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Title: Nafion induced surface confinement of oxygen in carbon-supported oxygen reduction catalysts

Journal Article · · Journal of Physical Chemistry. C

We studied the surface confinement of oxygen inside layers of Nafion self-assembled on carbon-supported oxygen reduction reaction (ORR) catalysts. It is demonstrated that oxygen accumulates in the hydrophobic component of the polymer remaining in contact with the carbon surface. Furthermore, the amount of surface confined oxygen increases with the degree of carbon surface graphitization, which promotes the self-assembly of the polymer. Planar macrocyclic ORR catalysts possessing a delocalized system of π electrons such as Co and Fe porphyrins and phthalocyanines have virtually no effect on the surface confinement of oxygen, in accordance with their structural similarity to graphitic carbon surfaces where they adsorb. Platinum particles in carbon-supported ORR catalysts with high metal contents (20%) disrupt the self-assembly of Nafion and virtually eliminate the oxygen confinement, but the phenomenon is still observed for low Pt loading (4.8%) catalysts.

Research Organization:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE; University of California Office of the President
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1334132
Report Number(s):
LA-UR-15-27304
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (50)

RRDE and Voltammetric Study of ORR on Pyrolyzed Fe/Polyaniline Catalyst. On the Origins of Variable Tafel Slopes journal March 2011
Is the Free Energy Change of Adsorption Correctly Calculated? journal July 2009
Molecular Oxygen Reduction in PEM Fuel Cells:  Evidence for the Simultaneous Presence of Two Active Sites in Fe-Based Catalysts journal August 2002
Nature of the Catalytic Centers of Porphyrin-Based Electrocatalysts for the ORR: A Correlation of Kinetic Current Density with the Site Density of Fe−N4 Centers
  • Koslowski, Ulrike I.; Abs-Wurmbach, Irmgard; Fiechter, Sebastian
  • The Journal of Physical Chemistry C, Vol. 112, Issue 39, p. 15356-15366 https://doi.org/10.1021/jp802456e
journal September 2008
Catalysts for the Oxygen Reduction from Heat-Treated Iron(III) Tetramethoxyphenylporphyrin Chloride:  Structure and Stability of Active Sites
  • Schulenburg, Hendrik; Stankov, Svetoslav; Schünemann, Volker
  • The Journal of Physical Chemistry B, Vol. 107, Issue 34, p. 9034-9041 https://doi.org/10.1021/jp030349j
journal August 2003
Effects of Axial Coordination of the Metal Center on the Activity of Iron Tetraphenylporphyrin as a Nonprecious Catalyst for Oxygen Reduction journal August 2014
The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction journal April 2006
Influence of Nitrogen Doping on Oxygen Reduction Electrocatalysis at Carbon Nanofiber Electrodes journal March 2005
Activity Descriptor Identification for Oxygen Reduction on Nonprecious Electrocatalysts: Linking Surface Science to Coordination Chemistry journal October 2013
Linear versus volcano correlations between electrocatalytic activity and redox and electronic properties of metallophthalocyanines journal December 1998
Density Functional Theory Study of Transitional Metal Macrocyclic Complexes' Dioxygen-Binding Abilities and Their Catalytic Activities toward Oxygen Reduction Reaction journal May 2007
Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces journal July 2012
Changing the Activity of Electrocatalysts for Oxygen Reduction by Tuning the Surface Electronic Structure journal April 2006
Theory of staircase voltammetry journal September 1965
On the use of Nafion® in electrochemical studies of carbon supported oxygen reduction catalysts in aqueous media journal November 2016
Characteristics of Self-Assembled Ultrathin Nafion Films journal April 2013
Activity, stability and degradation of multi walled carbon nanotube (MWCNT) supported Pt fuel cell electrocatalysts journal January 2010
Interaction of multi-walled carbon nanotubes with perfluorinated sulfonic acid ionomers and surface treatment studies journal May 2014
Performance Improvement in Direct Methanol Fuel Cell Cathode Using High Mesoporous Area Catalyst Support journal January 2005
In situ generated catalysts for NaBH4 hydrolysis studied by liquid-phase calorimetry: Influence of the nature of the metal journal April 2010
Palladium Nanoparticles Supported on Highly Oriented Pyrolytic Graphite: Preparation, Reactivity and Stability journal January 2015
Hydrogen Oxidation and Evolution Reaction Kinetics on Carbon Supported Pt, Ir, Rh, and Pd Electrocatalysts in Acidic Media journal November 2014
EDTA-Ce(III) Modified Pt Vulcan XC-72 Catalyst Synthesis for Methanol Oxidation in Acid Solution journal September 2013
An evaluation of the macro-homogeneous and agglomerate model for oxygen reduction in PEMFCs journal August 1998
Comparing the thin-film rotating disk electrode and the ultramicroelectrode with cavity techniques to study carbon-supported platinum for proton exchange membrane fuel cell applications journal January 2007
Mass Transport in Gas-Diffusion Electrodes: A Diagnostic Tool for Fuel-Cell Cathodes journal January 1998
Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems. journal April 1964
Effects of Ionomer Morphology on Oxygen Reduction on Pt journal January 2015
High surface area graphite as alternative support for proton exchange membrane fuel cell catalysts journal July 2009
Heat-Treated Carbon-Blacks as Supports for Platinum Catalysts journal July 1995
Benzene—O2 interaction potential from ab initio calculations journal April 1993
Oxygen adsorption on graphite and nanotubes journal January 2003
Formation and Structure of Perfluorosulfonated Ionomer Thin Film on a Graphite Surface journal September 2009
Quantum Size Effect Directed Selective Self-Assembling of Cobalt Phthalocyanine on Pb(111) Thin Films journal June 2008
The Entropies of Adsorbed Molecules journal October 2012
High-resolution scanning tunneling microscopy imaging of mesoscopic graphene sheets on an insulating surface journal May 2007
Pattern recognition approach to quantify the atomic structure of graphene journal August 2014
Gas Diffusion in the Dried and Hydrated Nafions journal January 1986
Oxygen permeation studies on alternative proton exchange membranes designed for elevated temperature operation journal June 2003
Properties of Nafion membranes under PEM water electrolysis conditions journal August 2011
Parallel cylindrical water nanochannels in Nafion fuel-cell membranes journal December 2007
Diffusion and Permeation of Oxygen, Nitrogen, Carbon Dioxide, and Nitrogen Dioxide through Polytetrafluoroethylene journal May 1970
Structure-to-property relationships in fuel cell catalyst supports: Correlation of surface chemistry and morphology with oxidation resistance of carbon blacks journal September 2012
Influence of Nafion® film on oxygen reduction reaction and hydrogen peroxide formation on Pt electrode for proton exchange membrane fuel cell journal December 2010
Characterization of Vulcan Electrochemically Oxidized under Simulated PEM Fuel Cell Conditions journal January 2004
Voltammetric studies of the redox mediator, cobalt phthalocyanine, with regard to its claimed electrocatalytic properties journal May 2010
Role of the glass transition temperature of Nafion 117 membrane in the preparation of the membrane electrode assembly in a direct methanol fuel cell (DMFC) journal September 2012
Novel method for preparation of PEMFC electrodes by the electrospray technique journal October 2005
Effects of hot pressing conditions on the performance of Nafion membranes coated by ink-jet printing of Pt/MWCNTs electrocatalyst for PEMFCs journal August 2012
Gas crossover and membrane degradation in polymer electrolyte fuel cells journal August 2006

Cited By (1)