Enhanced selectivity to H2 formation in decomposition of HCOOH on the Ag19@Pd60 core-shell nanocluster from first-principles

Jinwon Cho, Sangheon Lee, Jonghee Han, Sung Pil Yoon, SukWoo Nam, Sun Hee Choi, Seong Ahn Hong, Kwan Young Lee, Hyung Chul Ham

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition.

Original languageEnglish
Pages (from-to)8233-8237
Number of pages5
JournalJournal of Nanoscience and Nanotechnology
Volume15
Issue number10
DOIs
Publication statusPublished - 2015 Oct 1

Fingerprint

Nanoclusters
nanoclusters
Monolayers
selectivity
Ligands
Decomposition
decomposition
Tensile strain
Dehydrogenation
Fermi level
Binding energy
Density functional theory
Charge transfer
Catalyst activity
dehydrogenation
catalytic activity
Atoms
binding energy
charge transfer
density functional theory

Keywords

  • Ag-Pd core-shell
  • First-principles
  • H formation
  • HCOOH
  • Selectivity

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Chemistry(all)
  • Materials Science(all)
  • Bioengineering
  • Biomedical Engineering

Cite this

Enhanced selectivity to H2 formation in decomposition of HCOOH on the Ag19@Pd60 core-shell nanocluster from first-principles. / Cho, Jinwon; Lee, Sangheon; Han, Jonghee; Yoon, Sung Pil; Nam, SukWoo; Choi, Sun Hee; Hong, Seong Ahn; Lee, Kwan Young; Ham, Hyung Chul.

In: Journal of Nanoscience and Nanotechnology, Vol. 15, No. 10, 01.10.2015, p. 8233-8237.

Research output: Contribution to journalArticle

Cho, Jinwon ; Lee, Sangheon ; Han, Jonghee ; Yoon, Sung Pil ; Nam, SukWoo ; Choi, Sun Hee ; Hong, Seong Ahn ; Lee, Kwan Young ; Ham, Hyung Chul. / Enhanced selectivity to H2 formation in decomposition of HCOOH on the Ag19@Pd60 core-shell nanocluster from first-principles. In: Journal of Nanoscience and Nanotechnology. 2015 ; Vol. 15, No. 10. pp. 8233-8237.
@article{4860b3caefbf4aac80ab1e1a6588a1ad,
title = "Enhanced selectivity to H2 formation in decomposition of HCOOH on the Ag19@Pd60 core-shell nanocluster from first-principles",
abstract = "In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition.",
keywords = "Ag-Pd core-shell, First-principles, H formation, HCOOH, Selectivity",
author = "Jinwon Cho and Sangheon Lee and Jonghee Han and Yoon, {Sung Pil} and SukWoo Nam and Choi, {Sun Hee} and Hong, {Seong Ahn} and Lee, {Kwan Young} and Ham, {Hyung Chul}",
year = "2015",
month = "10",
day = "1",
doi = "10.1166/jnn.2015.11442",
language = "English",
volume = "15",
pages = "8233--8237",
journal = "Journal of Nanoscience and Nanotechnology",
issn = "1533-4880",
publisher = "American Scientific Publishers",
number = "10",

}

TY - JOUR

T1 - Enhanced selectivity to H2 formation in decomposition of HCOOH on the Ag19@Pd60 core-shell nanocluster from first-principles

AU - Cho, Jinwon

AU - Lee, Sangheon

AU - Han, Jonghee

AU - Yoon, Sung Pil

AU - Nam, SukWoo

AU - Choi, Sun Hee

AU - Hong, Seong Ahn

AU - Lee, Kwan Young

AU - Ham, Hyung Chul

PY - 2015/10/1

Y1 - 2015/10/1

N2 - In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition.

AB - In this study, using spin-polarized density functional theory calculation we examined the origin of enhanced catalytic activity toward H2 production from HCOOH in Ag19@Pd60 core-shell nanoclusters (a 79-atom truncated octahedral cluster models). First, we find that the Pd monolayer shell on the Ag core can greatly enhance the selectivity to H2 formation via HCOOH decomposition compared to the pure Pd79 cluster by substantially reducing the binding energy of key intermediate HCOO and in turn the barrier for dehydrogenation. This activity enhancement is related to the modification of d states in the Pd monolayer shell by the strong ligand effect between Ag core and Pd shell, rather than the tensile strain effect by Ag core. In particular, the absence of dz2-r2 density of states near the Fermi level in the Pd monolayer shell (which originated from the substantial charge transfer from Ag to Pd) is the main reason for the increased H2 production from HCOOH decomposition.

KW - Ag-Pd core-shell

KW - First-principles

KW - H formation

KW - HCOOH

KW - Selectivity

UR - http://www.scopus.com/inward/record.url?scp=84947286928&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84947286928&partnerID=8YFLogxK

U2 - 10.1166/jnn.2015.11442

DO - 10.1166/jnn.2015.11442

M3 - Article

VL - 15

SP - 8233

EP - 8237

JO - Journal of Nanoscience and Nanotechnology

JF - Journal of Nanoscience and Nanotechnology

SN - 1533-4880

IS - 10

ER -