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Title: 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

Abstract

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O 2). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O 2 or O 2-analog 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 selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO (g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behaviormore » with NO (g) probe molecules. Moreover, such sites are likely also reactive to O 2, possibly serving as the ORR active sites in the synthesized materials.« less

Authors:
 [1];  [1];  [1];  [2];  [2];  [3];  [3];  [4];  [2];  [2]; ORCiD logo [1]
  1. Univ. of Rochester, Rochester, NY (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1376622
DOE Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 30; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kneebone, Jared L., Daifuku, Stephanie L., Kehl, Jeffrey A., Wu, Gang, Chung, Hoon T., Hu, Michael Y., Alp, E. Ercan, More, Karren L., Zelenay, Piotr, Holby, Edward F., and Neidig, Michael L. 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. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b03779.
Kneebone, Jared L., Daifuku, Stephanie L., Kehl, Jeffrey A., Wu, Gang, Chung, Hoon T., Hu, Michael Y., Alp, E. Ercan, More, Karren L., Zelenay, Piotr, Holby, Edward F., & Neidig, Michael L. 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. United States. doi:10.1021/acs.jpcc.7b03779.
Kneebone, Jared L., Daifuku, Stephanie L., Kehl, Jeffrey A., Wu, Gang, Chung, Hoon T., Hu, Michael Y., Alp, E. Ercan, More, Karren L., Zelenay, Piotr, Holby, Edward F., and Neidig, Michael L. Thu . "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". United States. doi:10.1021/acs.jpcc.7b03779.
@article{osti_1376622,
title = {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},
author = {Kneebone, Jared L. and Daifuku, Stephanie L. and Kehl, Jeffrey A. and Wu, Gang and Chung, Hoon T. and Hu, Michael Y. and Alp, E. Ercan and More, Karren L. and Zelenay, Piotr and Holby, Edward F. and Neidig, Michael L.},
abstractNote = {While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for 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 towards O2 or O2-analog 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 selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO(g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO(g) probe molecules. Moreover, such sites are likely also reactive to O2, possibly serving as the ORR active sites in the synthesized materials.},
doi = {10.1021/acs.jpcc.7b03779},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 30,
volume = 121,
place = {United States},
year = {2017},
month = {7}
}

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