On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation: A Kinetic Study of Au/MO x Catalysts Prepared from Oleylamine-Capped Colloidal Nanoparticles

James E. Bruno, K. B. Sravan Kumar, Nicolas S. Dwarica, Alexander Hüther, Zhifeng Chen, Clemente S. Guzman, Emily R. Hand, William C. Moore, Robert M. Rioux, Lars C. Grabow, Bert D. Chandler

Research output: Contribution to journalArticle

Abstract

We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylamine-capped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ∼2.5 nm in diameter. The catalysts showed high alkene selectivity (>90 %) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25–40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen-bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal-support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1-octyne reaction orders (∼−0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non-competitive activated adsorption of H 2 on an alkyne-covered Au surface.

Original languageEnglish (US)
Pages (from-to)1650-1664
Number of pages15
JournalChemCatChem
Volume11
Issue number6
DOIs
StatePublished - Mar 20 2019

Fingerprint

Alkynes
alkynes
Hydrogenation
hydrogenation
Nanoparticles
Adsorption
catalysts
nanoparticles
Catalysts
Kinetics
adsorption
kinetics
electronics
Catalyst supports
Discrete Fourier transforms
Catalyst selectivity
Colloids
Alkenes
hydrogen
Reaction kinetics

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Bruno, James E. ; Sravan Kumar, K. B. ; Dwarica, Nicolas S. ; Hüther, Alexander ; Chen, Zhifeng ; Guzman, Clemente S. ; Hand, Emily R. ; Moore, William C. ; Rioux, Robert M. ; Grabow, Lars C. ; Chandler, Bert D. / On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation : A Kinetic Study of Au/MO x Catalysts Prepared from Oleylamine-Capped Colloidal Nanoparticles. In: ChemCatChem. 2019 ; Vol. 11, No. 6. pp. 1650-1664.
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abstract = "We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylamine-capped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ∼2.5 nm in diameter. The catalysts showed high alkene selectivity (>90 {\%}) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25–40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen-bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal-support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1-octyne reaction orders (∼−0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non-competitive activated adsorption of H 2 on an alkyne-covered Au surface.",
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Bruno, JE, Sravan Kumar, KB, Dwarica, NS, Hüther, A, Chen, Z, Guzman, CS, Hand, ER, Moore, WC, Rioux, RM, Grabow, LC & Chandler, BD 2019, 'On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation: A Kinetic Study of Au/MO x Catalysts Prepared from Oleylamine-Capped Colloidal Nanoparticles', ChemCatChem, vol. 11, no. 6, pp. 1650-1664. https://doi.org/10.1002/cctc.201801882

On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation : A Kinetic Study of Au/MO x Catalysts Prepared from Oleylamine-Capped Colloidal Nanoparticles. / Bruno, James E.; Sravan Kumar, K. B.; Dwarica, Nicolas S.; Hüther, Alexander; Chen, Zhifeng; Guzman, Clemente S.; Hand, Emily R.; Moore, William C.; Rioux, Robert M.; Grabow, Lars C.; Chandler, Bert D.

In: ChemCatChem, Vol. 11, No. 6, 20.03.2019, p. 1650-1664.

Research output: Contribution to journalArticle

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T1 - On the Limited Role of Electronic Support Effects in Selective Alkyne Hydrogenation

T2 - A Kinetic Study of Au/MO x Catalysts Prepared from Oleylamine-Capped Colloidal Nanoparticles

AU - Bruno, James E.

AU - Sravan Kumar, K. B.

AU - Dwarica, Nicolas S.

AU - Hüther, Alexander

AU - Chen, Zhifeng

AU - Guzman, Clemente S.

AU - Hand, Emily R.

AU - Moore, William C.

AU - Rioux, Robert M.

AU - Grabow, Lars C.

AU - Chandler, Bert D.

PY - 2019/3/20

Y1 - 2019/3/20

N2 - We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylamine-capped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ∼2.5 nm in diameter. The catalysts showed high alkene selectivity (>90 %) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25–40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen-bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal-support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1-octyne reaction orders (∼−0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non-competitive activated adsorption of H 2 on an alkyne-covered Au surface.

AB - We report a quantitative kinetic evaluation and study of support effects for partial alkyne hydrogenation using oleylamine-capped Au colloids as catalyst precursors. The amine capping agents can be removed under reducing conditions, generating supported Au nanoparticles of ∼2.5 nm in diameter. The catalysts showed high alkene selectivity (>90 %) at all conversions during alkyne partial hydrogenation. Catalytic activity, observed rate constants, and apparent activation energies (25–40 kJ/mol) were similar for all Au catalysts, indicating support effects are relatively small. Alkyne adsorption, probed with FTIR and DFT, showed adsorption on the support was associated with hydrogen-bonding interactions. DFT calculations indicate strong alkyne adsorption on Au sites, with the strongest adsorption sites at the metal-support interface (MSI). The catalysts had similar hydrogen reaction orders (0.7–0.9), and 1-octyne reaction orders (∼−0.2), suggesting a common mechanism. The reaction kinetics are most consistent with a mechanism involving the non-competitive activated adsorption of H 2 on an alkyne-covered Au surface.

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DO - 10.1002/cctc.201801882

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