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Title: Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography

Abstract

Further reduction of Pt in hydrogen fuel cells is hampered by reactant transport losses near the catalyst surface, especially for degraded catalysts. Strategically mitigating these performance losses requires an improved understanding of the catalyst nanostructure, which controls local transport and catalyst durability. We apply cryo-tomography in a scanning transmission electron microscope (STEM) to quantify the three-dimensional structure of carbon-supported Pt catalysts and correlate to their electrochemical accessibility. We present results for two carbon supports: Vulcan, a compact support with a large majority of Pt observed on the exterior, and HSC, a porous support with a majority of Pt observed within interior carbon pores, which have relatively constrictive openings. Increasing Pt content shifts the Pt distribution to the exterior on both carbon supports. By correlating to the electrochemical surface area, we find that all Pt surface area is accessible to protons in liquid. However, the interior Pt fraction quantitatively tracks Pt utilization losses at low humidity, indicating that the interior Pt is inaccessible to the proton-conducting ionomer, likely because narrow carbon pore openings block ionomer infiltration. These results imply different proton transport mechanisms for interior and exterior Pt, and quantitatively describe the catalyst structure, supporting development of transport and durability models.

Authors:
ORCiD logo; ; ; ORCiD logo; ; ; ; ; ; ;
Publication Date:
Research Org.:
General Motors Co., Warren, MI (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO)
OSTI Identifier:
1423148
Alternate Identifier(s):
OSTI ID: 1509886
Grant/Contract Number:  
EE0007271
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 165 Journal Issue: 3; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Carbon support; Nanostructure; Transport

Citation Formats

Padgett, Elliot, Andrejevic, Nina, Liu, Zhongyi, Kongkanand, Anusorn, Gu, Wenbin, Moriyama, Koji, Jiang, Yi, Kumaraguru, Swami, Moylan, Thomas E., Kukreja, Ratandeep, and Muller, David A. Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography. United States: N. p., 2018. Web. doi:10.1149/2.0541803jes.
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Padgett, Elliot, Andrejevic, Nina, Liu, Zhongyi, Kongkanand, Anusorn, Gu, Wenbin, Moriyama, Koji, Jiang, Yi, Kumaraguru, Swami, Moylan, Thomas E., Kukreja, Ratandeep, & Muller, David A. Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography. United States. https://doi.org/10.1149/2.0541803jes
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Padgett, Elliot, Andrejevic, Nina, Liu, Zhongyi, Kongkanand, Anusorn, Gu, Wenbin, Moriyama, Koji, Jiang, Yi, Kumaraguru, Swami, Moylan, Thomas E., Kukreja, Ratandeep, and Muller, David A. Thu . "Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography". United States. https://doi.org/10.1149/2.0541803jes.
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@article{osti_1423148,
title = {Editors' Choice—Connecting Fuel Cell Catalyst Nanostructure and Accessibility Using Quantitative Cryo-STEM Tomography},
author = {Padgett, Elliot and Andrejevic, Nina and Liu, Zhongyi and Kongkanand, Anusorn and Gu, Wenbin and Moriyama, Koji and Jiang, Yi and Kumaraguru, Swami and Moylan, Thomas E. and Kukreja, Ratandeep and Muller, David A.},
abstractNote = {Further reduction of Pt in hydrogen fuel cells is hampered by reactant transport losses near the catalyst surface, especially for degraded catalysts. Strategically mitigating these performance losses requires an improved understanding of the catalyst nanostructure, which controls local transport and catalyst durability. We apply cryo-tomography in a scanning transmission electron microscope (STEM) to quantify the three-dimensional structure of carbon-supported Pt catalysts and correlate to their electrochemical accessibility. We present results for two carbon supports: Vulcan, a compact support with a large majority of Pt observed on the exterior, and HSC, a porous support with a majority of Pt observed within interior carbon pores, which have relatively constrictive openings. Increasing Pt content shifts the Pt distribution to the exterior on both carbon supports. By correlating to the electrochemical surface area, we find that all Pt surface area is accessible to protons in liquid. However, the interior Pt fraction quantitatively tracks Pt utilization losses at low humidity, indicating that the interior Pt is inaccessible to the proton-conducting ionomer, likely because narrow carbon pore openings block ionomer infiltration. These results imply different proton transport mechanisms for interior and exterior Pt, and quantitatively describe the catalyst structure, supporting development of transport and durability models.},
doi = {10.1149/2.0541803jes},
journal = {Journal of the Electrochemical Society},
number = 3,
volume = 165,
place = {United States},
year = {Thu Feb 08 00:00:00 EST 2018},
month = {Thu Feb 08 00:00:00 EST 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1149/2.0541803jes
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Cited by: 95 works
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Figures / Tables:

Figure 1 Figure 1: Illustration of electron tomography procedure, shown for 50wt%Pt/Vulcan catalyst nanoparticles. High signal to noise ratio (SNR), distortion-free images are produced by summing aligned stacks of fast-acquisition STEM images. A tilt series of images, acquired as the specimen tilts from approximately −75° to 75° at 2° intervals, is alignedmore » to a common coordinate system and reconstructed to a 3D image of the specimen. The reconstruction is segmented to identify the material type represented in each voxel to allow quantitative analysis and more informative visualization, for instance here showing the carbon surface in gray, interior Pt particles in blue, and exterior Pt particles in red.« less
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Works referenced in this record:

Core-Protected Platinum Monolayer Shell High-Stability Electrocatalysts for Fuel-Cell Cathodes
journal, October 2010

  • Sasaki, Kotaro; Naohara, Hideo; Cai, Yun
  • Angewandte Chemie International Edition, Vol. 49, Issue 46, p. 8602-8607
  • DOI: 10.1002/anie.201004287

Carbon supports for low-temperature fuel cell catalysts
journal, April 2009

Solvothermal Synthesis of Platinum Alloy Nanoparticles for Oxygen Reduction Electrocatalysis
journal, May 2012

  • Carpenter, Michael K.; Moylan, Thomas E.; Kukreja, Ratandeep Singh
  • Journal of the American Chemical Society, Vol. 134, Issue 20
  • DOI: 10.1021/ja300756y

Recent Advances in the Application of Electron Tomography to Materials Chemistry
journal, August 2012

  • Leary, Rowan; Midgley, Paul A.; Thomas, John Meurig
  • Accounts of Chemical Research, Vol. 45, Issue 10
  • DOI: 10.1021/ar3001102

The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells
journal, March 2016

Record activity and stability of dealloyed bimetallic catalysts for proton exchange membrane fuel cells
journal, January 2015

  • Han, Binghong; Carlton, Christopher E.; Kongkanand, Anusorn
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE02144D

Activity, Stability, and Degradation Mechanisms of Dealloyed PtCu3 and PtCo3 Nanoparticle Fuel Cell Catalysts
journal, September 2011

Effects of carbon supports on Pt distribution, ionomer coverage and cathode performance for polymer electrolyte fuel cells
journal, May 2016

Gas transport inside and outside carbon supports of catalyst layers for PEM fuel cells
journal, November 2013

Influence of Ink Composition on the Electrochemical Properties of Pt/C Electrocatalysts
journal, March 2013

Computation of Minkowski Measures on 2d and 3d Binary Images
journal, June 2007

  • Legland, David; Kiêu, Kiên; Devaux, Marie-Françoise
  • Image Analysis & Stereology, Vol. 26, Issue 2
  • DOI: 10.5566/ias.v26.p83-92

Three-Dimensional Spatial Distributions of Pt Catalyst Nanoparticles on Carbon Substrates in Polymer Electrolyte Fuel Cells
journal, January 2011

Achieving High-Power PEM Fuel Cell Performance with an Ultralow-Pt-Content Core–Shell Catalyst
journal, February 2016

  • Kongkanand, Anusorn; Subramanian, Nalini P.; Yu, Yingchao
  • ACS Catalysis, Vol. 6, Issue 3
  • DOI: 10.1021/acscatal.5b02819

Transmission Electron Microtomography and Polymer Nanostructures
journal, February 2010

  • Jinnai, Hiroshi; Spontak, Richard J.; Nishi, Toshio
  • Macromolecules, Vol. 43, Issue 4
  • DOI: 10.1021/ma902035p

The Reconstruction of a Three-Dimensional Structure from Projections and its Application to Electron Microscopy
journal, June 1970

  • Crowther, R. A.; DeRosier, D. J.; Klug, A.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 317, Issue 1530
  • DOI: 10.1098/rspa.1970.0119

Effects of Microstructure of Carbon Support in the Catalyst Layer on the Performance of Polymer-Electrolyte Fuel Cells
journal, January 1996

  • Uchida, Makoto
  • Journal of The Electrochemical Society, Vol. 143, Issue 7
  • DOI: 10.1149/1.1836988

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces
journal, February 2014

The Impact of Platinum Loading on Oxygen Transport Resistance
journal, January 2012

  • Greszler, Thomas A.; Caulk, David; Sinha, Puneet
  • Journal of The Electrochemical Society, Vol. 159, Issue 12
  • DOI: 10.1149/2.061212jes

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

  • Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar
  • Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35
  • DOI: 10.1016/j.apcatb.2004.06.021

Platinum Monolayer Electrocatalysts for O2 Reduction:  Pt Monolayer on Pd(111) and on Carbon-Supported Pd Nanoparticles
journal, July 2004

  • Zhang, J.; Mo, Y.; Vukmirovic, M. B.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 30, p. 10955-10964
  • DOI: 10.1021/jp0379953

Multiscale Characterization of Some Commercial Carbon Blacks and Diesel Engine Soot
journal, October 2016

Synthesis and Oxygen Reduction Activity of Shape-Controlled Pt 3 Ni Nanopolyhedra
journal, February 2010

  • Zhang, Jun; Yang, Hongzhou; Fang, Jiye
  • Nano Letters, Vol. 10, Issue 2
  • DOI: 10.1021/nl903717z

Iterative methods for the three-dimensional reconstruction of an object from projections
journal, July 1972

A Critical Review of Modeling Transport Phenomena in Polymer-Electrolyte Fuel Cells
journal, January 2014

  • Weber, Adam Z.; Borup, Rodney L.; Darling, Robert M.
  • Journal of The Electrochemical Society, Vol. 161, Issue 12
  • DOI: 10.1149/2.0751412jes

(Plenary) Electrochemical Diagnostics and Modeling in Developing the PEMFC Cathode
journal, August 2016

  • Kongkanand, A.; Yarlagadda, V.; Garrick, T. R.
  • ECS Transactions, Vol. 75, Issue 14
  • DOI: 10.1149/07514.0025ecst

Analysis of proton exchange membrane fuel cell catalyst layers for reduction of platinum loading at Nissan
journal, December 2011

The Role of OOH Binding Site and Pt Surface Structure on ORR Activities
journal, January 2014

  • Jia, Qingying; Caldwell, Keegan; Ziegelbauer, Joseph M.
  • Journal of The Electrochemical Society, Vol. 161, Issue 14
  • DOI: 10.1149/2.1071412jes

Element-specific anisotropic growth of shaped platinum alloy nanocrystals
journal, December 2014

Imaging and Microanalysis of Thin Ionomer Layers by Scanning Transmission Electron Microscopy
journal, January 2014

  • Cullen, D. A.; Koestner, R.; Kukreja, R. S.
  • Journal of The Electrochemical Society, Vol. 161, Issue 10
  • DOI: 10.1149/2.1091410jes

The impact of the morphology of the carbon support on the activity and stability of nanoparticle fuel cell catalysts
journal, January 2016

  • Tuaev, Xenia; Rudi, Stefan; Strasser, Peter
  • Catalysis Science & Technology, Vol. 6, Issue 23
  • DOI: 10.1039/C6CY01679K

Molecular modeling of the proton density distribution in a water-filled slab-like nanopore bounded by Pt oxide and ionomer
journal, March 2016

Spatially Resolved Modeling of Electric Double Layers and Surface Chemistry for the Hydrogen Oxidation Reaction in Water-Filled Platinum–Carbon Electrodes
journal, April 2012

  • Zenyuk, Iryna V.; Litster, Shawn
  • The Journal of Physical Chemistry C, Vol. 116, Issue 18
  • DOI: 10.1021/jp300360m

Truncated Octahedral Pt 3 Ni Oxygen Reduction Reaction Electrocatalysts
journal, April 2010

  • Wu, Jianbo; Zhang, Junliang; Peng, Zhenmeng
  • Journal of the American Chemical Society, Vol. 132, Issue 14
  • DOI: 10.1021/ja100571h

Effect of the state of distribution of supported Pt nanoparticles on effective Pt utilization in polymer electrolyte fuel cells
journal, January 2013

  • Uchida, Makoto; Park, Young-Chul; Kakinuma, Katsuyoshi
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 27
  • DOI: 10.1039/c3cp51801a

Editors' Choice—Electrochemically Active Surface Area Measurement of Aged Pt Alloy Catalysts in PEM Fuel Cells by CO Stripping
journal, December 2016

  • Garrick, Taylor R.; Moylan, Thomas E.; Carpenter, Michael K.
  • Journal of The Electrochemical Society, Vol. 164, Issue 2
  • DOI: 10.1149/2.0381702jes

Spectroscopic in situ Measurements of the Relative Pt Skin Thicknesses and Porosities of Dealloyed PtM n (Ni, Co) Electrocatalysts
journal, December 2014

  • Caldwell, Keegan M.; Ramaker, David E.; Jia, Qingying
  • The Journal of Physical Chemistry C, Vol. 119, Issue 1
  • DOI: 10.1021/jp5098553

Synthesis and Characterization of 9 nm Pt–Ni Octahedra with a Record High Activity of 3.3 A/mg Pt for the Oxygen Reduction Reaction
journal, June 2013

  • Choi, Sang-Il; Xie, Shuifen; Shao, Minhua
  • Nano Letters, Vol. 13, Issue 7
  • DOI: 10.1021/nl401881z

Unexplained transport resistances for low-loaded fuel-cell catalyst layers
journal, January 2014

  • Weber, Adam Z.; Kusoglu, Ahmet
  • J. Mater. Chem. A, Vol. 2, Issue 41
  • DOI: 10.1039/C4TA02952F

Gas Transport Resistance in Polymer Electrolyte Thin Films on Oxygen Reduction Reaction Catalysts
journal, August 2015

The Impact of Carbon Stability on PEM Fuel Cell Startup and Shutdown Voltage Degradation
conference, January 2006

  • Yu, Paul T.; Gu, Wenbin; Makharia, Rohit
  • 210th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.2356199

Oxygen Reduction Reaction at Three-Phase Interfaces
journal, July 2010

  • Subbaraman, Ram; Strmcnik, Dusan; Paulikas, Arvydas P.
  • ChemPhysChem, Vol. 11, Issue 13
  • DOI: 10.1002/cphc.201000190

Characterizing Electrolyte and Platinum Interface in PEM Fuel Cells Using CO Displacement
journal, December 2016

  • Garrick, Taylor R.; Moylan, Thomas E.; Yarlagadda, Venkata
  • Journal of The Electrochemical Society, Vol. 164, Issue 2
  • DOI: 10.1149/2.0551702jes
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