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Title: Progress in the Development of Fe-Based PGM-Free Electrocatalysts for the Oxygen Reduction Reaction

Abstract

Development of alternative energy sources is crucial to tackle challenges encountered by the growing global energy demand. Hydrogen fuel, a promising way to store energy produced from renewable power sources, can be converted into electrical energy at high efficiency via direct electrochemical conversion in fuel cells, releasing water as the sole byproduct. One important drawback to current fuel-cell technology is the high content of platinum-group-metal (PGM) electrocatalysts required to perform the sluggish oxygen reduction reaction (ORR). Addressing this challenge, remarkable progress has been made in the development of low-cost PGM-free electrocatalysts synthesized from inexpensive, earth-abundant, and easily sourced materials such as iron, nitrogen, and carbon (Fe–N–C). PGM-free Fe–N–C electrocatalysts now exhibit ORR activities approaching that of PGM electrocatalysts but at a fraction of the cost, promising to significantly reduce overall fuel-cell technology costs. Here in this paper, recent developments in PGM-free electrocatalysis, demonstrating increased fuel-cell performance, as well as efforts aimed at understanding the key limiting factor, i.e., the nature of the PGM-free active site, are summarized. Further improvements will be accomplished through the controlled and/or rationally designed synthesis of materials with higher active-site densities, while at the same time establishing methods to mitigate catalyst degradation.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE). Fuel Cell Technologies Program (EE-3F); USDOE
OSTI Identifier:
1499359
Alternate Identifier(s):
OSTI ID: 1495531
Report Number(s):
LA-UR-18-29583
Journal ID: ISSN 0935-9648
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 31; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Energy Sciences; fuel cells; nonprecious metal electrocatalysts; oxygen reduction reaction (ORR); platinum‐group‐metal‐free (PGM‐free) electrocatalysts

Citation Formats

Martinez, Ulises, Komini Babu, Siddharth, Holby, Edward F., Yin, Xi, and Zelenay, Piotr. Progress in the Development of Fe-Based PGM-Free Electrocatalysts for the Oxygen Reduction Reaction. United States: N. p., 2019. Web. doi:10.1002/adma.201806545.
Martinez, Ulises, Komini Babu, Siddharth, Holby, Edward F., Yin, Xi, & Zelenay, Piotr. Progress in the Development of Fe-Based PGM-Free Electrocatalysts for the Oxygen Reduction Reaction. United States. https://doi.org/10.1002/adma.201806545
Martinez, Ulises, Komini Babu, Siddharth, Holby, Edward F., Yin, Xi, and Zelenay, Piotr. Thu . "Progress in the Development of Fe-Based PGM-Free Electrocatalysts for the Oxygen Reduction Reaction". United States. https://doi.org/10.1002/adma.201806545. https://www.osti.gov/servlets/purl/1499359.
@article{osti_1499359,
title = {Progress in the Development of Fe-Based PGM-Free Electrocatalysts for the Oxygen Reduction Reaction},
author = {Martinez, Ulises and Komini Babu, Siddharth and Holby, Edward F. and Yin, Xi and Zelenay, Piotr},
abstractNote = {Development of alternative energy sources is crucial to tackle challenges encountered by the growing global energy demand. Hydrogen fuel, a promising way to store energy produced from renewable power sources, can be converted into electrical energy at high efficiency via direct electrochemical conversion in fuel cells, releasing water as the sole byproduct. One important drawback to current fuel-cell technology is the high content of platinum-group-metal (PGM) electrocatalysts required to perform the sluggish oxygen reduction reaction (ORR). Addressing this challenge, remarkable progress has been made in the development of low-cost PGM-free electrocatalysts synthesized from inexpensive, earth-abundant, and easily sourced materials such as iron, nitrogen, and carbon (Fe–N–C). PGM-free Fe–N–C electrocatalysts now exhibit ORR activities approaching that of PGM electrocatalysts but at a fraction of the cost, promising to significantly reduce overall fuel-cell technology costs. Here in this paper, recent developments in PGM-free electrocatalysis, demonstrating increased fuel-cell performance, as well as efforts aimed at understanding the key limiting factor, i.e., the nature of the PGM-free active site, are summarized. Further improvements will be accomplished through the controlled and/or rationally designed synthesis of materials with higher active-site densities, while at the same time establishing methods to mitigate catalyst degradation.},
doi = {10.1002/adma.201806545},
journal = {Advanced Materials},
number = 31,
volume = 31,
place = {United States},
year = {Thu Feb 21 00:00:00 EST 2019},
month = {Thu Feb 21 00:00:00 EST 2019}
}

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  • Choi, Ja-Yeon; Yang, Lijun; Kishimoto, Takeaki
  • Energy & Environmental Science, Vol. 10, Issue 1
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Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst
journal, August 2017


Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells
journal, April 2009

  • Lefèvre, Michel; Proietti, Eric; Jaouen, Frédéric
  • Science, Vol. 324, Issue 5923, p. 71-74
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A comprehensive review on PEM water electrolysis
journal, April 2013

  • Carmo, Marcelo; Fritz, David L.; Mergel, Jürgen
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Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts
journal, January 2016


Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks
journal, January 2017


A density functional theory study of oxygen reduction reaction on non-PGM Fe–Nx–C electrocatalysts
journal, January 2014

  • Kattel, Shyam; Atanassov, Plamen; Kiefer, Boris
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 27
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New insights into non-precious metal catalyst layer designs for proton exchange membrane fuel cells: Improving performance and stability
journal, March 2017


Design criteria for stable Pt/C fuel cell catalysts
journal, January 2014

  • Meier, Josef C.; Galeano, Carolina; Katsounaros, Ioannis
  • Beilstein Journal of Nanotechnology, Vol. 5
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Water Management in PEM Fuel Cells with Non-Precious Metal Catalyst Electrodes
journal, July 2015

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Works referencing / citing this record:

On the Influence of Oxygen on the Degradation of Fe‐N‐C Catalysts
journal, February 2020

  • Kumar, Kavita; Dubau, Laetitia; Mermoux, Michel
  • Angewandte Chemie International Edition, Vol. 59, Issue 8
  • DOI: 10.1002/anie.201912451

Performance of Polymer Electrolyte Fuel Cell Electrodes with Atomically Dispersed (AD) Fe-C-N ORR Catalyst
journal, January 2019

  • Ahluwalia, R. K.; Wang, X.; Osmieri, L.
  • Journal of The Electrochemical Society, Vol. 166, Issue 14
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Revealing the nature of active sites in electrocatalysis
journal, January 2019

  • Garlyyev, Batyr; Fichtner, Johannes; Piqué, Oriol
  • Chemical Science, Vol. 10, Issue 35
  • DOI: 10.1039/c9sc02654a

Boosting the performance of the Fe–N–C catalyst for the oxygen reduction reaction by introducing single-walled carbon nanohorns as branches on carbon fibers
journal, January 2019

  • Zhang, Jianshuo; Liu, Yang; Yu, Zhoubin
  • Journal of Materials Chemistry A, Vol. 7, Issue 40
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Boosting the hydrogen evolution activity of a Co–N–C electrocatalyst by codoping with Al
journal, January 2019

  • Zhou, Xiao; Yu, Haoran; Liu, Yang
  • RSC Advances, Vol. 9, Issue 58
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Revealing the nature of active sites in electrocatalysis
journal, January 2019

  • Garlyyev, Batyr; Fichtner, Johannes; Piqué, Oriol
  • Chemical Science, Vol. 10, Issue 35
  • DOI: 10.1039/c9sc02654a

Oxygen Reduction Reactions on Single‐ or Few‐Atom Discrete Active Sites for Heterogeneous Catalysis
journal, September 2019

  • Sharifi, Tiva; Gracia‐Espino, Eduardo; Chen, Anran
  • Advanced Energy Materials, Vol. 10, Issue 11
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Platinum group metal-free catalysts boost cost competitiveness of fuel cell vehicles
journal, July 2019


Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals
journal, January 2019

  • Martinez, Ulises; Holby, Edward F.; Babu, Siddharth Komini
  • Journal of The Electrochemical Society, Vol. 166, Issue 7
  • DOI: 10.1149/2.0201907jes

In Situ and Operando Characterization of Proton Exchange Membrane Fuel Cells
journal, August 2019


On the Influence of Oxygen on the Degradation of Fe‐N‐C Catalysts
journal, January 2020

  • Kumar, Kavita; Dubau, Laetitia; Mermoux, Michel
  • Angewandte Chemie, Vol. 132, Issue 8
  • DOI: 10.1002/ange.201912451