In situ X-ray probing reveals fingerprints of surface platinum oxide

被引:98
作者
Friebel, Daniel [1 ]
Miller, Daniel J. [1 ]
O'Grady, Christopher P. [1 ]
Anniyev, Toyli [1 ]
Bargar, John [1 ]
Bergmann, Uwe [1 ]
Ogasawara, Hirohito [1 ]
Wikfeldt, Kjartan Thor [2 ]
Pettersson, Lars G. M. [2 ]
Nilsson, Anders [1 ]
机构
[1] SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA
[2] Stockholm Univ, AlbaNova Univ Ctr, FYSIKUM, S-10691 Stockholm, Sweden
关键词
OXYGEN-REDUCTION ELECTROCATALYSTS; HIGH-COVERAGE STRUCTURES; MONOLAYER ELECTROCATALYSTS; FUEL-CELL; ABSORPTION SPECTROSCOPY; ADSORPTION SITES; CLUSTERS; PT(111); NANOPARTICLES; XAS;
D O I
10.1039/c0cp01434f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In situ X-ray absorption spectroscopy (XAS) at the Pt L(3) edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard X-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF code and complementary extended X-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.
引用
收藏
页码:262 / 266
页数:5
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