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Title: Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst

Abstract

Platinum group metal–free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)–based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H2)–air fuel cell. We demonstrate H2-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. In current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The catalytic active site we proposed, carbon-embedded nitrogen-coordinated iron (FeN4), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [2]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1376619
Alternate Identifier(s):
OSTI ID: 1458952
Report Number(s):
LA-UR-16-25762
Journal ID: ISSN 0036-8075
Grant/Contract Number:  
AC05-00OR22725; AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Science
Additional Journal Information:
Journal Volume: 357; Journal Issue: 6350; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Energy Sciences; fuel cell, oxygen reduction reaction, PGM-free catalysts

Citation Formats

Chung, Hoon T., Cullen, David A., Higgins, Drew, Sneed, Brian T., Holby, Edward F., More, Karren L., and Zelenay, Piotr. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. United States: N. p., 2017. Web. doi:10.1126/science.aan2255.
Chung, Hoon T., Cullen, David A., Higgins, Drew, Sneed, Brian T., Holby, Edward F., More, Karren L., & Zelenay, Piotr. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. United States. doi:10.1126/science.aan2255.
Chung, Hoon T., Cullen, David A., Higgins, Drew, Sneed, Brian T., Holby, Edward F., More, Karren L., and Zelenay, Piotr. Fri . "Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst". United States. doi:10.1126/science.aan2255. https://www.osti.gov/servlets/purl/1376619.
@article{osti_1376619,
title = {Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst},
author = {Chung, Hoon T. and Cullen, David A. and Higgins, Drew and Sneed, Brian T. and Holby, Edward F. and More, Karren L. and Zelenay, Piotr},
abstractNote = {Platinum group metal–free (PGM-free) metal-nitrogen-carbon catalysts have emerged as a promising alternative to their costly platinum (Pt)–based counterparts in polymer electrolyte fuel cells (PEFCs) but still face some major challenges, including (i) the identification of the most relevant catalytic site for the oxygen reduction reaction (ORR) and (ii) demonstration of competitive PEFC performance under automotive-application conditions in the hydrogen (H2)–air fuel cell. We demonstrate H2-air performance gains achieved with an iron-nitrogen-carbon catalyst synthesized with two nitrogen precursors that developed hierarchical porosity. In current densities recorded in the kinetic region of cathode operation, at fuel cell voltages greater than ~0.75 V, were the same as those obtained with a Pt cathode at a loading of 0.1 milligram of Pt per centimeter squared. The catalytic active site we proposed, carbon-embedded nitrogen-coordinated iron (FeN4), was directly visualized with aberration-corrected scanning transmission electron microscopy, and the contributions of these active sites associated with specific lattice-level carbon structures were explored computationally.},
doi = {10.1126/science.aan2255},
journal = {Science},
number = 6350,
volume = 357,
place = {United States},
year = {2017},
month = {8}
}

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Cited by: 113 works
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Figures / Tables:

Fig. 1 Fig. 1: Hierarchical pore structure. (A) Micropore and mesopore size distributions. The micropore size distribution had peaks associated with three pore widths: 0.8, 1.1, and 1.5 nm; (B) and (C) SEM images of PANI-Fe-C and (CM+PANI)-Fe-C catalysts, respectively, demonstrating the effect of CM in macropore formation.

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.