Developments in onset potential estimation for oxygen evolution reaction seeks to overcome several disadvantages in existing methods. For example, in the current tangent intersection method from the Nonfaradaic to Faradaic region, the electrocatalyst with large pseudocapacitance shows a negative slope near the onset potential in the Nonfaradaic zone. In such systems, the intersection of tangents from the Nonfaradaic to Faradaic region fails to give the onset potential. Similarly, onset potential determination from the fixed current density (10 mA/cm2) can be inaccurate for electrocatalysts having a large pseudocapacitive current. In addition, the commonly utilized methods do not provide insight into the underlying physicochemical properties that modulate reactivity around the onset potential. We propose an approach based on reaction mechanism analysis integrated with electrochemical impedance to detect the onset potential via the capacitance variation generated from the intermediate species of OER. We demonstrate our proposed method via experiments on oxygen evolution reaction in the acidic medium on platinum as the model system. The impedance analysis of such a system from the Nonfaradaic to Faradaic region shows the capacitance generated from the intermediate species (S-OH) shows the maxima at the onset potential. Further, the Tafel analysis showed the S-OH step as the rate-determining step (RDS) in a low overpotential region. Additionally, the onset potential obtained from the tangent intersection from the Nonfaradaic to Faradaic region matches that obtained from the impedance analysis. We are in the process of extending the proposed approach to more complex systems with multiple product evolutions.
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