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200 150 100 50 0 -50 -100 -1.2 GC-CNPs GC-CNPs@CeO2 GC-CNPs@CeO2-x -0.8 -0.4 0.0 0.4 0.8 1.2 i / A/g E vs. NHE / V Figure 6.41. – Cycled Voltammetry performed using the as-prepared electrodes deposit over GC electrodes in 0.5 M VO2+ and 1M H2SO4. Scan rate: 10 mVs-1. On the contrary, enhanced oxidation processes are obtained using the CeO2 and CeO2-x NPs, indicating the positive effect of the CeO2 coating and the doped improvement as oxygen vacancies are generated. Comparing both electrodes, the most pronounced peaks appeared using CeO2-x. For example, in case of the cathodic peak current-to-weight ratio values of 45 and 190 Ag-1 were obtained for CeO2 and CeO2-x, respectively. The same trends were observed for the anodic peak, 10 and 81 Ag-1 for CeO2 and CeO2-x electrodes, respectively. Consequently, the ratio of the redox peak current (Ipa/Ipc) value obtained for CeO2 electrode was 0.17 and for CeO2-x electrode 0.72, closer to their ideal value unity for one electrode transfer process (Table 6.7). Moreover, the potential peak separation carried out by CeO2 (ΔV= 290 mV) is larger than that of CeO2-x (ΔV= 140 mV), indicating higher reversibility for the second cited. The origin of the improved electrochemical behaviour can be caused by an increment of charge and electron transfer properties, as oxygen-vacancies are induced in the lattice of the CeO2 after thermal treatment in reductive atmosphere, which is analogous to the behaviour of other metal oxides89. These oxygen-vacancies are known to be electron donors, determining the surface and electronic properties of CeO2, which improves the charge transport in CeO2 as well as the electron transfer at the interface42. Indeed, electrochemical impedance spectroscopy measurement of GF@CeO2 and GF@CeO2-x electrodes showed that the charge-transfer resistance of GF@CeO2-x for VO2+/VO2+ reaction is remarkably smaller than the GF@CeO2 electrode (Figure 6.42). 136PDF Image | Redox Flow Batteries Vanadium to Earth Quinones
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