skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network

Abstract

Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A∙cm-3 at 0.9 V or 450 A∙cm-3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed.

Authors:
 [1];  [2];  [3];  [4];  [2]
  1. Argonne National Lab., Argonne, IL (United States). Chemical Sciences and Engineering Div.; Beihang Univ., Beijing (China). School of Materials Science and Engineering.
  2. Argonne National Lab., Argonne, IL (United States). Chemical Sciences and Engineering Div.
  3. Argonne National Lab., Argonne, IL (United States). Chemical Sciences and Engineering Div.; Alcoa Technical Center, New Kinsington, PA (United States)
  4. National Univ. of Singapore (Singapore). Dept. of Chemical and Biomolecular Engineering.
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO)
OSTI Identifier:
1215638
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 112; Journal Issue: 34; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; 36 MATERIALS SCIENCE; 33 ADVANCED PROPULSION SYSTEMS; nanofibrous; nonprecious metal catalyst; metal-organic framework; fuel cell; oxygen reduction

Citation Formats

Shui, Jianglan, Chen, Chen, Grabstanowicz, Lauren, Zhao, Dan, and Liu, Di -Jia. Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network. United States: N. p., 2015. Web. doi:10.1073/pnas.1507159112.
Shui, Jianglan, Chen, Chen, Grabstanowicz, Lauren, Zhao, Dan, & Liu, Di -Jia. Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network. United States. https://doi.org/10.1073/pnas.1507159112
Shui, Jianglan, Chen, Chen, Grabstanowicz, Lauren, Zhao, Dan, and Liu, Di -Jia. 2015. "Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network". United States. https://doi.org/10.1073/pnas.1507159112. https://www.osti.gov/servlets/purl/1215638.
@article{osti_1215638,
title = {Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network},
author = {Shui, Jianglan and Chen, Chen and Grabstanowicz, Lauren and Zhao, Dan and Liu, Di -Jia},
abstractNote = {Fuel cell vehicles, the only all-electric technology with a demonstrated >300 miles per fill travel range, use Pt as the electrode catalyst. The high price of Pt creates a major cost barrier for large-scale implementation of polymer electrolyte membrane fuel cells. Nonprecious metal catalysts (NPMCs) represent attractive low-cost alternatives. However, a significantly lower turnover frequency at the individual catalytic site renders the traditional carbon-supported NPMCs inadequate in reaching the desired performance afforded by Pt. Unconventional catalyst design aiming at maximizing the active site density at much improved mass and charge transports is essential for the next-generation NPMC. We report here a method of preparing highly efficient, nanofibrous NPMC for cathodic oxygen reduction reaction by electrospinning a polymer solution containing ferrous organometallics and zeolitic imidazolate framework followed by thermal activation. The catalyst offers a carbon nanonetwork architecture made of microporous nanofibers decorated by uniformly distributed high-density active sites. In a single-cell test, the membrane electrode containing such a catalyst delivered unprecedented volumetric activities of 3.3 A∙cm-3 at 0.9 V or 450 A∙cm-3 extrapolated at 0.8 V, representing the highest reported value in the literature. Improved fuel cell durability was also observed.},
doi = {10.1073/pnas.1507159112},
url = {https://www.osti.gov/biblio/1215638}, journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 34,
volume = 112,
place = {United States},
year = {Tue Aug 25 00:00:00 EDT 2015},
month = {Tue Aug 25 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 325 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs
journal, March 2005


The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction
journal, April 2006


A class of non-precious metal composite catalysts for fuel cells
journal, September 2006


Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction
journal, September 2013


Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction
journal, February 2009


Graphene-Based Carbon Nitride Nanosheets as Efficient Metal-Free Electrocatalysts for Oxygen Reduction Reactions
journal, May 2011


Cobalt Imidazolate Framework as Precursor for Oxygen Reduction Reaction Electrocatalysts
journal, January 2011


Average turn-over frequency of O2 electro-reduction for Fe/N/C and Co/N/C catalysts in PEFCs
journal, May 2007


Increasing the activity of Fe/N/C catalysts in PEM fuel cell cathodes using carbon blacks with a high-disordered carbon content
journal, October 2008


Iron imidazolate framework as precursor for electrocatalysts in polymer electrolyte membrane fuel cells
journal, January 2012


A New Fuel Cell Cathode Catalyst
journal, March 1964


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


Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells
journal, August 2011


A Highly Active and Support-Free Oxygen Reduction Catalyst Prepared from Ultrahigh-Surface-Area Porous Polyporphyrin
journal, June 2013


Highly Efficient Non-Precious Metal Electrocatalysts Prepared from One-Pot Synthesized Zeolitic Imidazolate Frameworks
journal, December 2013


High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011


Heat-Treated Fe/N/C Catalysts for O2 Electroreduction:  Are Active Sites Hosted in Micropores?
journal, March 2006


Optimized Synthesis of Fe/N/C Cathode Catalysts for PEM Fuel Cells: A Matter of Iron-Ligand Coordination Strength
journal, May 2013


Non-precious metal oxygen reduction catalyst for PEM fuel cells based on nitroaniline precursor
journal, April 2008


Cross-Laboratory Experimental Study of Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction
journal, July 2009


Platinum Nanowires Produced by Electrospinning
journal, April 2009


Rapid Room-Temperature Synthesis of Zeolitic Imidazolate Frameworks by Using Mechanochemistry
journal, November 2010


Impact of Preparation and Handling on the Hydrogen Storage Properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5)
journal, November 2007


Rapid Room-Temperature Synthesis of Zeolitic Imidazolate Frameworks by Using Mechanochemistry
journal, November 2010


Graphene-Based Carbon Nitride Nanosheets as Efficient Metal-Free Electrocatalysts for Oxygen Reduction Reactions
journal, May 2011


A Highly Active and Support-Free Oxygen Reduction Catalyst Prepared from Ultrahigh-Surface-Area Porous Polyporphyrin
journal, June 2013


Optimized Synthesis of Fe/N/C Cathode Catalysts for PEM Fuel Cells: A Matter of Iron-Ligand Coordination Strength
journal, May 2013


Works referencing / citing this record:

Integrating PGM‐Free Catalysts into Catalyst Layers and Proton Exchange Membrane Fuel Cell Devices
journal, December 2018


57 Fe Mössbauer Spectroscopy Characterization of Electrocatalysts
journal, December 2018


Metal-Organic Framework-Based Nanomaterials for Electrocatalysis
journal, May 2016


Design Strategies toward Advanced MOF-Derived Electrocatalysts for Energy-Conversion Reactions
journal, June 2017


Molecular Design of Single‐Atom Catalysts for Oxygen Reduction Reaction
journal, February 2020


The Solid-Phase Synthesis of an Fe-N-C Electrocatalyst for High-Power Proton-Exchange Membrane Fuel Cells
journal, January 2018


Surface Fluorination to Boost the Stability of the Fe/N/C Cathode in Proton Exchange Membrane Fuel Cells
journal, November 2017


Recent Progress of Carbon-Based Materials in Oxygen Reduction Reaction Catalysis
journal, January 2018


Heteroatom-Doped Carbon Materials for Electrocatalysis
journal, June 2017


Microporous Solids En Route to Heterogeneous Electrocatalysis: The Oxygen Reduction Reaction
journal, December 2019


Hollow Carbon Nanopolyhedra for Enhanced Electrocatalysis via Confined Hierarchical Porosity
journal, April 2017


Design and Integration of Molecular-Type Catalysts in Fuel-Cell Technology
journal, June 2018


Application of Nanomaterials Prepared by Thermolysis of Metal Chelates
book, January 2018


Influence of sulfur in the precursor mixture on the structural composition of Fe-N-C catalysts
journal, January 2018


Electrochemical investigation of Pt–Pd nanoparticles formation–reduction kinetics and nucleation mechanisms
journal, September 2019


Strategies for Enhancing the Electrocatalytic Activity of M–N/C Catalysts for the Oxygen Reduction Reaction
journal, May 2018


Rational Design and Synthesis of Low-Temperature Fuel Cell Electrocatalysts
journal, March 2018


Nanomaterials derived from metal–organic frameworks
journal, December 2017


In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts
journal, October 2016


Zigzag carbon as efficient and stable oxygen reduction electrocatalyst for proton exchange membrane fuel cells
journal, September 2018


A complex metal-organic framework catalyst for microwave-assisted radical polymerization
journal, October 2018


Biochemistry-inspired direct synthesis of nitrogen and phosphorus dual-doped microporous carbon spheres for enhanced electrocatalysis
journal, January 2016


Fe–N-functionalized carbon electrocatalyst derived from a zeolitic imidazolate framework for oxygen reduction: Fe and NH 3 treatment effects
journal, January 2018


Redox-active and semi-conducting donor–acceptor conjugated microporous polymers as metal-free ORR catalysts
journal, January 2018


On the role of hydroxide species in sulphur- and nitrogen-doped cobalt-based carbon catalysts for the oxygen evolution reaction
journal, January 2018


Anodic engineering towards high-performance direct methanol fuel cells with non-precious-metal cathode catalysts
journal, January 2020


Single-atomic cobalt sites embedded in hierarchically ordered porous nitrogen-doped carbon as a superior bifunctional electrocatalyst
journal, November 2018


Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst
journal, August 2017


Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells
journal, January 2019


The Challenge of Achieving a High Density of Fe-Based Active Sites in a Highly Graphitic Carbon Matrix
journal, February 2019


Recent Progress in the Identification of Active Sites in Pyrolyzed Fe−N/C Catalysts and Insights into Their Role in Oxygen Reduction Reaction
journal, September 2017


Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction
journal, December 2018


The Solid-Phase Synthesis of an Fe-N-C Electrocatalyst for High-Power Proton-Exchange Membrane Fuel Cells
journal, January 2018


Identification of Catalytic Sites for Oxygen Reduction in Metal/Nitrogen‐Doped Carbons with Encapsulated Metal Nanoparticles
journal, January 2020


A Dynamically Stabilized Single‐Nickel Electrocatalyst for Selective Reduction of Oxygen to Hydrogen Peroxide
journal, July 2018


Fe 2 N/S/N Codecorated Hierarchical Porous Carbon Nanosheets for Trifunctional Electrocatalysis
journal, October 2018


High performance platinum single atom electrocatalyst for oxygen reduction reaction
journal, July 2017


Phosphor and nitrogen co-doped rutile TiO 2 covered on TiN for oxygen reduction reaction in acidic media
journal, January 2019


Layer-by-layer decoration of MOFs on electrospun nanofibers
journal, January 2018


Planar polymer electrolyte membrane fuel cells: powering portable devices from hydrogen
journal, January 2020


Metal–Organic Frameworks (MOFs) and MOF-Derived Materials for Energy Storage and Conversion
journal, November 2018


Zirconium Oxynitride-Catalyzed Oxygen Reduction Reaction at Polymer Electrolyte Fuel Cell Cathodes
journal, February 2017


High performance platinum single atom electrocatalyst for oxygen reduction reaction
journal, July 2017


Pt-free carbon-based fuel cell catalyst prepared from spherical polyimide for enhanced oxygen diffusion
journal, March 2016


Recent developments of nano-structured materials as the catalysts for oxygen reduction reaction
journal, April 2018