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

Title: Correlating the electrocatalytic stability of platinum monolayer catalysts with their structural evolution in the oxygen reduction reaction

Abstract

Platinum monolayer (Pt ML) core–shell electrocatalysts for the oxygen reduction reaction (ORR) have attracted great attention because of their exceptional activity and stability for promising practical applications in fuel cells. In this paper, we describe our in-depth investigation of the relationship between the ORR activity and structure of the Pt ML/Pd/C catalyst during the stability test. By virtue of the rotating disk electrode technique, an accelerated degradation test with the potential window of 0.65 to 1.05 V was applied to the Pt ML/Pd/C to interrogate its long-term reliability in the ORR, the change of its electrochemical surface area, and its surface composition and components. The Pt ML/Pd/C catalyst displayed a volcano-like mass/dollar activity profile in the stability test up to 100k cycles. The overall loss of the activity was recorded to be as low as 17% of the initial value. The ORR activity increased in the initial 20k cycles because the freshly prepared Pt ML did not entirely encompass the whole Pd core, but it was integrated to a full coverage with a more stable configuration during the potential cycling owing to its self-healing property. Then, the activity decreased at a much slower rate than the standard Pt/C because themore » Pd–Pt core–shell structure due to its structural self-retaining property remained intact and impeded the electrochemical Ostwald ripening of the entire particles. Changes in the morphology and configuration of Pt ML were mapped by combining our experimental investigation with model analyses. Finally, the proposed self-healing and self-retaining mechanisms account for the structure-dependent stability in the ORR and play cornerstone roles in formulating ORR core–shell electrocatalysts.« less

Authors:
ORCiD logo [1];  [2];  [2];  [2]; ORCiD logo [3]; ORCiD logo [3];  [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [2];  [2]
  1. Harbin Institute of Technology (China); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Harbin Institute of Technology (China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1488522
Alternate Identifier(s):
OSTI ID: 1477520
Report Number(s):
BNL-209808-2018-JAAM
Journal ID: ISSN 2050-7488; JMCAET
Grant/Contract Number:  
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 42; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Chen, Guangyu, Kuttiyiel, Kurian A., Li, Meng, Su, Dong, Du, Lei, Du, Chunyu, Gao, Yunzhi, Fei, Weidong, Yin, Geping, Sasaki, Kotaro, and Adzic, Radoslav R. Correlating the electrocatalytic stability of platinum monolayer catalysts with their structural evolution in the oxygen reduction reaction. United States: N. p., 2018. Web. doi:10.1039/C8TA06686H.
Chen, Guangyu, Kuttiyiel, Kurian A., Li, Meng, Su, Dong, Du, Lei, Du, Chunyu, Gao, Yunzhi, Fei, Weidong, Yin, Geping, Sasaki, Kotaro, & Adzic, Radoslav R. Correlating the electrocatalytic stability of platinum monolayer catalysts with their structural evolution in the oxygen reduction reaction. United States. doi:10.1039/C8TA06686H.
Chen, Guangyu, Kuttiyiel, Kurian A., Li, Meng, Su, Dong, Du, Lei, Du, Chunyu, Gao, Yunzhi, Fei, Weidong, Yin, Geping, Sasaki, Kotaro, and Adzic, Radoslav R. Mon . "Correlating the electrocatalytic stability of platinum monolayer catalysts with their structural evolution in the oxygen reduction reaction". United States. doi:10.1039/C8TA06686H. https://www.osti.gov/servlets/purl/1488522.
@article{osti_1488522,
title = {Correlating the electrocatalytic stability of platinum monolayer catalysts with their structural evolution in the oxygen reduction reaction},
author = {Chen, Guangyu and Kuttiyiel, Kurian A. and Li, Meng and Su, Dong and Du, Lei and Du, Chunyu and Gao, Yunzhi and Fei, Weidong and Yin, Geping and Sasaki, Kotaro and Adzic, Radoslav R.},
abstractNote = {Platinum monolayer (PtML) core–shell electrocatalysts for the oxygen reduction reaction (ORR) have attracted great attention because of their exceptional activity and stability for promising practical applications in fuel cells. In this paper, we describe our in-depth investigation of the relationship between the ORR activity and structure of the PtML/Pd/C catalyst during the stability test. By virtue of the rotating disk electrode technique, an accelerated degradation test with the potential window of 0.65 to 1.05 V was applied to the PtML/Pd/C to interrogate its long-term reliability in the ORR, the change of its electrochemical surface area, and its surface composition and components. The PtML/Pd/C catalyst displayed a volcano-like mass/dollar activity profile in the stability test up to 100k cycles. The overall loss of the activity was recorded to be as low as 17% of the initial value. The ORR activity increased in the initial 20k cycles because the freshly prepared PtML did not entirely encompass the whole Pd core, but it was integrated to a full coverage with a more stable configuration during the potential cycling owing to its self-healing property. Then, the activity decreased at a much slower rate than the standard Pt/C because the Pd–Pt core–shell structure due to its structural self-retaining property remained intact and impeded the electrochemical Ostwald ripening of the entire particles. Changes in the morphology and configuration of PtML were mapped by combining our experimental investigation with model analyses. Finally, the proposed self-healing and self-retaining mechanisms account for the structure-dependent stability in the ORR and play cornerstone roles in formulating ORR core–shell electrocatalysts.},
doi = {10.1039/C8TA06686H},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 42,
volume = 6,
place = {United States},
year = {2018},
month = {9}
}

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

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Surface segregation and stability of core–shell alloy catalysts for oxygen reduction in acid medium
journal, January 2010

  • Ramírez-Caballero, Gustavo E.; Ma, Yuguang; Callejas-Tovar, Rafael
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 9
  • DOI: 10.1039/b917899f

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

Instability of Supported Platinum Nanoparticles in Low-Temperature Fuel Cells
journal, November 2007


Shaping binary metal nanocrystals through epitaxial seeded growth
journal, July 2007

  • Habas, Susan E.; Lee, Hyunjoo; Radmilovic, Velimir
  • Nature Materials, Vol. 6, Issue 9
  • DOI: 10.1038/nmat1957

Dissolution-Resistant Core−Shell Materials for Acid Medium Oxygen Reduction Electrocatalysts
journal, January 2010

  • Ramírez-Caballero, Gustavo E.; Balbuena, Perla B.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 4
  • DOI: 10.1021/jz1000165

Platinum Monolayer Electrocatalysts: Tunable Activity, Stability, and Self-Healing Properties
journal, September 2012


Preparation and Structural Analysis of Carbon-Supported Co Core/Pt Shell Electrocatalysts Using Electroless Deposition Methods
journal, August 2009

  • Beard, K. D.; Borrelli, David; Cramer, Alison M.
  • ACS Nano, Vol. 3, Issue 9
  • DOI: 10.1021/nn900214g

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

Bimetallic IrNi core platinum monolayer shell electrocatalysts for the oxygen reduction reaction
journal, January 2012

  • Kuttiyiel, Kurian A.; Sasaki, Kotaro; Choi, YongMan
  • Energy Environ. Sci., Vol. 5, Issue 1
  • DOI: 10.1039/C1EE02067F

Platinum-Alloy Cathode Catalyst Degradation in Proton Exchange Membrane Fuel Cells: Nanometer-Scale Compositional and Morphological Changes
journal, January 2010

  • Chen, Shuo; Gasteiger, Hubert A.; Hayakawa, Katsuichiro
  • Journal of The Electrochemical Society, Vol. 157, Issue 1
  • DOI: 10.1149/1.3258275

Controlling the Catalytic Activity of Platinum-Monolayer Electrocatalysts for Oxygen Reduction with Different Substrates
journal, March 2005

  • Zhang, Junliang; Vukmirovic, Miomir B.; Xu, Ye
  • Angewandte Chemie International Edition, Vol. 44, Issue 14, p. 2132-2135
  • DOI: 10.1002/anie.200462335

Communication—Electrochemical Stability of Pt/Pd(111) Model Core-Shell Structure in 80°C Perchloric Acid
journal, January 2017

  • Todoroki, N.; Bando, Y.; Tani, Y.
  • Journal of The Electrochemical Society, Vol. 164, Issue 9
  • DOI: 10.1149/2.0571709jes

Scientific Aspects of Polymer Electrolyte Fuel Cell Durability and Degradation
journal, October 2007

  • Borup, Rod; Meyers, Jeremy; Pivovar, Bryan
  • Chemical Reviews, Vol. 107, Issue 10
  • DOI: 10.1021/cr050182l

Platinum-Coated Palladium Nanotubes as Oxygen Reduction Reaction Electrocatalysts
journal, April 2012

  • Alia, Shaun M.; Jensen, Kurt O.; Pivovar, Bryan S.
  • ACS Catalysis, Vol. 2, Issue 5
  • DOI: 10.1021/cs200682c

A method to prepare single crystal electrodes of reactive metals: application to Pd(hkl)
journal, May 1999


Electrocatalyst approaches and challenges for automotive fuel cells
journal, June 2012


Metal monolayer deposition by replacement of metal adlayers on electrode surfaces
journal, March 2001


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

On the importance of correcting for the uncompensated Ohmic resistance in model experiments of the Oxygen Reduction Reaction
journal, August 2010


Multimetallic Core/Interlayer/Shell Nanostructures as Advanced Electrocatalysts
journal, October 2014

  • Kang, Yijin; Snyder, Joshua; Chi, Miaofang
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl5028205

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

Understanding and Controlling Nanoporosity Formation for Improving the Stability of Bimetallic Fuel Cell Catalysts
journal, February 2013

  • Gan, Lin; Heggen, Marc; O’Malley, Rachel
  • Nano Letters, Vol. 13, Issue 3
  • DOI: 10.1021/nl304488q

Instability of Pt∕C Electrocatalysts in Proton Exchange Membrane Fuel Cells
journal, January 2005

  • Ferreira, P. J.; la O’, G. J.; Shao-Horn, Y.
  • Journal of The Electrochemical Society, Vol. 152, Issue 11
  • DOI: 10.1149/1.2050347

Evolution of nanoporosity in dealloying
journal, March 2001

  • Erlebacher, Jonah; Aziz, Michael J.; Karma, Alain
  • Nature, Vol. 410, Issue 6827, p. 450-453
  • DOI: 10.1038/35068529

Degradation of Carbon-Supported Pt Bimetallic Nanoparticles by Surface Segregation
journal, November 2009

  • Mayrhofer, Karl J. J.; Hartl, Katrin; Juhart, Viktorija
  • Journal of the American Chemical Society, Vol. 131, Issue 45
  • DOI: 10.1021/ja9074216

Size and Shape Effects of Pd@Pt Core–Shell Nanoparticles: Unique Role of Surface Contraction and Local Structural Flexibility
journal, July 2013

  • An, Wei; Liu, Ping
  • The Journal of Physical Chemistry C, Vol. 117, Issue 31
  • DOI: 10.1021/jp4057785

Design of Pt-Shell Nanoparticles with Alloy Cores for the Oxygen Reduction Reaction
journal, September 2013

  • Zhang, Liang; Iyyamperumal, Ravikumar; Yancey, David F.
  • ACS Nano, Vol. 7, Issue 10
  • DOI: 10.1021/nn403788a

Tuning Oxygen Reduction Reaction Activity via Controllable Dealloying A Model Study of Ordered Cu3Pt/C Intermetallic Nanocatalysts
journal, September 2012

  • Wang, Deli; Yu, Yingchao; Xin, Huolin L.
  • Nano Letters, Vol. 12, Issue 10, p. 5230-5238
  • DOI: 10.1021/nl302404g

Pt monolayer on Au-stabilized PdNi core–shell nanoparticles for oxygen reduction reaction
journal, November 2013


Highly stable Pt monolayer on PdAu nanoparticle electrocatalysts for the oxygen reduction reaction
journal, January 2012

  • Sasaki, Kotaro; Naohara, Hideo; Choi, YongMan
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms2124

High-performance transition metal-doped Pt3Ni octahedra for oxygen reduction reaction
journal, June 2015


Durable PEM Fuel Cell Electrode Materials: Requirements and Benchmarking Methodologies
conference, January 2006

  • Makharia, Rohit; Kocha, Shyam; Yu, Paul
  • 208th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.2214540

Surface science studies of model fuel cell electrocatalysts
journal, April 2002


Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters
journal, January 2007


Oxygen Reduction on Well-Defined Core−Shell Nanocatalysts: Particle Size, Facet, and Pt Shell Thickness Effects
journal, December 2009

  • Wang, Jia X.; Inada, Hiromi; Wu, Lijun
  • Journal of the American Chemical Society, Vol. 131, Issue 47
  • DOI: 10.1021/ja9067645

Preparation and Characterization of PdFe Nanoleaves as Electrocatalysts for Oxygen Reduction Reaction
journal, March 2011

  • Zhang, Zhiyong; More, Karren L.; Sun, Kai
  • Chemistry of Materials, Vol. 23, Issue 6
  • DOI: 10.1021/cm1034134

Multimetallic Au/FePt 3 Nanoparticles as Highly Durable Electrocatalyst
journal, March 2011

  • Wang, Chao; van der Vliet, Dennis; More, Karren L.
  • Nano Letters, Vol. 11, Issue 3
  • DOI: 10.1021/nl102369k

Understanding the electrocatalysis of oxygen reduction on platinum and its alloys
journal, January 2012

  • Stephens, Ifan E. L.; Bondarenko, Alexander S.; Grønbjerg, Ulrik
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee03590a

The Effect of Size on the Oxygen Electroreduction Activity of Mass-Selected Platinum Nanoparticles
journal, March 2012

  • Perez-Alonso, Francisco J.; McCarthy, David N.; Nierhoff, Anders
  • Angewandte Chemie International Edition, Vol. 51, Issue 19
  • DOI: 10.1002/anie.201200586

Underpotential and bulk deposition of copper on Pd(111) in sulfuric acid solution studied by in situ scanning tunneling microscopy
journal, January 2001

  • Okada, Jun; Inukai, Junji; Itaya, Kingo
  • Physical Chemistry Chemical Physics, Vol. 3, Issue 16
  • DOI: 10.1039/b101093j

Surface segregation energies in transition-metal alloys
journal, June 1999


Evolution of Pt and Pt-Alloy Catalytic Surfaces Under Oxygen Reduction Reaction in Acid Medium
journal, April 2012


Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

Electrocatalysis on Platinum Nanoparticles: Particle Size Effect on Oxygen Reduction Reaction Activity
journal, September 2011

  • Shao, Minhua; Peles, Amra; Shoemaker, Krista
  • Nano Letters, Vol. 11, Issue 9
  • DOI: 10.1021/nl2017459

Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts
journal, December 2015


Alloys of platinum and early transition metals as oxygen reduction electrocatalysts
journal, September 2009

  • Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.
  • Nature Chemistry, Vol. 1, Issue 7, p. 552-556
  • DOI: 10.1038/nchem.367