Molecular Control of Electrocatalysis: From Speciation and Coordination Spheres to Interfaces

Abstract: The local environment surrounding a catalytic active site can profoundly influence reaction rates, selectivity, and mechanism. Our group seeks to understand these effects at the molecular level and exploit them to control electrocatalytic reactivity. In the first part of this talk, I will highlight our work with molecular electrocatalysts, focusing on how catalyst speciation and precisely positioned functional groups in the second coordination sphere can alter reaction rates, mechanisms, and product selectivity. These insights are guiding our efforts to access increasingly complex transformations relevant to valorization of abundant small molecules and organic substrates. In the second part, I will extend these concepts to molecularly engineered electrode interfaces, where self-assembled monolayers provide opportunities to tune the local reaction environment at molecular length scales from a metal electrode surface. Using operando spectroscopy and complementary electrochemical methods, we are developing a molecular-level understanding of these dynamic interfaces and exploring strategies to manipulate coverage, stability under applied potentials, and ultimately reactivity. Together, this work illustrates how molecular design can be used to understand and ultimately control electrocatalytic outcomes.