Direct Spectroscopic Observation of the Structural Origin of Peroxide Generation from Co-Based Pyrolyzed Porphyrins for ORR Applications

Pyrolyzed transition metal based porphyrins present an attractive alternative to state of the art Pt-based electrocatalysts for fuel cell applications based on their comparatively low cost. Unfortunately, the large array of precursors and synthetic strategies has led to considerable ambiguity regarding the specific structure/property relationships that give rise to their activity for oxygen reduction. Specifically, considerable debate exists in actual chemical structure of the pyrolyzed reaction centers, and their relationship to membrane-damaging peroxide yield. In this manuscript a comprehensive electrochemical and spectroscopic study of pyrolyzed CoTMPP produced via a self-templating process is presented. The resulting electrocatalysts are not carbon-supported, but are highly porous self-supported pyropolymers. Rotating ring disk electrode measurements showed that the materials pyrolyzed at 700 °C exhibited the highest performance, whereas pyrolysis at 800 °C resulted in a significant increase in the p...

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