Recent approaches for interpreting thermocatalytic systems using electrochemical methodologies have emerged. The advantages of electrochemical techniques, which include, but are not limited to, evaluating half-reaction activities and providing real-time feedback, not only allow the estimation of thermocatalytic activities of catalysts for various types of reactions (i.e., oxidative dehydrogenation and hydrogenation) but also significantly enhance catalytic activities based on electrochemical principles. Herein, we explore methods for interpreting thermocatalytic reactions and enhancing their activity across four key points. First, electrochemical techniques such as linear sweep voltammetry (LSV) and Tafel analysis were employed to estimate thermocatalytic reaction rates using a short-circuit model based on mixed potential theory. Second, we explain how spontaneous polarization between two catalysts during thermocatalytic turnover can significantly leverage the catalytic rate. Then, we suggest that this spontaneous polarization generates a measurable galvanic current, providing direct evidence of redox coupling, with the current magnitude correlating proportionally to the catalytic rate. Finally, we show that polarization not only activates each half-reaction but also mitigates catalyst leaching by stabilizing it within a controlled range of the Pourbaix diagram. These four key findings deepen our understanding of the electrochemical influences on thermocatalysis and open new pathways for designing more stable and efficient catalytic systems.
