Exploring attached-buffer effects and Gibbs–Donnan equilibria in ionomeric energy-transduction materials

We report on applications of polymer-based electrode coatings as organizing scaffolds for assembling cobalt phthalocyanine electrocatalysts for the CO₂ reduction reaction, including how the presence of more basic imidazolyl- <i>versus</i> pyridyl- polymer functional groups enhances catalytic activity. We also describe the electrocatalytic activity of these constructs under varying (1) applied bias potentials, (2) proton activity, and (3) supporting electrolyte conditions that alter the ionic properties of the materials. These results are presented in the context of improving fundamental understandings of attached-buffer effects and Gibbs-Donnan equilibria relevant to polymer-encapsulated electrocatalysts.