Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts
Abstract
Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OH adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of PtML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs bymore »
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
- Columbia Univ., New York, NY (United States). Chemical Engineering
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1335400
- Report Number(s):
- BNL-111842-2016-JA
Journal ID: ISSN 2155-5435; R&D Project: MA510MAEA; KC0302010
- Grant/Contract Number:
- SC00112704; SC0012335
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Sasaki, Kotaro, Marinkovic, Nebojsa, Isaacs, Hugh S., and Adzic, Radoslav R. Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts. United States: N. p., 2015.
Web. doi:10.1021/acscatal.5b01862.
Sasaki, Kotaro, Marinkovic, Nebojsa, Isaacs, Hugh S., & Adzic, Radoslav R. Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts. United States. https://doi.org/10.1021/acscatal.5b01862
Sasaki, Kotaro, Marinkovic, Nebojsa, Isaacs, Hugh S., and Adzic, Radoslav R. Tue .
"Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts". United States. https://doi.org/10.1021/acscatal.5b01862. https://www.osti.gov/servlets/purl/1335400.
@article{osti_1335400,
title = {Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts},
author = {Sasaki, Kotaro and Marinkovic, Nebojsa and Isaacs, Hugh S. and Adzic, Radoslav R.},
abstractNote = {Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OH adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of PtML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs by the place exchange process above 1.11 V.},
doi = {10.1021/acscatal.5b01862},
journal = {ACS Catalysis},
number = 1,
volume = 6,
place = {United States},
year = {Tue Nov 17 00:00:00 EST 2015},
month = {Tue Nov 17 00:00:00 EST 2015}
}
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