Direct observation of the oxygenated species during oxygen reduction on a platinum fuel cell cathode

Hernan Sanchez Casalongue, Sarp Kaya, Venkatasubramanian Viswanathan, Daniel J. Miller, Daniel Friebel, Heine A. Hansen, Jens K. Nørskov, Anders Nilsson, Hirohito Ogasawara*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review


The performance of polymer electrolyte membrane fuel cells is limited by the reduction at the cathode of various oxygenated intermediates in the four-electron pathway of the oxygen reduction reaction. Here we use ambient pressure X-ray photoelectron spectroscopy, and directly probe the correlation between the adsorbed species on the surface and the electrochemical potential. We demonstrate that, during the oxygen reduction reaction, hydroxyl intermediates on the cathode surface occur in several configurations with significantly different structures and reactivities. In particular, we find that near the open-circuit potential, non-hydrated hydroxyl is the dominant surface species. On the basis of density functional theory calculations, we show that the removal of hydration enhances the reactivity of oxygen species. Tuning the hydration of hydroxyl near the triple phase boundary will be crucial for designing more active fuel cell cathodes.

Original languageEnglish
Article number2817
JournalNature Communications
Number of pages6
Publication statusPublished - 2013
Externally publishedYes


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