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Title: Active-Phase Formation and Stability of Gd/Pt(111) Electrocatalysts for Oxygen Reduction: An In Situ Grazing Incidence X-Ray Diffraction Study

Journal Article · · Chemistry - A European Journal
ORCiD logo [1];  [2];  [2];  [3];  [4];  [5];  [6]; ORCiD logo [2]
  1. Univ. of Copenhagen, Copenhagen (Denmark); Technical Univ. of Denmark, Lyngby (Denmark); Stanford Univ., Stanford, CA (United States)
  2. Technical Univ. of Denmark, Lyngby (Denmark)
  3. Univ. of Copenhagen, Copenhagen (Denmark); Technical Univ. of Denmark, Lyngby (Denmark)
  4. Stanford Univ., Stanford, CA (United States)
  5. Univ. of Copenhagen, Copenhagen (Denmark)
  6. Technical Univ. of Denmark, Lyngby (Denmark); Imperial College London, England (United Kingdom)

Alloys of platinum and gadolinium present significant activity enhancement over pure Pt for the oxygen reduction reaction (ORR), both in the form of extended electrode surfaces and nanoparticulate catalysts. The active phase consists of a compressed Pt overlayer formed on Pt5Gd electrodes upon exposure to the electrolyte by acid leaching. Here, we investigate the formation, strain and correlation lengths of the active Pt overlayer by using in situ synchrotron grazing incidence X–ray diffraction on Gd/Pt(111) single–crystalline electrodes. The overlayer forms upon exposure to electrolyte under open circuit conditions; the compressive strain relaxes slightly upon repeated electrochemical cycling in the potential range 0.6 to 1.0 V versus the reversible hydrogen electrode (RHE). Furthermore, the strain relaxes strongly when exposing the electrode to 1.2 V versus RHE, and the thickness of the crystalline portion of the overlayer increases with potential above 1.3 V versus RHE.

Research Organization:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515; 9455; DFF-4093-00104; EliteForsk travel grant
OSTI ID:
1476110
Journal Information:
Chemistry - A European Journal, Vol. 24, Issue 47; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (60)

The Priority and Challenge of High-Power Performance of Low-Platinum Proton-Exchange Membrane Fuel Cells journal March 2016
Experimental Methodologies to Understand Degradation of Nanostructured Electrocatalysts for PEM Fuel Cells: Advances and Opportunities journal June 2016
From ultra-high vacuum to the electrochemical interface: X-ray scattering studies of model electrocatalysts journal January 2009
Toward sustainable fuel cells journal December 2016
Scalable Synthesis of Carbon-Supported Platinum–Lanthanide and −Rare-Earth Alloys for Oxygen Reduction journal January 2018
Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces journal February 2014
Correlation between diffusion barriers and alloying energy in binary alloys journal January 2016
Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs journal March 2005
Benchmarking Pt and Pt-lanthanide sputtered thin films for oxygen electroreduction: fabrication and rotating disk electrode measurements journal September 2017
Oxygen Reduction Reaction Activity for Strain-Controlled Pt-Based Model Alloy Catalysts: Surface Strains and Direct Electronic Effects Induced by Alloying Elements journal July 2016
Preparation of monocrystalline Pt microelectrodes and electrochemical study of the plane surfaces cut in the direction of the {111} and {110} planes journal February 1980
The atomic simulation environment—a Python library for working with atoms journal June 2017
Mass-selected nanoparticles of PtxY as model catalysts for oxygen electroreduction journal July 2014
Investigating the coverage dependent behaviour of CO on Gd/Pt(111) journal January 2016
Elucidation of the Oxygen Reduction Volcano in Alkaline Media using a Copper-Platinum(111) Alloy journal February 2018
Segregation and stability at Pt3Ni(111) surfaces and Pt75Ni25 nanoparticles journal September 2008
Pt 5 Gd as a Highly Active and Stable Catalyst for Oxygen Electroreduction
  • Escudero-Escribano, María; Verdaguer-Casadevall, Arnau; Malacrida, Paolo
  • Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja306348d
journal September 2012
Structural Reorganization of Pt(111) Electrodes by Electrochemical Oxidation and Reduction journal March 2017
Probing the nanoscale structure of the catalytically active overlayer on Pt alloys with rare earths journal November 2016
Influence of adsorbed hydroxyl and carbon monoxide on potential-induced reconstruction of Au(100) as examined by scanning tunneling microscopy journal January 1994
Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction journal November 2016
Electrocatalyst approaches and challenges for automotive fuel cells journal June 2012
New Platinum Alloy Catalysts for Oxygen Electroreduction Based on Alkaline Earth Metals journal April 2017
Enhanced activity and stability of Pt–La and Pt–Ce alloys for oxygen electroreduction: the elucidation of the active surface phase journal January 2014
Membrane and Catalyst Performance Targets for Automotive Fuel Cells by FCCJ Membrane, Catalyst, MEA WG conference January 2011
Energy and fuels from electrochemical interfaces journal December 2016
Towards the elucidation of the high oxygen electroreduction activity of Pt x Y: surface science and electrochemical studies of Y/Pt(111) journal January 2014
Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction journal March 2016
Elucidation of the Oxygen Reduction Volcano in Alkaline Media using a Copper-Platinum(111) Alloy journal February 2018
Initial stages of Pt(111) electrooxidation: dynamic and structural studies by surface X-ray diffraction journal January 2017
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles journal October 2011
Probing the structure, the composition and the ORR activity of Pt3Co/C nanocrystallites during a 3422h PEMFC ageing test journal October 2013
Enhancement of the Electroreduction of Oxygen on Pt Alloys with Fe, Ni, and Co journal January 1999
Real-space grid implementation of the projector augmented wave method journal January 2005
Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts journal April 2010
Pt Gd alloy formation on Pt(111): Preparation and structural characterization journal October 2016
Tuning the Activity of Pt(111) for Oxygen Electroreduction by Subsurface Alloying
  • Stephens, Ifan E. L.; Bondarenko, Alexander S.; Perez-Alonso, Francisco J.
  • Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja111690g
journal April 2011
Record activity and stability of dealloyed bimetallic catalysts for proton exchange membrane fuel cells journal January 2015
The enhanced activity of mass-selected Pt Gd nanoparticles for oxygen electroreduction journal August 2015
Tuning Adsorption via Strain and Vertical Ligand Effects journal May 2010
Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction journal December 2017
Electrochemistry and the Future of the Automobile journal June 2010
Benchmarking high surface area electrocatalysts in a gas diffusion electrode: measurement of oxygen reduction activities under realistic conditions journal January 2018
Effect of Surface Composition on Electronic Structure, Stability, and Electrocatalytic Properties of Pt-Transition Metal Alloys:  Pt-Skin versus Pt-Skeleton Surfaces journal July 2006
Beyond the top of the volcano? – A unified approach to electrocatalytic oxygen reduction and oxygen evolution journal November 2016
Correlation of surface site formation to nanoisland growth in the electrochemical roughening of Pt(111) journal February 2018
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals journal March 1999
Understanding the electrocatalysis of oxygen reduction on platinum and its alloys journal January 2012
The path towards sustainable energy journal December 2016
Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces journal February 2007
Surface X-ray diffraction studies of single crystal electrocatalysts journal November 2016
Benchmarking Pt-based electrocatalysts for low temperature fuel cell reactions with the rotating disk electrode: oxygen reduction and hydrogen oxidation in the presence of CO (review article) journal October 2015
Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals journal June 2004
In situ X-ray probing reveals fingerprints of surface platinum oxide journal January 2011
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode journal November 2004
Water dissociation on well-defined platinum surfaces: The electrochemical perspective journal March 2013
In‐situ x‐ray reflectivity study of incipient oxidation of Pt(111) surface in electrolyte solutions journal March 1994
Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis journal January 2015
Scherrer grain-size analysis adapted to grazing-incidence scattering with area detectors journal October 2009
Alloys of platinum and early transition metals as oxygen reduction electrocatalysts journal September 2009

Cited By (4)


Figures / Tables (9)