(669c) An Alternative Electrode Model for Understanding Reductive Microenvironments

Certain electrochemical reactions, like CO₂ reduction, are sensitive to competing reaction mechanisms and thus elucidating their reductive microenvironments is imperative to designing better catalysts. In this presentation, we propose a novel electrode model using density functional theory (DFT) and thermochemical data to describe reduction pathways as well as mechanisms that lead to corrosion on the electrode surface. Our study challenges the use of the computational hydrogen electrode as the primary tool for computational catalysis. For instance, in alkaline hydrogen evolution reaction, we rationalize why H* might not be the sole descriptor. We plan to discuss the capabilities of our electrode model: from describing cation effects to how surface pH affects certain reaction steps. The thermodynamic implications of our model can be incorporated into experiments and reactor designs to optimize microenvironments for reduction reactions.