Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies

Gaurav Kumar, Luke Tibbitts, Jaclyn Newell, Basu Panthi, Ahana Mukhopadhyay, Robert M. Rioux, Christopher J. Pursell, Michael Janik, Bert D. Chandler

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal-support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles.

Original languageEnglish (US)
Pages (from-to)268-274
Number of pages7
JournalNature Chemistry
Volume10
Issue number3
DOIs
StatePublished - Mar 1 2018

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Discrete Fourier transforms
Electronic equipment
Metals
Oxides
Nanoparticles
Catalysts
Benzyl Alcohol
Metal nanoparticles
Catalyst supports
Density functional theory
Catalyst activity
Alcohols
Oxidation
Electrons

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Kumar, Gaurav ; Tibbitts, Luke ; Newell, Jaclyn ; Panthi, Basu ; Mukhopadhyay, Ahana ; Rioux, Robert M. ; Pursell, Christopher J. ; Janik, Michael ; Chandler, Bert D. / Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies. In: Nature Chemistry. 2018 ; Vol. 10, No. 3. pp. 268-274.
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Kumar, G, Tibbitts, L, Newell, J, Panthi, B, Mukhopadhyay, A, Rioux, RM, Pursell, CJ, Janik, M & Chandler, BD 2018, 'Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies', Nature Chemistry, vol. 10, no. 3, pp. 268-274. https://doi.org/10.1038/NCHEM.2911

Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies. / Kumar, Gaurav; Tibbitts, Luke; Newell, Jaclyn; Panthi, Basu; Mukhopadhyay, Ahana; Rioux, Robert M.; Pursell, Christopher J.; Janik, Michael; Chandler, Bert D.

In: Nature Chemistry, Vol. 10, No. 3, 01.03.2018, p. 268-274.

Research output: Contribution to journalArticle

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