Role of Heteronuclear Interactions in Selective H2 Formation from HCOOH Decomposition on Bimetallic Pd/M (M = Late Transition FCC Metal) Catalysts

Jinwon Cho, Sangheon Lee, Sung Pil Yoon, Jonghee Han, SukWoo Nam, Kwan Young Lee, Hyung Chul Ham

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

In this study, by using spin-polarized density functional theory calculations, we have elucidated the role of heteronuclear interactions in determining the selective H2 formation from HCOOH decomposition on bimetallic Pdshell/Mcore (M = late transition FCC metal (Rh, Pt, Ir, Cu, Au, Ag)) catalysts. We found that the catalysis of HCOOH decomposition strongly depends on the variation of surface charge polarization (ligand effect) and lattice distance (strain effect), which are caused by the heteronuclear interactions between surface Pd and core M atoms. In particular, the contraction of surface Pd-Pd bond distance and the increase in electron density in surface Pd atoms in comparison to the pure Pd case are responsible for the enhancement of the selectivity to H2 formation via HCOOH decomposition. Our calculations also unraveled that the d band center location and the density of states for the d band (particularly dz2, dyz, and dxz) near the Fermi level are the important indicators that explain the impact of strain and ligand effects in catalysis, respectively. That is, the surface lattice contraction (expansion) leads to the downshift (upshift) of d band centers in comparison to the pure Pd case, while the electronic charge increase (decrease) in surface Pd atoms results in the depletion (augmentation) of the density of states for dz2, dyz, and dxz orbitals. Our study highlights the importance of properly tailoring the surface lattice distance (d band center) and surface charge polarization (the density of states for dz2, dyz, and dxz orbitals near the Fermi level) by tuning the heteronuclear interactions in bimetallic Pdshell/Mcore catalysts for enhancing the catalysis of HCOOH decomposition toward H2 production, as well as other chemical reactions. (Figure Presented).

Original languageEnglish
Pages (from-to)2553-2562
Number of pages10
JournalACS Catalysis
Volume7
Issue number4
DOIs
Publication statusPublished - 2017 Apr 7

Fingerprint

Transition metals
Decomposition
Catalysts
Catalysis
Surface charge
Fermi level
Atoms
Ligands
Polarization
Density functional theory
Carrier concentration
Chemical reactions
Tuning

Keywords

  • bimetallic catalysts
  • core-shell
  • H production
  • HCOOH
  • lattice distance
  • surface charge polarization

ASJC Scopus subject areas

  • Catalysis

Cite this

Role of Heteronuclear Interactions in Selective H2 Formation from HCOOH Decomposition on Bimetallic Pd/M (M = Late Transition FCC Metal) Catalysts. / Cho, Jinwon; Lee, Sangheon; Yoon, Sung Pil; Han, Jonghee; Nam, SukWoo; Lee, Kwan Young; Ham, Hyung Chul.

In: ACS Catalysis, Vol. 7, No. 4, 07.04.2017, p. 2553-2562.

Research output: Contribution to journalArticle

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abstract = "In this study, by using spin-polarized density functional theory calculations, we have elucidated the role of heteronuclear interactions in determining the selective H2 formation from HCOOH decomposition on bimetallic Pdshell/Mcore (M = late transition FCC metal (Rh, Pt, Ir, Cu, Au, Ag)) catalysts. We found that the catalysis of HCOOH decomposition strongly depends on the variation of surface charge polarization (ligand effect) and lattice distance (strain effect), which are caused by the heteronuclear interactions between surface Pd and core M atoms. In particular, the contraction of surface Pd-Pd bond distance and the increase in electron density in surface Pd atoms in comparison to the pure Pd case are responsible for the enhancement of the selectivity to H2 formation via HCOOH decomposition. Our calculations also unraveled that the d band center location and the density of states for the d band (particularly dz2, dyz, and dxz) near the Fermi level are the important indicators that explain the impact of strain and ligand effects in catalysis, respectively. That is, the surface lattice contraction (expansion) leads to the downshift (upshift) of d band centers in comparison to the pure Pd case, while the electronic charge increase (decrease) in surface Pd atoms results in the depletion (augmentation) of the density of states for dz2, dyz, and dxz orbitals. Our study highlights the importance of properly tailoring the surface lattice distance (d band center) and surface charge polarization (the density of states for dz2, dyz, and dxz orbitals near the Fermi level) by tuning the heteronuclear interactions in bimetallic Pdshell/Mcore catalysts for enhancing the catalysis of HCOOH decomposition toward H2 production, as well as other chemical reactions. (Figure Presented).",
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N2 - In this study, by using spin-polarized density functional theory calculations, we have elucidated the role of heteronuclear interactions in determining the selective H2 formation from HCOOH decomposition on bimetallic Pdshell/Mcore (M = late transition FCC metal (Rh, Pt, Ir, Cu, Au, Ag)) catalysts. We found that the catalysis of HCOOH decomposition strongly depends on the variation of surface charge polarization (ligand effect) and lattice distance (strain effect), which are caused by the heteronuclear interactions between surface Pd and core M atoms. In particular, the contraction of surface Pd-Pd bond distance and the increase in electron density in surface Pd atoms in comparison to the pure Pd case are responsible for the enhancement of the selectivity to H2 formation via HCOOH decomposition. Our calculations also unraveled that the d band center location and the density of states for the d band (particularly dz2, dyz, and dxz) near the Fermi level are the important indicators that explain the impact of strain and ligand effects in catalysis, respectively. That is, the surface lattice contraction (expansion) leads to the downshift (upshift) of d band centers in comparison to the pure Pd case, while the electronic charge increase (decrease) in surface Pd atoms results in the depletion (augmentation) of the density of states for dz2, dyz, and dxz orbitals. Our study highlights the importance of properly tailoring the surface lattice distance (d band center) and surface charge polarization (the density of states for dz2, dyz, and dxz orbitals near the Fermi level) by tuning the heteronuclear interactions in bimetallic Pdshell/Mcore catalysts for enhancing the catalysis of HCOOH decomposition toward H2 production, as well as other chemical reactions. (Figure Presented).

AB - In this study, by using spin-polarized density functional theory calculations, we have elucidated the role of heteronuclear interactions in determining the selective H2 formation from HCOOH decomposition on bimetallic Pdshell/Mcore (M = late transition FCC metal (Rh, Pt, Ir, Cu, Au, Ag)) catalysts. We found that the catalysis of HCOOH decomposition strongly depends on the variation of surface charge polarization (ligand effect) and lattice distance (strain effect), which are caused by the heteronuclear interactions between surface Pd and core M atoms. In particular, the contraction of surface Pd-Pd bond distance and the increase in electron density in surface Pd atoms in comparison to the pure Pd case are responsible for the enhancement of the selectivity to H2 formation via HCOOH decomposition. Our calculations also unraveled that the d band center location and the density of states for the d band (particularly dz2, dyz, and dxz) near the Fermi level are the important indicators that explain the impact of strain and ligand effects in catalysis, respectively. That is, the surface lattice contraction (expansion) leads to the downshift (upshift) of d band centers in comparison to the pure Pd case, while the electronic charge increase (decrease) in surface Pd atoms results in the depletion (augmentation) of the density of states for dz2, dyz, and dxz orbitals. Our study highlights the importance of properly tailoring the surface lattice distance (d band center) and surface charge polarization (the density of states for dz2, dyz, and dxz orbitals near the Fermi level) by tuning the heteronuclear interactions in bimetallic Pdshell/Mcore catalysts for enhancing the catalysis of HCOOH decomposition toward H2 production, as well as other chemical reactions. (Figure Presented).

KW - bimetallic catalysts

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KW - lattice distance

KW - surface charge polarization

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