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Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts

Journal Article · · Nature Catalysis
 [1];  [2];  [3];  [1];  [4];  [4];  [5];  [6];  [7];  [8];  [9];  [1];  [9];  [9];  [3];  [10];  [11];  [12];  [1]
  1. Univ. at Buffalo, NY (United States)
  2. Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), Indianapolis, IN (United States); Purdue Univ., West Lafayette, IN (United States)
  3. Univ. of Pittsburgh, PA (United States)
  4. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
  5. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
  6. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  7. Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Univ. of Chicago, IL (United States)
  8. Univ. of South Carolina, Columbia, SC (United States)
  9. Oregon State Univ., Corvallis, OR (United States)
  10. Indiana Univ.-Purdue Univ. Indianapolis (IUPUI), Indianapolis, IN (United States)
  11. Argonne National Laboratory (ANL), Argonne, IL (United States)
  12. INRS Énergie Matériaux Télécommunications Research Centre, Québec (Canada)
+ Show Author Affiliations
Fe–N–C catalysts are the most promising platinum group metal-free oxygen-reduction catalysts, but they suffer from a low density of active metal sites and the so-called activity–stability trade-off. Here we report an Fe–N–C catalyst prepared by adding an optimal amount of H2 to the traditional inert atmosphere during the thermal activation. The presence of H2 significantly increases the total density of FeN4 sites, suppressing the unstable pyrrolic-N-coordinated S1 sites and favouring the stable pyridinic-N-coordinated S2 sites with shortened Fe–N bond lengths. Here, we propose that the intrinsically stable S2 sites are probably arranged in well-graphitized carbon layers, and the S1 sites exist in less-graphitized carbon. H2 could remove unstable S1 sites and retain stable S2 sites during the pyrolysis to break the challenging activity–stability trade-off. The Fe–N–C catalyst in membrane electrode assemblies maintains a current density of 67 mA cm-2 at 0.8 V (H2–air) after 30,000 voltage cycles (0.60 to 0.95 V under H2–air), achieving encouraging durability and performance simultaneously.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)
Grant/Contract Number:
AC02-06CH11357; AC05-00OR22725
OSTI ID:
2281111
Journal Information:
Nature Catalysis, Journal Name: Nature Catalysis Journal Issue: 12 Vol. 6; ISSN 2520-1158
Publisher:
Springer NatureCopyright Statement
Country of Publication:
United States
Language:
English

References (64)

Electrocatalysis with Single-Metal Atom Sites in Doped Carbon Matrices book February 2022
57 Fe Mössbauer Spectroscopy Characterization of Electrocatalysts journal December 2018
Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction journal December 2018
PGM‐Free Cathode Catalysts for PEM Fuel Cells: A Mini‐Review on Stability Challenges journal December 2018
Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion journal November 2019
On the Influence of Oxygen on the Degradation of Fe‐N‐C Catalysts journal February 2020
Chemical Vapor Deposition for Atomically Dispersed and Nitrogen Coordinated Single Metal Site Catalysts journal September 2020
Engineering Atomically Dispersed FeN 4 Active Sites for CO 2 Electroreduction journal November 2020
Space‐Confined Anchoring of Fe−Nx on Concave N‐Doped Carbon Cubes for Catalyzing Oxygen Reduction journal February 2022
Energetics and thermodynamic stability of potential Fe(II)‐hexa‐aza‐active sites for O2 reduction in PEM fuel cells journal November 2022
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Surface linear potential sweep voltammetry journal May 1974
The surface energy of metals journal August 1998
Single-Iron Site Catalysts with Self-Assembled Dual-size Architecture and Hierarchical Porosity for Proton-Exchange Membrane Fuel Cells journal December 2020
Facile synthesis of MOF-derived concave cube nanocomposite by self-templated toward lightweight and wideband microwave absorption journal January 2022
Recent advances of Fe–N–C pyrolyzed catalysts for the oxygen reduction reaction journal October 2020
Pitfalls in X-ray absorption spectroscopy analysis and interpretation: A practical guide for general users journal December 2021
Durability evaluation of a Fe–N–C catalyst in polymer electrolyte fuel cell environment via accelerated stress tests journal December 2020
PGM-Free Oxygen-Reduction Catalyst Development for Proton-Exchange Membrane Fuel Cells: Challenges, Solutions, and Promises journal January 2022
Role of Local Carbon Structure Surrounding FeN 4 Sites in Boosting the Catalytic Activity for Oxygen Reduction journal May 2017
Identifying Iron–Nitrogen/Carbon Active Structures for Oxygen Reduction Reaction under the Effect of Electrode Potential journal March 2020
Fe–N–C Electrocatalyst and Its Electrode: Are We Talking about the Same Material? journal January 2023
High Power Density Platinum Group Metal-free Cathodes for Polymer Electrolyte Fuel Cells journal December 2019
Fe–N–C Electrocatalysts’ Durability: Effects of Single Atoms’ Mobility and Clustering journal December 2020
Recent Insights into the Oxygen-Reduction Electrocatalysis of Fe/N/C Materials journal September 2019
Understanding Active Sites in Pyrolyzed Fe–N–C Catalysts for Fuel Cell Cathodes by Bridging Density Functional Theory Calculations and 57 Fe Mössbauer Spectroscopy journal September 2019
Fe–N–C Catalyst Graphitic Layer Structure and Fuel Cell Performance journal June 2017
Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction journal April 2013
Resolving the Dilemma of Fe–N–C Catalysts by the Selective Synthesis of Tetrapyrrolic Active Sites via an Imprinting Strategy journal October 2021
Identification of the Catalytically Dominant Iron Environment in Iron- and Nitrogen-Doped Carbon Catalysts for the Oxygen Reduction Reaction journal August 2022
On an Easy Way To Prepare Metal–Nitrogen Doped Carbon with Exclusive Presence of MeN 4 -type Sites Active for the ORR journal January 2016
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation journal September 2017
O 2 Reduction in PEM Fuel Cells: Activity and Active Site Structural Information for Catalysts Obtained by the Pyrolysis at High Temperature of Fe Precursors journal November 2000
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode journal November 2004
Heat-Treated Fe/N/C Catalysts for O2 Electroreduction:  Are Active Sites Hosted in Micropores? journal March 2006
O 2 Reduction Mechanism on Non-Noble Metal Catalysts for PEM Fuel Cells. Part I: Experimental Rates of O 2 Electroreduction, H 2 O 2 Electroreduction, and H 2 O 2 Disproportionation journal July 2009
In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts journal October 2016
Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells journal August 2011
Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials journal August 2015
A pyridinic Fe-N4 macrocycle models the active sites in Fe/N-doped carbon electrocatalysts journal October 2020
Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells journal July 2022
Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells journal March 2019
Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation journal July 2019
Identification of durable and non-durable FeNx sites in Fe–N–C materials for proton exchange membrane fuel cells journal December 2020
Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells journal November 2020
Solving the activity–stability trade-off riddle journal January 2021
High loading of single atomic iron sites in Fe–NC oxygen reduction catalysts for proton exchange membrane fuel cells journal April 2022
Standardized protocols for evaluating platinum group metal-free oxygen reduction reaction electrocatalysts in polymer electrolyte fuel cells journal May 2022
Iron-catalyzed graphitization of biomass journal January 2015
High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites journal January 2019
Methanol tolerance of atomically dispersed single metal site catalysts: mechanistic understanding and high-performance direct methanol fuel cells journal January 2020
Atomically dispersed single iron sites for promoting Pt and Pt 3 Co fuel cell catalysts: performance and durability improvements journal January 2021
Hydrogen generation via ammonia decomposition on highly efficient and stable Ru-free catalysts: approaching complete conversion at 450 °C journal January 2022
Accurate and efficient algorithm for Bader charge integration journal February 2011
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways journal February 2014
Inhomogeneous Electron Gas journal November 1964
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Special points for Brillouin-zone integrations journal June 1976
Ab initiomolecular dynamics for liquid metals journal January 1993
Generalized Gradient Approximation Made Simple journal October 1996
Raman Spectrum of Graphene and Graphene Layers journal October 2006
Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells journal April 2009
High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt journal April 2011
Microstructure, Morphology and General Physical Properties book January 1993

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25 ENERGY STORAGE
Fe-N-C catalysts
durability
fuel cells
oxygen reduction reaction
single metal sites