Role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys: A first-principles study

Hyung Chul Ham; Dhivya Manogaran; Gyeong S. Hwang; Jonghee Han; Hyoung Juhn Kim; Suk Woo Nam; Tae Hoon Lim

doi:10.1016/j.apsusc.2015.01.182

Role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys: A first-principles study

Hyung Chul Ham, Dhivya Manogaran, Gyeong S. Hwang, Jonghee Han, Hyoung Juhn Kim, Suk Woo Nam, Tae Hoon Lim

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

Using spin-polarized density functional calculations, we investigate the role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys through a study of the energetics, charge transfer, geometric and electronic structures of CO on various Pd/Pt ensembles (monomer/dimer/trimer/tetramer). We find that the effect of Pd ensembles on the reduction of CO chemisorption energy is much larger than the Pt ensemble case. In particular, small-sized Pd ensembles like monomer show a substantial reduction of CO chemisorption energy compared to the pure Pd (1 1 1) surface, while there are no significant size and shape effects of Pt ensembles on CO chemisorption energy. This is related to two factors: (1) the steeper potential energy surface (PES) of CO in Pd (1 1 1) than in Pt (1 1 1), indicating that the effect of switch of binding site preference on CO chemisorption energy is much larger in Pd ensembles than in Pt ensembles, and (2) down-shift of d-band in Pd ensembles/up-shift of d-band in Pt ensembles as compared to the corresponding pure Pd (1 1 1)/Pt (1 1 1) surfaces, suggesting more reduced activity of Pd ensembles toward CO adsorption than the Pt ensemble case. We also present the different bonding mechanism of CO on Pd/Pt ensembles by the analysis of orbital resolved density of state.

Original language	English
Pages (from-to)	409-418
Number of pages	10
Journal	Applied Surface Science
Volume	332
DOIs	https://doi.org/10.1016/j.apsusc.2015.01.182
Publication status	Published - 2015 Mar 30

Bibliographical note

Funding Information:
This work is supported by the Welch Foundation ( F-1535 ) and KIST institutional program for Korea Institute of Science and Technology . The authors would also like to thank the Texas Advanced Computing Center for use of their computing resources.

Publisher Copyright:
© 2015 Elsevier B.V. All rights reserved.

Keywords

AuPd
AuPt
CO adsorption
Ensembles
First-principles

ASJC Scopus subject areas

General Chemistry
Condensed Matter Physics
General Physics and Astronomy
Surfaces and Interfaces
Surfaces, Coatings and Films

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10.1016/j.apsusc.2015.01.182

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title = "Role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys: A first-principles study",

abstract = "Using spin-polarized density functional calculations, we investigate the role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys through a study of the energetics, charge transfer, geometric and electronic structures of CO on various Pd/Pt ensembles (monomer/dimer/trimer/tetramer). We find that the effect of Pd ensembles on the reduction of CO chemisorption energy is much larger than the Pt ensemble case. In particular, small-sized Pd ensembles like monomer show a substantial reduction of CO chemisorption energy compared to the pure Pd (1 1 1) surface, while there are no significant size and shape effects of Pt ensembles on CO chemisorption energy. This is related to two factors: (1) the steeper potential energy surface (PES) of CO in Pd (1 1 1) than in Pt (1 1 1), indicating that the effect of switch of binding site preference on CO chemisorption energy is much larger in Pd ensembles than in Pt ensembles, and (2) down-shift of d-band in Pd ensembles/up-shift of d-band in Pt ensembles as compared to the corresponding pure Pd (1 1 1)/Pt (1 1 1) surfaces, suggesting more reduced activity of Pd ensembles toward CO adsorption than the Pt ensemble case. We also present the different bonding mechanism of CO on Pd/Pt ensembles by the analysis of orbital resolved density of state.",

keywords = "AuPd, AuPt, CO adsorption, Ensembles, First-principles",

author = "Ham, {Hyung Chul} and Dhivya Manogaran and Hwang, {Gyeong S.} and Jonghee Han and Kim, {Hyoung Juhn} and Nam, {Suk Woo} and Lim, {Tae Hoon}",

note = "Funding Information: This work is supported by the Welch Foundation ( F-1535 ) and KIST institutional program for Korea Institute of Science and Technology . The authors would also like to thank the Texas Advanced Computing Center for use of their computing resources. Publisher Copyright: {\textcopyright} 2015 Elsevier B.V. All rights reserved.",

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doi = "10.1016/j.apsusc.2015.01.182",

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T2 - A first-principles study

AU - Ham, Hyung Chul

AU - Manogaran, Dhivya

AU - Hwang, Gyeong S.

AU - Han, Jonghee

AU - Kim, Hyoung Juhn

AU - Nam, Suk Woo

AU - Lim, Tae Hoon

N1 - Funding Information: This work is supported by the Welch Foundation ( F-1535 ) and KIST institutional program for Korea Institute of Science and Technology . The authors would also like to thank the Texas Advanced Computing Center for use of their computing resources. Publisher Copyright: © 2015 Elsevier B.V. All rights reserved.

PY - 2015/3/30

Y1 - 2015/3/30

N2 - Using spin-polarized density functional calculations, we investigate the role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys through a study of the energetics, charge transfer, geometric and electronic structures of CO on various Pd/Pt ensembles (monomer/dimer/trimer/tetramer). We find that the effect of Pd ensembles on the reduction of CO chemisorption energy is much larger than the Pt ensemble case. In particular, small-sized Pd ensembles like monomer show a substantial reduction of CO chemisorption energy compared to the pure Pd (1 1 1) surface, while there are no significant size and shape effects of Pt ensembles on CO chemisorption energy. This is related to two factors: (1) the steeper potential energy surface (PES) of CO in Pd (1 1 1) than in Pt (1 1 1), indicating that the effect of switch of binding site preference on CO chemisorption energy is much larger in Pd ensembles than in Pt ensembles, and (2) down-shift of d-band in Pd ensembles/up-shift of d-band in Pt ensembles as compared to the corresponding pure Pd (1 1 1)/Pt (1 1 1) surfaces, suggesting more reduced activity of Pd ensembles toward CO adsorption than the Pt ensemble case. We also present the different bonding mechanism of CO on Pd/Pt ensembles by the analysis of orbital resolved density of state.

AB - Using spin-polarized density functional calculations, we investigate the role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys through a study of the energetics, charge transfer, geometric and electronic structures of CO on various Pd/Pt ensembles (monomer/dimer/trimer/tetramer). We find that the effect of Pd ensembles on the reduction of CO chemisorption energy is much larger than the Pt ensemble case. In particular, small-sized Pd ensembles like monomer show a substantial reduction of CO chemisorption energy compared to the pure Pd (1 1 1) surface, while there are no significant size and shape effects of Pt ensembles on CO chemisorption energy. This is related to two factors: (1) the steeper potential energy surface (PES) of CO in Pd (1 1 1) than in Pt (1 1 1), indicating that the effect of switch of binding site preference on CO chemisorption energy is much larger in Pd ensembles than in Pt ensembles, and (2) down-shift of d-band in Pd ensembles/up-shift of d-band in Pt ensembles as compared to the corresponding pure Pd (1 1 1)/Pt (1 1 1) surfaces, suggesting more reduced activity of Pd ensembles toward CO adsorption than the Pt ensemble case. We also present the different bonding mechanism of CO on Pd/Pt ensembles by the analysis of orbital resolved density of state.

KW - AuPd

KW - AuPt

KW - CO adsorption

KW - Ensembles

KW - First-principles

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VL - 332

SP - 409

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JO - Applied Surface Science

JF - Applied Surface Science

ER -

Role of different Pd/Pt ensembles in determining CO chemisorption on Au-based bimetallic alloys: A first-principles study

Abstract

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Keywords

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