Kinetics of V5+/V4+ Redox Reaction: An Analysis Based on Eyring Equation

Tuesday, 11 October 2022: 17:20
Room 302 (The Hilton Atlanta)
M. Neergat (Indian Institute of Technology Bombay) and A. Tripathi (IITBOMBAY)
Electrocatalysis of redox reactions important to energy conversion and storage devices are widely reported in the literature [1–3]. In this work, the current-voltage curves (i-V curves) of V5+/V4+ redox reaction are recorded in a three-electrode configuration on Vulcan XC-72 modified glassy carbon rotating disk electrode at various temperatures. The enthalpy of activation (ΔH#) and pre-exponential factor at various overpotentials are estimated from the slope and intercepts of Eyring plots, respectively. Measured current is corrected for solution resistance and mass-transfer resistance to obtain the kinetic current. The analyses show that the electrocatalysis of V5+/V4+ redox reactions is due to the increase in the value of pre-exponential factor. The trend in the charge-transfer coefficients with the overpotential confirms the adsorbate effect on the electrode surface. Therefore, ΔH# and pre-exponential factor can be estimated from the Eyring plot only when there is no electrode surface coverage.

References:

  1. R. K. Singh, R. Devivaraprasad, T. Kar, A. Chakraborty and M. Neergat, J. Electrochem. Soc., 162, F489 (2015).
  2. B. Bapi, T. Kar, A. Chakraborty and M. Neergat, J. Electroanal. Chem., 805, 184 (2017).
  3. P. Leuaa, D. Priyadarshani, A.K. Tripathi and M. Neergat, J. Electroanal. Chem., 878, 114590 (2020).