Oxidation of silanes to silanols on Pd nanoparticles: H2 desorption accelerated by surface oxygen atom

Takashi Kamachi, Ken Ichi Shimizu, Daisuke Yoshihiro, Kazunobu Igawa, Katsuhiko Tomooka, Kazunari Yoshizawa

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The oxidation of silane to silanol on the clean and oxygen-covered Pd(111) surface is investigated with periodic density functional theory calculations to gain a better understanding of the effect of surface oxygen atom on Pd nanoparticle catalysts. The calculations confirmed that this catalytic reaction is initiated by the dissociative adsorption of silane on the Pd surface. The resultant silyl group is attacked by a water molecule to form silanol and an H atom on the Pd surface with inversion of configuration at the Si center. An activation energy of 11.3 kcal/mol is required for the water addition, and the transition state for this step is energetically highest in the entire reaction profile. These computational results are in good agreement with our stereochemical and kinetic studies. The H atoms on the Pd surface inhibit further reaction, and therefore, they should be removed to achieve the catalytic activity experimentally. We found that the role of the surface oxygen atom is to facilitate the desorption of H2 from the Pd surface without the formation of OH and H2O. The introduction of surface oxygen atoms can enhance the catalytic ability of metal nanoparticles for green organic reactions.

Original languageEnglish
Pages (from-to)22967-22973
Number of pages7
JournalJournal of Physical Chemistry C
Volume117
Issue number44
DOIs
Publication statusPublished - Nov 7 2013

Fingerprint

Silanes
silanes
oxygen atoms
Desorption
desorption
Oxygen
Nanoparticles
Atoms
Oxidation
nanoparticles
oxidation
silanol
Water
Metal nanoparticles
water
Density functional theory
atoms
catalytic activity
Catalyst activity
Activation energy

All Science Journal Classification (ASJC) codes

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

Cite this

Oxidation of silanes to silanols on Pd nanoparticles : H2 desorption accelerated by surface oxygen atom. / Kamachi, Takashi; Shimizu, Ken Ichi; Yoshihiro, Daisuke; Igawa, Kazunobu; Tomooka, Katsuhiko; Yoshizawa, Kazunari.

In: Journal of Physical Chemistry C, Vol. 117, No. 44, 07.11.2013, p. 22967-22973.

Research output: Contribution to journalArticle

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AU - Tomooka, Katsuhiko

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AB - The oxidation of silane to silanol on the clean and oxygen-covered Pd(111) surface is investigated with periodic density functional theory calculations to gain a better understanding of the effect of surface oxygen atom on Pd nanoparticle catalysts. The calculations confirmed that this catalytic reaction is initiated by the dissociative adsorption of silane on the Pd surface. The resultant silyl group is attacked by a water molecule to form silanol and an H atom on the Pd surface with inversion of configuration at the Si center. An activation energy of 11.3 kcal/mol is required for the water addition, and the transition state for this step is energetically highest in the entire reaction profile. These computational results are in good agreement with our stereochemical and kinetic studies. The H atoms on the Pd surface inhibit further reaction, and therefore, they should be removed to achieve the catalytic activity experimentally. We found that the role of the surface oxygen atom is to facilitate the desorption of H2 from the Pd surface without the formation of OH and H2O. The introduction of surface oxygen atoms can enhance the catalytic ability of metal nanoparticles for green organic reactions.

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