Importance of ligand effect in selective hydrogen formation via formic acid decomposition on the bimetallic Pd/Ag catalyst from first-principles

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

Research output: Contribution to journalArticle

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Abstract

The critical role of the Ag-Pd ligand effect (which is tuned by changing the number of Pd atomic layers) in determining the dehydrogenation and dehydration of HCOOH on the bimetallic Pd/Ag catalysts was elucidated by using the spin-polarized density functional theory (DFT) calculations. Our calculations suggest that the selectivity to H2 production from HCOOH on the bimetallic Pd/Ag catalysts strongly depends on the Pd atomic layer thickness at near surface. In particular, the thinnest Pd monolayer in the Pd/Ag system is responsible for enhancing the selectivity of HCOOH decomposition toward H2 production by reducing the surface binding strength of specific intermediates such as HCOO and HCO. The dominant Ag-Pd ligand effect by the substantial charge donation to the Pd surface from the subsurface Ag [which significantly reduce the density of state (particularly, dz2-r2 orbital) near the Fermi level] proves to be a key factor for the selective hydrogen production from HCOOH decomposition, whereas the expansive (tensile) strain imposed by the underlying Ag substrate plays a minor role. This work hints on the importance of properly engineering the surface activity of the Ag-Pd core-shell catalysts by the interplay between ligand and strain effects.

Original languageEnglish
Pages (from-to)22553-22560
Number of pages8
JournalJournal of Physical Chemistry C
Volume118
Issue number39
DOIs
Publication statusPublished - 2014 Jan 1

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formic acid
Formic acid
Hydrogen
Ligands
Decomposition
decomposition
catalysts
ligands
Catalysts
hydrogen
selectivity
Tensile strain
hydrogen production
Dehydrogenation
Hydrogen production
dehydrogenation
Fermi level
Dehydration
dehydration
Density functional theory

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Importance of ligand effect in selective hydrogen formation via formic acid decomposition on the bimetallic Pd/Ag catalyst from first-principles. / Cho, Jinwon; Lee, Sangheon; Han, Jonghee; Yoon, Sung Pil; Nam, SukWoo; Choi, Sun Hee; Lee, Kwan Young; Ham, Hyung Chul.

In: Journal of Physical Chemistry C, Vol. 118, No. 39, 01.01.2014, p. 22553-22560.

Research output: Contribution to journalArticle

Cho, Jinwon ; Lee, Sangheon ; Han, Jonghee ; Yoon, Sung Pil ; Nam, SukWoo ; Choi, Sun Hee ; Lee, Kwan Young ; Ham, Hyung Chul. / Importance of ligand effect in selective hydrogen formation via formic acid decomposition on the bimetallic Pd/Ag catalyst from first-principles. In: Journal of Physical Chemistry C. 2014 ; Vol. 118, No. 39. pp. 22553-22560.
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