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

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

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.0031806jes· OSTI ID:1420208

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1420208
Alternate ID(s):
OSTI ID: 1437368
Journal Information:
Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Vol. 165 Journal Issue: 6; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 56 works
Citation information provided by
Web of Science

References (45)

Pt Degradation Mechanism in Concentrated Sulfuric Acid Studied Using Rotating Ring−Disk Electrode and Electrochemical Quartz Crystal Microbalance journal August 2009
Consumption Rate of Pt under Potential Cycling journal January 2007
Identification and Quantification of Oxygen Species Adsorbed on Pt(111) Single-Crystal and Polycrystalline Pt Electrodes by Photoelectron Spectroscopy journal February 2009
New Insight into Platinum Dissolution from Nanoparticulate Platinum-Based Electrocatalysts Using Highly Sensitive In Situ Concentration Measurements journal December 2013
Growth limits in platinum oxides formed on Pt-skin layers on Pt–Co bimetallic nanoparticles journal January 2011
Platinum Dissolution in Fuel Cell Electrodes: Enhanced Degradation from Surface Area Assessment in Automotive Accelerated Stress Tests journal January 2015
Instability of Pt∕C Electrocatalysts in Proton Exchange Membrane Fuel Cells journal January 2005
Determination of O and OH Adsorption Sites and Coverage in Situ on Pt Electrodes from Pt L 23 X-ray Absorption Spectroscopy journal April 2005
Towards a comprehensive understanding of platinum dissolution in acidic media journal January 2014
Ion association at liquid|liquid interfaces journal October 1997
Platinum dissolution and deposition in the polymer electrolyte membrane of a PEM fuel cell as studied by potential cycling journal January 2006
Surface Platinum Electrooxidation in the Presence of Oxygen journal January 2012
Durability of platinum-based fuel cell electrocatalysts: Dissolution of bulk and nanoscale platinum journal November 2016
Examination of the activity and durability of PEMFC catalysts in liquid electrolytes journal October 2010
Direct observation of the oxygenated species during oxygen reduction on a platinum fuel cell cathode journal December 2013
Oxidation-reduction-induced roughening of platinum (1 1 1) surface journal April 1994
Kinetic Model of Platinum Dissolution in PEMFCs journal January 2003
Electrocatalyst Durability under Simulated Automotive Drive Cycles conference January 2008
The influence of chloride impurities on Pt/C fuel cell catalyst corrosion journal January 2014
Surface-oxide growth at platinum electrodes in aqueous H2SO4 journal April 2004
Platinum-Alloy Cathode Catalyst Degradation in Proton Exchange Membrane Fuel Cells: Nanometer-Scale Compositional and Morphological Changes journal January 2010
Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments journal March 2016
Applications of surface X-ray scattering to electrochemistry problems journal July 2002
A Comparative Study on Gold and Platinum Dissolution in Acidic and Alkaline Media journal January 2014
Dissolution of Platinum: Limits for the Deployment of Electrochemical Energy Conversion? journal November 2012
Dynamics of Particle Growth and Electrochemical Surface Area Loss due to Platinum Dissolution journal December 2013
Effect of Voltage on Platinum Dissolution journal January 2006
Effect of Particle Size and Operating Conditions on Pt3Co PEMFC Cathode Catalyst Durability journal May 2015
Channel-Flow Double-Electrode Study on the Dissolution and Deposition Potentials of Platinum under Potential Cycles journal January 2009
Dissolution of Oxygen Reduction Electrocatalysts in an Acidic Environment:  Density Functional Theory Study journal August 2006
Dissolution of platinum in acidic media journal December 2008
PEM fuel cell electrocatalyst durability measurements journal December 2006
Theoretical Study on Dissolution and Reprecipitation Mechanism of Pt Complex in Pt Electrocatalyst journal January 2011
Intermediate stages of electrochemical oxidation of single-crystalline platinum revealed by in situ Raman spectroscopy journal August 2016
Dissolution Mechanism of Platinum in Sulfuric Acid Solution journal January 2012
Growth and Properties of Oxide Films on Platinum journal January 2006
Kinetics and mechanism of electrochemical reduction of multilayer oxides on a smooth platinum electrode surface in acidic electrolyte journal May 1978
In‐situ x‐ray reflectivity study of incipient oxidation of Pt(111) surface in electrolyte solutions journal March 1994
The Space Confinement Approach Using Hollow Graphitic Spheres to Unveil Activity and Stability of Pt-Co Nanocatalysts for PEMFC journal July 2017
Initial stages of Pt(111) electrooxidation: dynamic and structural studies by surface X-ray diffraction journal January 2017
Elucidating the oxide growth mechanism on platinum at the cathode in PEM fuel cells journal January 2014
Thermodynamics and Kinetics of Platinum Dissolution from Carbon-Supported Electrocatalysts in Aqueous Media under Potentiostatic and Potentiodynamic Conditions journal January 2013
In Situ and Real-Time Monitoring of Oxide Growth in a Few Monolayers at Surfaces of Platinum Nanoparticles in Aqueous Media journal May 2009
Importance of non-intrinsic platinum dissolution in Pt/C composite fuel cell catalysts journal January 2017
Dissolution and Migration of Platinum in PEMFCs Investigated for Start/Stop Cycling and High Potential Degradation journal February 2011