Adsorption Characteristics of Perfluorosulfonic Acid Membrane Decomposition Products on a Platinum Electrode: An EQCM Study

Christ, Jason M.; Staub, Charles B.; Richards, Ryan; Dinh, Huyen N.

doi:10.1149/2.0841813jes

Title: Adsorption Characteristics of Perfluorosulfonic Acid Membrane Decomposition Products on a Platinum Electrode: An EQCM Study

Abstract

As hydrogen fuel cell vehicles move closer to mass commercialization, understanding the voltage losses due to contamination on low loading catalyst layers has become critical. It is imperative that contamination mechanisms are understood to mitigate these losses. In some cases, chemical breakdown of the polymer membrane can lead to formation of small molecules that can infiltrate and adsorb onto the catalyst layer, resulting in lower fuel cell performance and durability. Surface coverages of perfluorinated acid model compounds, representing polymer electrolyte membrane (PEM) chemical degradation products, were studied using an electrochemical quartz crystal microbalance (EQCM) with a polycrystalline platinum electrode. Perfluorosulfonic acid model compounds with a terminal sulfonic acid group exhibited no adsorption and no mass change. A similar model compound with a terminal carboxylic acid functional group exhibited higher surface coverage and stronger adsorption strength. Perfluorinated diacids, representing degradation products of a Nafion and 3M membrane, both showed mass increases well into the Pt oxide region, suggesting that the compounds were not fully displaced by surface oxides and that the terminal sulfonic acid group played a secondary role in the adsorption. Both perfluorinated chain length and functional group were found to play important roles in Pt surface adsorption characteristics.

Authors:

Christ, Jason M.; Staub, Charles B.; Richards, Ryan;

Publication Date:: Sat Oct 06 00:00:00 EDT 2018

Research Org.:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO)

OSTI Identifier:: 1476662

Alternate Identifier(s):: OSTI ID: 1478311

Report Number(s):: NREL/JA-5900-72621
Journal ID: ISSN 0013-4651; /jes/165/13/F1103.atom

Grant/Contract Number:: AC36-08GO28308

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: 13; Journal ID: ISSN 0013-4651

Publisher:: The Electrochemical Society

Country of Publication:: United States

Language:: English

Subject:: 30 DIRECT ENERGY CONVERSION; 36 MATERIALS SCIENCE; fuel cells; PEM; contaminants; EQCMB; PFSA

Citation Formats


                    Christ, Jason M., Staub, Charles B., Richards, Ryan, and Dinh, Huyen N. Adsorption Characteristics of Perfluorosulfonic Acid Membrane Decomposition Products on a Platinum Electrode: An EQCM Study.  United States: N. p., 2018. 
Web.  doi:10.1149/2.0841813jes.

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                    Christ, Jason M., Staub, Charles B., Richards, Ryan, & Dinh, Huyen N. Adsorption Characteristics of Perfluorosulfonic Acid Membrane Decomposition Products on a Platinum Electrode: An EQCM Study.  United States.  https://doi.org/10.1149/2.0841813jes

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                    Christ, Jason M., Staub, Charles B., Richards, Ryan, and Dinh, Huyen N. Sat .  
"Adsorption Characteristics of Perfluorosulfonic Acid Membrane Decomposition Products on a Platinum Electrode: An EQCM Study".  United States.  https://doi.org/10.1149/2.0841813jes.

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@article{osti_1476662,

  title        = {Adsorption Characteristics of Perfluorosulfonic Acid Membrane Decomposition Products on a Platinum Electrode: An EQCM Study},

  author       = {Christ, Jason M. and Staub, Charles B. and Richards, Ryan and Dinh, Huyen N.},

  abstractNote = {As hydrogen fuel cell vehicles move closer to mass commercialization, understanding the voltage losses due to contamination on low loading catalyst layers has become critical. It is imperative that contamination mechanisms are understood to mitigate these losses. In some cases, chemical breakdown of the polymer membrane can lead to formation of small molecules that can infiltrate and adsorb onto the catalyst layer, resulting in lower fuel cell performance and durability. Surface coverages of perfluorinated acid model compounds, representing polymer electrolyte membrane (PEM) chemical degradation products, were studied using an electrochemical quartz crystal microbalance (EQCM) with a polycrystalline platinum electrode. Perfluorosulfonic acid model compounds with a terminal sulfonic acid group exhibited no adsorption and no mass change. A similar model compound with a terminal carboxylic acid functional group exhibited higher surface coverage and stronger adsorption strength. Perfluorinated diacids, representing degradation products of a Nafion and 3M membrane, both showed mass increases well into the Pt oxide region, suggesting that the compounds were not fully displaced by surface oxides and that the terminal sulfonic acid group played a secondary role in the adsorption. Both perfluorinated chain length and functional group were found to play important roles in Pt surface adsorption characteristics.},

  doi          = {10.1149/2.0841813jes},

  journal      = {Journal of the Electrochemical Society},

  number       = 13,

  volume       = 165,

  place        = {United States},

  year         = {Sat Oct 06 00:00:00 EDT 2018},

  month        = {Sat Oct 06 00:00:00 EDT 2018}

}

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Title: Adsorption Characteristics of Perfluorosulfonic Acid Membrane Decomposition Products on a Platinum Electrode: An EQCM Study

Abstract

Citation Formats

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Potentiostatic charge displacement by exchanging adsorbed species on Pt(111) electrodes—acidic electrolytes with specific anion adsorption journal, August 1994

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A surface‐electrochemical basis for the direct logarithmic growth law for initial stages of extension of anodic oxide films formed at noble metals journal, December 1990

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PEMFC contamination model: Foreign cation exchange with ionomer protons
journal, August 2011

A surface‐electrochemical basis for the direct logarithmic growth law for initial stages of extension of anodic oxide films formed at noble metals
journal, December 1990

An FTIR study on the adsorption of acetate at the basal planes of platinum single-crystal electrodes
journal, October 1994

Electrochemical quartz crystal microbalance studies of adsorption and desorption of self-assembled monolayers of alkyl thiols on gold
journal, December 1993

Pt-Oxide Coverage-Dependent Oxygen Reduction Reaction (ORR) Kinetics
journal, January 2012

Chemical Degradation of Nafion Membranes under Mimic Fuel Cell Conditions as Investigated by Solid-State NMR Spectroscopy
journal, August 2010

Chemical Stability of Perfluorobis(sulfonyl)imide-Acid (PFIA) Ionomers in Open Circuit Voltage (OCV) Accelerated Test Conditions
journal, January 2018

Increasing Fuel Cell Efficiency by Using Ultra-Low Equivalent Weight Ionomers
journal, January 2017

Characterizing Leachant Contaminants from Fuel Cell Assembly Aids, a Prelude to Effects on Performance
journal, March 2013

Influence of Decomposition Products from Perfluorosulfonic Acid Membrane on Fuel Cell Performance
journal, January 2008

Assessing the adaptability to varying fuel supply of an autothermal reformer
journal, September 2008

Discovery of the Potential of Minimum Mass for Platinum Electrodes
journal, April 2011

Evaluating the Influence of PEMFC System Contaminants on the Performance of Pt Catalyst via Cyclic Voltammetry
journal, October 2013

Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts
journal, January 2014

Study of acetate adsorption at the platinum electrode/acid electrolyte interface using “blocking effects”: Influences of acetate adsorption on ethanol fuel cell electrodes
journal, March 2012

Influence of toluene contamination at the hydrogen Pt/C anode in a proton exchange membrane fuel cell
journal, November 2010

Effect, mechanism and recovery of nitrogen oxides poisoning on oxygen reduction reaction at Pt/C catalysts
journal, January 2011

Chemical Durability Studies of Perfluorinated Sulfonic Acid Polymers and Model Compounds under Mimic Fuel Cell Conditions
journal, November 2007

Interfacial structure of atomically flat polycrystalline Pt electrodes and modified Sauerbrey equation
journal, January 2017

Understanding the effects of Contaminants from Balance of Plant Assembly Aids Materials on PEMFCs -In Situ Studies
journal, March 2013

Surface-oxide growth at platinum electrodes in aqueous H2SO4
journal, April 2004

Model for the contamination of fuel cell anode catalyst in the presence of fuel stream impurities
journal, September 2005

Impact of Sulfur Dioxide on the Oxygen Reduction Reaction at Pt/Vulcan Carbon Electrocatalysts
journal, January 2007

Site-Specific vs Specific Adsorption of Anions on Pt and Pt-Based Alloys
journal, July 2007

Oxygen reduction reaction on Pt(111): effects of bromide
journal, June 1999

Surface-Enhanced Infrared Absorption
book, January 2006

PEMFC contaminant tolerance limit – Foreign cations in ionomers
journal, May 2011

Concentration Effects of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Activity for Three Platinum Catalysts
journal, January 2014

Carbon monoxide poisoning of proton exchange membrane fuel cells
journal, January 2001

In Situ Surface-Enhanced Raman Spectroscopic Studies of Nafion Adsorption on Au and Pt Electrodes
journal, December 2011

Influence of ammonia on membrane-electrode assemblies in polymer electrolyte fuel cells
journal, November 2009

Influence of the Surface Roughness of Platinum Electrodes on the Calibration of the Electrochemical Quartz-Crystal Nanobalance
journal, June 2017

Influence of Electrolyte Composition and pH on Platinum Electrochemical and/or Chemical Dissolution in Aqueous Acidic Media
journal, March 2015

Study of anion adsorption on polycrystalline Pt by electrochemical quartz crystal microbalance
journal, October 2000

Evaluating Polymeric Materials as Potential Sources of PEMFC System Contaminants
conference, January 2010

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

Potential-Dependent Adsorption and Desorption of Perfluorosulfonated Ionomer on a Platinum Electrode Surface Probed by Electrochemical Quartz Crystal Microbalance and Atomic Force Microscopy
journal, July 2013

The Development of New Membranes for Proton Exchange Membrane Fuel Cells
conference, January 2007

Pt-Oxide Coverage-Dependent Oxygen Reduction Reaction (ORR) Kinetics
journal, October 2011