Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3 d transition metals) alloy catalyst from first-principles

Chang Eun Kim, Dong Hee Lim, Jong Hyun Jang, Hyoung Juhn Kim, Sung Pil Yoon, Jonghee Han, SukWoo Nam, Seong Ahn Hong, Aloysius Soon, Hyung Chul Ham

Research output: Contribution to journalArticle

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Abstract

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

Original languageEnglish
Article number034707
JournalJournal of Chemical Physics
Volume142
Issue number3
DOIs
Publication statusPublished - 2015 Jan 21
Externally publishedYes

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Transition metal alloys
Gold
Skin
transition metals
gold
catalysts
Catalysts
Oxygen
Atoms
oxygen
atoms
Surface charge
Fermi level
Electronic structure
Transition metals
Density functional theory
Fuel cells
durability
Durability
fuel cells

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3 d transition metals) alloy catalyst from first-principles. / Kim, Chang Eun; Lim, Dong Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, SukWoo; Hong, Seong Ahn; Soon, Aloysius; Ham, Hyung Chul.

In: Journal of Chemical Physics, Vol. 142, No. 3, 034707, 21.01.2015.

Research output: Contribution to journalArticle

Kim, Chang Eun ; Lim, Dong Hee ; Jang, Jong Hyun ; Kim, Hyoung Juhn ; Yoon, Sung Pil ; Han, Jonghee ; Nam, SukWoo ; Hong, Seong Ahn ; Soon, Aloysius ; Ham, Hyung Chul. / Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3 d transition metals) alloy catalyst from first-principles. In: Journal of Chemical Physics. 2015 ; Vol. 142, No. 3.
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