A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

5 years ago

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

Jared L. Kneebone, Michael L. Neidig, E. Ercan Alp, Stephanie L. Daifuku, Piotr Zelenay, Edward F. Holby, Karren L. More, Michael Y. Hu, Hoon T. Chung, Jeffrey A. Kehl, Gang Wu

Nonprecious metal M–N–C (M = Fe or Co) catalysts that are effective for the oxygen-reduction reaction in polymer-electrolyte fuel cells have been developed, but no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for the reaction with dioxygen (O₂). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive toward O₂ or O₂-analogue molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe active sites in complex ORR catalysts that combines an effective probe molecule (NO_(g)), Mössbauer spectroscopy, and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO_(g) treatment of electrochemically reduced PANI–⁵⁷Fe–C leads to a selective reaction with only a subset of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe–ligand vibrations associated with the site reactive toward NO_(g). DFT calculations of the vibrational properties of a selection of previously proposed active-site structures suggest that graphene zigzag edge-hosted Fe–N structures may be responsible for the observed vibrational behavior with NO_(g) probe molecules. Furthermore, such sites are likely also reactive to O₂, possibly serving as the ORR active sites in the synthesized materials.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b03779

DOI: 10.1021/acs.jpcc.7b03779