A Survey of Reaction Energetics for Diverse Small Molecule Activation: Where Do Molecular Electrocatalysts Go From Here?

Abstract The invention of technologies that can activate, transform, and upgrade small molecules is a significant challenge. The starting point for many such technologies is molecular catalysts. Their well‐defined active sites, multitude of tools to characterize their reactions, and their synthetic flexibility makes such molecules logical starting points. However, it is increasingly clear that challenges exist in the applications of molecular catalysts at the scales needed to address modern chemical and energy demands. In this review, we discuss selected classes of molecular electrocatalysts and highlight their development and key features. Of special interest are proton‐coupled transformations of H 2 , O 2 , N 2 , CO 2 , and related small molecules. We also frame important thermodynamic features for different catalysts using new approaches and ask forward looking questions about their applications in practical systems.