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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

Abstract

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 Pt 5Gd 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.

Authors:
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)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1476110
Grant/Contract Number:  
AC02-76SF00515; 9455; DFF-4093-00104; EliteForsk travel grant
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 47; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; active phase; electrocatalysis; oxygen reduction reaction; platinum; X-ray diffraction

Citation Formats

Escudero-Escribano, María, Pedersen, Anders F., Ulrikkeholm, Elisabeth T., Jensen, Kim D., Hansen, Martin H., Rossmeisl, Jan, Stephens, Ifan E. L., and Chorkendorff, Ib. Active-Phase Formation and Stability of Gd/Pt(111) Electrocatalysts for Oxygen Reduction: An In Situ Grazing Incidence X-Ray Diffraction Study. United States: N. p., 2018. Web. doi:10.1002/chem.201801587.
Escudero-Escribano, María, Pedersen, Anders F., Ulrikkeholm, Elisabeth T., Jensen, Kim D., Hansen, Martin H., Rossmeisl, Jan, Stephens, Ifan E. L., & Chorkendorff, Ib. Active-Phase Formation and Stability of Gd/Pt(111) Electrocatalysts for Oxygen Reduction: An In Situ Grazing Incidence X-Ray Diffraction Study. United States. doi:10.1002/chem.201801587.
Escudero-Escribano, María, Pedersen, Anders F., Ulrikkeholm, Elisabeth T., Jensen, Kim D., Hansen, Martin H., Rossmeisl, Jan, Stephens, Ifan E. L., and Chorkendorff, Ib. Tue . "Active-Phase Formation and Stability of Gd/Pt(111) Electrocatalysts for Oxygen Reduction: An In Situ Grazing Incidence X-Ray Diffraction Study". United States. doi:10.1002/chem.201801587. https://www.osti.gov/servlets/purl/1476110.
@article{osti_1476110,
title = {Active-Phase Formation and Stability of Gd/Pt(111) Electrocatalysts for Oxygen Reduction: An In Situ Grazing Incidence X-Ray Diffraction Study},
author = {Escudero-Escribano, María and Pedersen, Anders F. and Ulrikkeholm, Elisabeth T. and Jensen, Kim D. and Hansen, Martin H. and Rossmeisl, Jan and Stephens, Ifan E. L. and Chorkendorff, Ib},
abstractNote = {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.},
doi = {10.1002/chem.201801587},
journal = {Chemistry - A European Journal},
number = 47,
volume = 24,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 5 works
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Figures / Tables:

Figure 1 Figure 1: Schematic representation of the in situ X-ray diffraction setup and three-electrode electrochemical cell for characterisation of Gd/Pt(l 11) single-crystal electrodes in the hanging meniscus configuration used at SSRL. This setup enabled the evaluation of the Pt overlayer formation and evolution in situ, during the electrochemical experiments on Gd/Pt(111)more » surfaces.« less

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    Works referencing / citing this record:

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.