Electrocatalytic Syntheses with Interfacial Control

Synthesis driven by renewable electricity offers a sustainable, scalable, decentralized, and energy-efficient route to furnish value-added products. As electrocatalytic reactions occur at the interface between solid electrodes and liquid electrolytes, designing selective reactions requires methods to study this interface and predict how changes in its structure affect reaction outcomes. In this talk, I will disclose two recent discoveries from my group using in-situ spectroscopy, electrochemical analyses, and simulations to unravel the catalytic interfacial structure and guide reaction development. First, we have found that carboxylates bind to oxide electrode surfaces, enhancing the selectivity for non-Kolbe oxidation to alkenes by suppressing the parasitic oxygen evolution reaction. Second, we have uncovered a paradigm that deploys catalytic electrode surfaces to develop reductive fragment-based electrophile coupling reactions. The addition of Lewis acids pre-organizes the surface, enabling a carbon-centered radical (obtained via electrocatalytic activation) to efficiently add to the carbonyl. Our studies lay a foundation to develop sustainable synthetic methodologies by tuning the interfacial structure at catalytic, reusable electrodes at the molecular level.