Lattice-Strain Control of Exceptional Activity in Dealloyed Core-Shell Fuel Cell Catalysts [electronic resource]

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Tác giả:

Ngôn ngữ: eng

Ký hiệu phân loại: 623.45 Ammunition and other destructive agents

Thông tin xuất bản: Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2011

Mô tả vật lý: Medium: ED : , digital, PDF file.

Bộ sưu tập: Metadata

ID: 256878

We present a combined experimental and theoretical approach to demonstrate how lattice strain can be used to continuously tune the catalytic activity of the oxygen reduction reaction (ORR) on bimetallic nanoparticles that have been dealloyed. The sluggish kinetics of the ORR is a key barrier to the adaptation of fuel cells and currently limits their widespread use. Dealloyed Pt-Cu bimetallic nanoparticles, however, have been shown to exhibit uniquely high reactivity for this reaction. We first present evidence for the formation of a core-shell structure during dealloying, which involves removal of Cu from the surface and subsurface of the precursor nanoparticles. We then show that the resulting Pt-rich surface shell exhibits compressive strain that depends on the composition of the precursor alloy. We next demonstrate the existence of a downward shift of the Pt d-band, resulting in weakening of the bond strength of intermediate oxygenated species due to strain. Finally, we combine synthesis, strain, and catalytic reactivity in an experimental/theoretical reactivity-strain relationship which provides guidelines for the rational design of strained oxygen reduction electrocatalysts. The stoichiometry of the precursor, together with the dealloying conditions, provides experimental control over the resulting surface strain and thereby allows continuous tuning of the surface electrocatalytic reactivity - a concept that can be generalized to other catalytic reactions.
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