Oxygen Reduction on Organic Mixed Ionic-Electronic Conducting Polymer Electrodes

Organic mixed ionic-electronic conductors (OMIECs) are a class of conjugated semiconducting polymers with tunable electronic and ionic transport properties enabled through polaron-forming ion insertion redox reactions. The energy to form these conductive polaronic states can be controlled through rational design of the polymer backbone to enable predominantly electron/cation (n-type) or hole/anion (p-type) transport. Simultaneously, electrolyte uptake into the bulk of the electrode can be controlled through incorporation of polar/non-polar sidechains. The ability to tune the energy of the redox-active states, the majority charge carrier, and the local reaction environment offers an opportunity to independently optimize activity and selectivity in electrochemical energy conversion processes with a single-phase electrode. In this talk, I will discuss our efforts to develop OMIECs as electrocatalysts for the oxygen reduction reaction. The electronic and chemical origins of reactivity are interrogated through pH-dependent electroanalytical characterization, operando spectroscopy, charge-transport measurements, and ab initio /microkinetic simulations. The nature of the polaronic states provide a generalized framework to understand pathway selectivity towards the 2-electron H 2 O 2 or 4-electron H 2 O product and serve as a design principle in developing this emerging class of metal-free electrocatalysts.