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Title: The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media

Abstract

In this paper, we investigated the performance of several carbon-supported RuxPty electrocatalysts for their alkaline hydrogen oxidation and oxygen reduction performance in the presence of carbonate and compared their performance with monometallic, carbon-supported Pt. Our results indicate a strong dependence of HOR upon pH for the monometallic Pt catalysts (22 mV/pH) and a weak dependence upon pH for the Ru-containing electrocatalysts (3.7, 2.5, and 4.7 mV/pH on Ru0.2Pt0.8, Ru0.4Pt0.6, and Ru0.8Pt0.2, respectively). These results are consistent with our previous findings that illustrate a change in rds from electron transfer (on monometallic Pt) to dissociative hydrogen adsorption (on RuxPty catalysts). Analysis of the kinetic currents to determine the rate-determining step via Tafel slope analysis provides additional data supporting this conclusion. There is no difference in the performance at comparable pH values in the presence or absence of carbonate on monometallic Pt indicating that water/hydroxide is the primary proton acceptor for alkaline HOR in 0.1 M KOH aqueous electrolyte. Finally, we observe no pH or carbonate dependence for the ORR on monometallic Pt.

Authors:
 [1];  [1];  [1];  [2];  [1];  [3]
  1. Univ. of Tennessee, Knoxville, TN (United States). Chemical and Biomolecular Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
  3. Univ. of Tennessee, Knoxville, TN (United States). Chemical and Biomolecular Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1335336
Grant/Contract Number:  
AC05-00OR22725; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 163; Journal Issue: 3; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkaline; carbonate; hydrogen oxidation; oxygen reduction; platinum; ruthenium

Citation Formats

John, Samuel St., Atkinson, Robert W., Roy, Asa, Unocic, Raymond R., Papandrew, Alexander B., and Zawodzinski, Thomas A. The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media. United States: N. p., 2016. Web. doi:10.1149/2.1071603jes.
John, Samuel St., Atkinson, Robert W., Roy, Asa, Unocic, Raymond R., Papandrew, Alexander B., & Zawodzinski, Thomas A. The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media. United States. https://doi.org/10.1149/2.1071603jes
John, Samuel St., Atkinson, Robert W., Roy, Asa, Unocic, Raymond R., Papandrew, Alexander B., and Zawodzinski, Thomas A. Mon . "The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media". United States. https://doi.org/10.1149/2.1071603jes. https://www.osti.gov/servlets/purl/1335336.
@article{osti_1335336,
title = {The Effect of Carbonate and pH on Hydrogen Oxidation and Oxygen Reduction on Pt-Based Electrocatalysts in Alkaline Media},
author = {John, Samuel St. and Atkinson, Robert W. and Roy, Asa and Unocic, Raymond R. and Papandrew, Alexander B. and Zawodzinski, Thomas A.},
abstractNote = {In this paper, we investigated the performance of several carbon-supported RuxPty electrocatalysts for their alkaline hydrogen oxidation and oxygen reduction performance in the presence of carbonate and compared their performance with monometallic, carbon-supported Pt. Our results indicate a strong dependence of HOR upon pH for the monometallic Pt catalysts (22 mV/pH) and a weak dependence upon pH for the Ru-containing electrocatalysts (3.7, 2.5, and 4.7 mV/pH on Ru0.2Pt0.8, Ru0.4Pt0.6, and Ru0.8Pt0.2, respectively). These results are consistent with our previous findings that illustrate a change in rds from electron transfer (on monometallic Pt) to dissociative hydrogen adsorption (on RuxPty catalysts). Analysis of the kinetic currents to determine the rate-determining step via Tafel slope analysis provides additional data supporting this conclusion. There is no difference in the performance at comparable pH values in the presence or absence of carbonate on monometallic Pt indicating that water/hydroxide is the primary proton acceptor for alkaline HOR in 0.1 M KOH aqueous electrolyte. Finally, we observe no pH or carbonate dependence for the ORR on monometallic Pt.},
doi = {10.1149/2.1071603jes},
journal = {Journal of the Electrochemical Society},
number = 3,
volume = 163,
place = {United States},
year = {2016},
month = {1}
}

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Works referenced in this record:

Pt–Ru catalyzed hydrogen oxidation in alkaline media: oxophilic effect or electronic effect?
journal, January 2015

  • Wang, Ying; Wang, Gongwei; Li, Guangwei
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE02564D

Improving the hydrogen oxidation reaction rate by promotion of hydroxyl adsorption
journal, February 2013

  • Strmcnik, Dusan; Uchimura, Masanobu; Wang, Chao
  • Nature Chemistry, Vol. 5, Issue 4
  • DOI: 10.1038/nchem.1574

New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism
journal, January 2014

  • Durst, J.; Siebel, A.; Simon, C.
  • Energy Environ. Sci., Vol. 7, Issue 7
  • DOI: 10.1039/c4ee00440j

Ruthenium-Alloy Electrocatalysts with Tunable Hydrogen Oxidation Kinetics in Alkaline Electrolyte
journal, June 2015

  • St. John, Samuel; Atkinson, Robert W.; Unocic, Raymond R.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 24
  • DOI: 10.1021/acs.jpcc.5b03284

Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy
journal, January 2015

  • Sheng, Wenchao; Zhuang, Zhongbin; Gao, Minrui
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6848

Mathematical Modeling of the Concentration Profile of Carbonate Ions in an Anion Exchange Membrane Fuel Cell
journal, January 2011

  • Siroma, Z.; Watanabe, S.; Yasuda, K.
  • Journal of The Electrochemical Society, Vol. 158, Issue 6
  • DOI: 10.1149/1.3576120

Anion-exchange membranes in electrochemical energy systems
journal, January 2014

  • Varcoe, John R.; Atanassov, Plamen; Dekel, Dario R.
  • Energy & Environmental Science, Vol. 7, Issue 10, p. 3135-3191
  • DOI: 10.1039/C4EE01303D

A Carbon Dioxide Tolerant Aqueous-Electrolyte-Free Anion-Exchange Membrane Alkaline Fuel Cell
journal, February 2008

  • Adams, Latifah A.; Poynton, Simon D.; Tamain, Christelle
  • ChemSusChem, Vol. 1, Issue 1-2
  • DOI: 10.1002/cssc.200700013

Hydrogen and Methanol Oxidation Reaction in Hydroxide and Carbonate Alkaline Media
journal, January 2011

  • Vega, Jose A.; Smith, Shawna; Mustain, William E.
  • Journal of The Electrochemical Society, Vol. 158, Issue 4
  • DOI: 10.1149/1.3543918

Oxygen Reduction Activity of Vapor-Grown Platinum Nanotubes
journal, January 2013

  • Papandrew, Alexander B.; Atkinson, Robert W.; Goenaga, Gabriel A.
  • Journal of The Electrochemical Society, Vol. 160, Issue 8
  • DOI: 10.1149/2.090308jes

Advanced Electrodes for Solid Acid Fuel Cells by Platinum Deposition on CsH 2 PO 4
journal, April 2011

  • Papandrew, Alexander B.; Chisholm, Calum R. I.; Elgammal, Ramez A.
  • Chemistry of Materials, Vol. 23, Issue 7
  • DOI: 10.1021/cm101147y

Activity and Evolution of Vapor Deposited Pt-Pd Oxygen Reduction Catalysts for Solid Acid Fuel Cells
journal, December 2012

  • Papandrew, Alexander B.; Chisholm, Calum R. I.; Zecevic, Strahinja K.
  • Journal of The Electrochemical Society, Vol. 160, Issue 2
  • DOI: 10.1149/2.002303jes

Ruthenium as a CO-tolerant hydrogen oxidation catalyst for solid acid fuel cells
journal, January 2015

  • Papandrew, Alexander B.; Atkinson III, Robert W.; Unocic, Raymond R.
  • Journal of Materials Chemistry A, Vol. 3, Issue 7
  • DOI: 10.1039/C4TA06451H

Electrochemical Hydrogen Separation via Solid Acid Membranes
journal, January 2014

  • Papandrew, Alexander B.; Wilson, David L.; M. Cantillo, Nelly
  • Journal of The Electrochemical Society, Vol. 161, Issue 5
  • DOI: 10.1149/2.078405jes

Experimental Methods for Quantifying the Activity of Platinum Electrocatalysts for the Oxygen Reduction Reaction
journal, August 2010

  • Garsany, Yannick; Baturina, Olga A.; Swider-Lyons, Karen E.
  • Analytical Chemistry, Vol. 82, Issue 15
  • DOI: 10.1021/ac100306c

Electrochemical surface area measurements of platinum- and palladium-based nanoparticles
journal, June 2013


Anion exchange membranes for alkaline fuel cells: A review
journal, July 2011

  • Merle, Géraldine; Wessling, Matthias; Nijmeijer, Kitty
  • Journal of Membrane Science, Vol. 377, Issue 1-2, p. 1-35
  • DOI: 10.1016/j.memsci.2011.04.043

In Situ X‐Ray Absorption Studies of a Pt‐Ru Electrocatalyst
journal, October 1995

  • McBreen, James; Mukerjee, Sanjeev
  • Journal of The Electrochemical Society, Vol. 142, Issue 10
  • DOI: 10.1149/1.2049993

Impact of solute concentration on the electrocatalytic conversion of dissolved gases in buffered solutions
journal, August 2015


Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations
journal, October 2010

  • Skúlason, Egill; Tripkovic, Vladimir; Björketun, Mårten E.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 42
  • DOI: 10.1021/jp1048887

Diffusion of oxygen and hydrogen in aqueous potassium hydroxide solutions
journal, April 1970

  • Tham, Min J.; Walker, Robert Dixon; Gubbins, Keith E.
  • The Journal of Physical Chemistry, Vol. 74, Issue 8
  • DOI: 10.1021/j100703a015

The Solubility and Diffusivity of Oxygen in Electrolytic Solutions
journal, January 1965

  • Gubbins, Keith E.; Walker, Robert D.
  • Journal of The Electrochemical Society, Vol. 112, Issue 5
  • DOI: 10.1149/1.2423575

Solubility of Hydrogen in Potassium Hydroxide and Sulfuric Acid. Salting-out and Hydration
journal, March 1966

  • Ruetschi, P.; Amlie, R. F.
  • The Journal of Physical Chemistry, Vol. 70, Issue 3
  • DOI: 10.1021/j100875a018

In situ analysis of optimum surface atom coordination for Pt nanoparticle oxygen reduction electrocatalysts
journal, December 2013


Structural effects in electrocatalysis: oxygen reduction on platinum low index single-crystal surfaces in perchloric acid solutions
journal, October 1994

  • Marković, N. M.; Adžić, R. R.; Cahan, B. D.
  • Journal of Electroanalytical Chemistry, Vol. 377, Issue 1-2
  • DOI: 10.1016/0022-0728(94)03467-2

Electrocatalysis of oxygen reduction and small alcohol oxidation in alkaline media
journal, January 2007

  • Spendelow, Jacob S.; Wieckowski, Andrzej
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 21
  • DOI: 10.1039/b703315j

Works referencing / citing this record:

The Effect of Ambient Carbon Dioxide on Anion-Exchange Membrane Fuel Cells
journal, March 2018


Origin of Superior HOR/HER Activity of Bimetallic Pt-Ru Catalysts in Alkaline Media Identified via Ru@Pt Core-Shell Nanoparticles
journal, January 2018

  • Schwämmlein, Jan N.; Stühmeier, Björn M.; Wagenbauer, Klaus
  • Journal of The Electrochemical Society, Vol. 165, Issue 5
  • DOI: 10.1149/2.0791805jes

Anion Exchange Membrane Fuel Cell Performance in the Presence of Carbon Dioxide: An Investigation into the Self-Purging Mechanism
journal, January 2019

  • Wrubel, Jacob A.; Peracchio, Aldo A.; Cassenti, Brice N.
  • Journal of The Electrochemical Society, Vol. 166, Issue 12
  • DOI: 10.1149/2.0801912jes