Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S.; Adzic, Radoslav R.

doi:10.1021/acscatal.5b01862

Title: Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

Journal Article · Tue Nov 17 00:00:00 EST 2015 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.5b01862· OSTI ID:1335400

Sasaki, Kotaro ^[1]; Marinkovic, Nebojsa ^[2]; Isaacs, Hugh S. ^[1]; Adzic, Radoslav R. ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
Columbia Univ., New York, NY (United States). Chemical Engineering

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 Pt_ML 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.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC00112704; SC0012335

OSTI ID:: 1335400

Report Number(s):: BNL-111842-2016-JA; R&D Project: MA510MAEA; KC0302010

Journal Information:: ACS Catalysis, Vol. 6, Issue 1; ISSN 2155-5435

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 71 works

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