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Title: Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements

An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potential limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt 2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtO x (x > 1), to Pt 2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtO x. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on themore » potential cycle and UPL.« less
Authors:
ORCiD logo [1] ;  [1] ;  [2] ;  [1] ;  [2] ;  [1] ;  [1] ; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Grant/Contract Number:
AC02-06CH11357
Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 6; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Co dissolution; Pt dissolution; PtCo alloy PEMFC cathode catalyst
OSTI Identifier:
1420208
Alternate Identifier(s):
OSTI ID: 1437368

Ahluwalia, Rajesh K., Papadias, Dionissios D., Kariuki, Nancy N., Peng, Jui-Kun, Wang, Xiaoping, Tsai, Yifen, Graczyk, Donald G., and Myers, Deborah J.. Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements. United States: N. p., Web. doi:10.1149/2.0031806jes.
Ahluwalia, Rajesh K., Papadias, Dionissios D., Kariuki, Nancy N., Peng, Jui-Kun, Wang, Xiaoping, Tsai, Yifen, Graczyk, Donald G., & Myers, Deborah J.. Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements. United States. doi:10.1149/2.0031806jes.
Ahluwalia, Rajesh K., Papadias, Dionissios D., Kariuki, Nancy N., Peng, Jui-Kun, Wang, Xiaoping, Tsai, Yifen, Graczyk, Donald G., and Myers, Deborah J.. 2018. "Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements". United States. doi:10.1149/2.0031806jes.
@article{osti_1420208,
title = {Potential Dependence of Pt and Co Dissolution from Platinum-Cobalt Alloy PEFC Catalysts Using Time-Resolved Measurements},
author = {Ahluwalia, Rajesh K. and Papadias, Dionissios D. and Kariuki, Nancy N. and Peng, Jui-Kun and Wang, Xiaoping and Tsai, Yifen and Graczyk, Donald G. and Myers, Deborah J.},
abstractNote = {An electrochemical flow cell system with catalyst-ionomer ink deposited on glassy carbon is used to investigate the aqueous stability of commercial PtCo alloys under cyclic potentials. An on-line inductively coupled plasma-mass spectrometer, capable of real-time measurements, is used to resolve the anodic and cathodic dissolution of Pt and Co during square-wave and triangle-wave potential cycles. We observe Co dissolution at all potentials, distinct peaks in anodic and cathodic Pt dissolution rates above 0.9 V, and potential-dependent Pt and Co dissolution rates. The amount of Pt that dissolves cathodically is smaller than the amount that dissolves anodically if the upper potential limit (UPL) is lower than 0.9 V. At the highest UPL investigated, 1.0 V, the cathodic dissolution greatly exceeds the anodic dissolution. A non-ideal solid solution model indicates that the anodic dissolution can be associated with the electrochemical oxidation of Pt and PtOH to Pt2+, and the cathodic dissolution to electrochemical reduction of a higher Pt oxide, PtOx (x > 1), to Pt2+. Pt also dissolves oxidatively during the cathodic scans but in smaller amounts than due to the reductive dissolution of PtOx. The relative amounts Pt dissolving oxidatively as Pt and PtOH depend on the potential cycle and UPL.},
doi = {10.1149/2.0031806jes},
journal = {Journal of the Electrochemical Society},
number = 6,
volume = 165,
place = {United States},
year = {2018},
month = {2}
}