(247c) Rigorous Kinetic Analysis of Electrocatalytic Reactions

Electrification of chemical reactions may provide a route to mitigating carbon emissions involved in generating diverse molecules and materials that constitute the physical world. At the very heart of this electrification is the development of catalysts that can facilitate the molecular-level bond breaking and forming steps needed to sustainably synthesize chemicals using electrical potential as a driving force. Mechanistic understanding of these electrocatalytic reactions can be obtained through careful measurement of the order dependence of reaction rate on the reactants participating in the reaction. Although rigorous kinetic studies are often conducted for thermocatalytic reactions, they are less commonly done for electrocatalytic reactions. In this tutorial, we will discuss how to develop rigorous thermodynamic understanding of electrocatalytic systems, including the measurement of thermodynamic activities of non-ideal chemical reactants such as water. Then, we will discuss how to use this thermodynamic foundation to conduct sound kinetic analyses, including the use of Bayesian statistics for measuring relevant electrochemical quantities.