Kinetic study of a direct water synthesis over silica-supported gold nanoparticles

David G. Barton, Simon Podkolzin

Research output: Contribution to journalArticle

101 Citations (Scopus)

Abstract

The reaction mechanism of water formation from H 2 and O 2 was studied over a series of silica-supported gold nanoparticles. The metal particle size distributions were estimated with TEM and XRD measurements. Hydrogen and oxygen adsorption calorimetry was used to probe the nature and properties of surface species formed by these molecules. DFT calculations with Au 5, Au 13, and Au 55 clusters and with Au(111) and Au(211) periodic slabs were performed to estimate the thermodynamic stability and reactivity of surface species. Kinetic measurements were performed by varying the reactant partial pressures at 433 K and by varying the temperature from 383 to 483 K at 2.5 kPa of O 2 and 5 kPa of H 2. The measured apparent power law kinetic parameters were similar for all catalysts in this study: hydrogen order of 0.7-0.8, oxygen order of 0.1-0.2, and activation energy of 37-41 kJ/mol. Catalysts with Si-MFI (Silicalite-1) and Ti-MFI (TS-1 with 1 wt % Ti) exhibited similar activities. The activities of these catalysts with the MFI crystalline supports were 60-70 times higher than that of an analogous catalyst with an amorphous silica support. Water addition in the inlet stream at 3 vol % did not affect the reaction rates. The mechanism of water formation over gold is proposed to proceed through the formation of OOH and H 2O 2 intermediates. A rate expression derived based on this mechanism accurately describes the experimental kinetic data. The higher activity of the MFI-supported catalysts is attributed to a higher concentration of gold particles comparable in size to Au 13, which can fit inside MFI pores. DFT results suggest that such intermediate-size gold particles are most reactive toward water formation. Smaller particles are proposed to be less reactive due to the instability of the OOH intermediate whereas larger particles are less reactive due to the instability of adsorbed oxygen.

Original languageEnglish (US)
Pages (from-to)2262-2274
Number of pages13
JournalJournal of Physical Chemistry B
Volume109
Issue number6
DOIs
StatePublished - Feb 17 2005
Externally publishedYes

Fingerprint

Silicon Dioxide
Gold
Silica
Catalyst supports
gold
Nanoparticles
silicon dioxide
catalysts
nanoparticles
Catalysts
Kinetics
Water
kinetics
synthesis
Oxygen
Discrete Fourier transforms
Hydrogen
water
oxygen
Calorimetry

All Science Journal Classification (ASJC) codes

  • Materials Chemistry
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

Cite this

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title = "Kinetic study of a direct water synthesis over silica-supported gold nanoparticles",
abstract = "The reaction mechanism of water formation from H 2 and O 2 was studied over a series of silica-supported gold nanoparticles. The metal particle size distributions were estimated with TEM and XRD measurements. Hydrogen and oxygen adsorption calorimetry was used to probe the nature and properties of surface species formed by these molecules. DFT calculations with Au 5, Au 13, and Au 55 clusters and with Au(111) and Au(211) periodic slabs were performed to estimate the thermodynamic stability and reactivity of surface species. Kinetic measurements were performed by varying the reactant partial pressures at 433 K and by varying the temperature from 383 to 483 K at 2.5 kPa of O 2 and 5 kPa of H 2. The measured apparent power law kinetic parameters were similar for all catalysts in this study: hydrogen order of 0.7-0.8, oxygen order of 0.1-0.2, and activation energy of 37-41 kJ/mol. Catalysts with Si-MFI (Silicalite-1) and Ti-MFI (TS-1 with 1 wt {\%} Ti) exhibited similar activities. The activities of these catalysts with the MFI crystalline supports were 60-70 times higher than that of an analogous catalyst with an amorphous silica support. Water addition in the inlet stream at 3 vol {\%} did not affect the reaction rates. The mechanism of water formation over gold is proposed to proceed through the formation of OOH and H 2O 2 intermediates. A rate expression derived based on this mechanism accurately describes the experimental kinetic data. The higher activity of the MFI-supported catalysts is attributed to a higher concentration of gold particles comparable in size to Au 13, which can fit inside MFI pores. DFT results suggest that such intermediate-size gold particles are most reactive toward water formation. Smaller particles are proposed to be less reactive due to the instability of the OOH intermediate whereas larger particles are less reactive due to the instability of adsorbed oxygen.",
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Kinetic study of a direct water synthesis over silica-supported gold nanoparticles. / Barton, David G.; Podkolzin, Simon.

In: Journal of Physical Chemistry B, Vol. 109, No. 6, 17.02.2005, p. 2262-2274.

Research output: Contribution to journalArticle

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