cm/s) 100 mV/s, 298K, 0.1M TBAPF6 in ACN 2.10(5) × 10-5 2.5(5) × 10-3 2.09(4) × 10-5 2.3(1) × 10-3 -1.7 -1.2 -0.7 -0.2 0.3 0.8 1.3 For more details see Eq. S1 for D and Eq. S2 for k0 Ewe (V vs AgNO3/Ag) 4 3 2 1 0 -1 -2 -3 -4 -5 -1.6 C● ↔C+ -1.14V -1.1 ΔE OCV = 2.12 V ΔEmin = 1.90 V -0.6 -0.1 0.4 Ewe (V vs AgNO3/Ag) 0.98V C+ ↔C●++ 298K, 0.1M TBAPF6 in ACN 0.9 1.4 6 I (10-5 A) I (10-5 A)PDF Image | Organic Redox Flow Battery Helical Carbeniun Ion
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