Electrochemical kinetics is a field of electrochemistry studying the rate of electrochemical processes. The electrochemical reactions occur at the interface between an electrode and an electrolyte, there are accompanying phenomena to electrochemical reaction which contribute to the overall reaction rate. The different combinations of parameters and working electrode types make for a long list of techniques,including chromoamperometry, chromopotentiometry, voltammetry, polarography, cyclic voltammetry, linear sweep techniques,chronoamperometry, chronopotentiometry, pulsed techniques and others. In electrochemical transient analysis for investigating the electrochemical kinetics, you might use so many electrochemical methods, including galvanostatic and potentiostatic methods.

Thank you Dr. Chen for your prompt response. My point is which will be better? Chronopotentiometry or Chronoamperometry to analyse the electron transfer kinetics.

The answer is, it depends what you are trying to measure

Thank you Dr Paul Milham. I am particular for electrochemical sensor with f-block metal oxides.

Potentiostatic analysis is most common for evaluating kinetics for electrochemical sensors.

Holding Voltage constant while monitoring current flow that accompanies the reduction; I think would be more reasonable. You can the then fit the currents into 1st order or 2nd order kinetic integrated rate laws/models to decipher overall rate.

However remember to take into account that diffusion process will compete to become more important at reaction proceeds BUT negligible in the early stages of electroreduction/oxidation when the surface is mostly pristine/fresh.