Coupling Theory to Electrode Design for Electrocatalysis

Proton-coupled electron-transfer (PCET) reactions are ubiquitous in electrochemical energy conversion processes and underpin several biological pathways.1,2 While successful mechanistic investigations of PCET reactions only began relatively recently (seeing a major uptick starting around 2003), there have been widespread attempts to incorporate PCET schemes into newly developed electrocatalysts.3,4 The primary benefit to the concerted proton-/electron-transfer reactions is their ability to avoid high-energy intermediates that plague stepwise proton-/electron-transfer steps. A persistent question has been, given the dramatic expansion of methods to immobilize electrocatalysts at an electrode interface, what chemical knobs can be turned in tuning the energetics of new interfacial PCET electrocatalysts? The recent work by Jackson, Pegis, and Surendranath begins to provide an answer to this question.