Is it single-metal homogeneous or polymetallic heterogeneous catalysis? Further investigation of the catalytically active species in benzene hydrogenation beginning with [RhCp*Cl 2] 2 via operando-XAFS, kinetic and poisoning studies

Ercan Bayram; John C. Linehan; Richard G. Finke; John Fulton; John A.S. Roberts; Tricia D. Smurthwaite; Saim Ozkar; Nathaniel K. Szymczak

Is it single-metal homogeneous or polymetallic heterogeneous catalysis? Further investigation of the catalytically active species in benzene hydrogenation beginning with [RhCp*Cl ₂] ₂ via operando-XAFS, kinetic and poisoning studies

Ercan Bayram, John C. Linehan, Richard G. Finke, John Fulton, John A.S. Roberts, Tricia D. Smurthwaite, Saim Ozkar, Nathaniel K. Szymczak

Pacific Northwest National Laboratory

Research output: Contribution to journal › Conference article

Abstract

Previous investigation (Hagen et al. J. Am. Chem. Soc. 2005, 127, 4423) for benzene hydrogenation starting with [RhCp*Cl ₂] ₂ at 100 °C and 50 atm initial H ₂ pressure concluded that the true catalyst was most likely Rh(0) nanoparticles on the basis of sigmoidal kinetics, Rh(0) precipitate, and positive Hg(0) poisoning studies. There was, at the time, no other plausible hypothesis for the true catalyst in light of the extant data. Further investigation via operando-XAFS provides a new hypothesis for the active catalyst: ligated Rh ₄ sub-nanometer clusters that constitute ∼98% of the total soluble Rh in solution. Kinetics and quantitative poisoning studies support this hypothesis. The results are of significant interest since determining the nature of the true catalyst continues to be a central, often vexing issue, in any and all catalytic reactions.

Original language	English
Journal	ACS National Meeting Book of Abstracts
Publication status	Published - Dec 1 2011
Event	242nd ACS National Meeting and Exposition - Denver, CO, United States Duration: Aug 28 2011 → Sep 1 2011

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)

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Bayram, E., Linehan, J. C., Finke, R. G., Fulton, J., Roberts, J. A. S., Smurthwaite, T. D., Ozkar, S., & Szymczak, N. K. (2011). Is it single-metal homogeneous or polymetallic heterogeneous catalysis? Further investigation of the catalytically active species in benzene hydrogenation beginning with [RhCp*Cl ₂] ₂ via operando-XAFS, kinetic and poisoning studies. ACS National Meeting Book of Abstracts.

Is it single-metal homogeneous or polymetallic heterogeneous catalysis? Further investigation of the catalytically active species in benzene hydrogenation beginning with [RhCp*Cl ₂] ₂ via operando-XAFS, kinetic and poisoning studies. / Bayram, Ercan; Linehan, John C.; Finke, Richard G.; Fulton, John; Roberts, John A.S.; Smurthwaite, Tricia D.; Ozkar, Saim; Szymczak, Nathaniel K.

In: ACS National Meeting Book of Abstracts, 01.12.2011.

Research output: Contribution to journal › Conference article

Bayram, E, Linehan, JC, Finke, RG, Fulton, J, Roberts, JAS, Smurthwaite, TD, Ozkar, S & Szymczak, NK 2011, 'Is it single-metal homogeneous or polymetallic heterogeneous catalysis? Further investigation of the catalytically active species in benzene hydrogenation beginning with [RhCp*Cl ₂] ₂ via operando-XAFS, kinetic and poisoning studies', ACS National Meeting Book of Abstracts.

Bayram, Ercan ; Linehan, John C. ; Finke, Richard G. ; Fulton, John ; Roberts, John A.S. ; Smurthwaite, Tricia D. ; Ozkar, Saim ; Szymczak, Nathaniel K. / Is it single-metal homogeneous or polymetallic heterogeneous catalysis? Further investigation of the catalytically active species in benzene hydrogenation beginning with [RhCp*Cl ₂] ₂ via operando-XAFS, kinetic and poisoning studies. In: ACS National Meeting Book of Abstracts. 2011.

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title = "Is it single-metal homogeneous or polymetallic heterogeneous catalysis? Further investigation of the catalytically active species in benzene hydrogenation beginning with [RhCp*Cl 2] 2 via operando-XAFS, kinetic and poisoning studies",

abstract = "Previous investigation (Hagen et al. J. Am. Chem. Soc. 2005, 127, 4423) for benzene hydrogenation starting with [RhCp*Cl 2] 2 at 100 °C and 50 atm initial H 2 pressure concluded that the true catalyst was most likely Rh(0) nanoparticles on the basis of sigmoidal kinetics, Rh(0) precipitate, and positive Hg(0) poisoning studies. There was, at the time, no other plausible hypothesis for the true catalyst in light of the extant data. Further investigation via operando-XAFS provides a new hypothesis for the active catalyst: ligated Rh 4 sub-nanometer clusters that constitute ∼98% of the total soluble Rh in solution. Kinetics and quantitative poisoning studies support this hypothesis. The results are of significant interest since determining the nature of the true catalyst continues to be a central, often vexing issue, in any and all catalytic reactions.",

author = "Ercan Bayram and Linehan, {John C.} and Finke, {Richard G.} and John Fulton and Roberts, {John A.S.} and Smurthwaite, {Tricia D.} and Saim Ozkar and Szymczak, {Nathaniel K.}",

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AU - Bayram, Ercan

AU - Linehan, John C.

AU - Finke, Richard G.

AU - Fulton, John

AU - Roberts, John A.S.

AU - Smurthwaite, Tricia D.

AU - Ozkar, Saim

AU - Szymczak, Nathaniel K.

PY - 2011/12/1

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N2 - Previous investigation (Hagen et al. J. Am. Chem. Soc. 2005, 127, 4423) for benzene hydrogenation starting with [RhCp*Cl 2] 2 at 100 °C and 50 atm initial H 2 pressure concluded that the true catalyst was most likely Rh(0) nanoparticles on the basis of sigmoidal kinetics, Rh(0) precipitate, and positive Hg(0) poisoning studies. There was, at the time, no other plausible hypothesis for the true catalyst in light of the extant data. Further investigation via operando-XAFS provides a new hypothesis for the active catalyst: ligated Rh 4 sub-nanometer clusters that constitute ∼98% of the total soluble Rh in solution. Kinetics and quantitative poisoning studies support this hypothesis. The results are of significant interest since determining the nature of the true catalyst continues to be a central, often vexing issue, in any and all catalytic reactions.

AB - Previous investigation (Hagen et al. J. Am. Chem. Soc. 2005, 127, 4423) for benzene hydrogenation starting with [RhCp*Cl 2] 2 at 100 °C and 50 atm initial H 2 pressure concluded that the true catalyst was most likely Rh(0) nanoparticles on the basis of sigmoidal kinetics, Rh(0) precipitate, and positive Hg(0) poisoning studies. There was, at the time, no other plausible hypothesis for the true catalyst in light of the extant data. Further investigation via operando-XAFS provides a new hypothesis for the active catalyst: ligated Rh 4 sub-nanometer clusters that constitute ∼98% of the total soluble Rh in solution. Kinetics and quantitative poisoning studies support this hypothesis. The results are of significant interest since determining the nature of the true catalyst continues to be a central, often vexing issue, in any and all catalytic reactions.

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