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 Linehan, Richard G. Finke, John Fulton, John Roberts, Tricia D. Smurthwaite, Saim Ozkar, Nathaniel K. Szymczak

Research output: Chapter in Book/Report/Conference proceedingConference contribution

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 languageEnglish
Title of host publicationACS National Meeting Book of Abstracts
Publication statusPublished - 2011
Event242nd ACS National Meeting and Exposition - Denver, CO, United States
Duration: Aug 28 2011Sep 1 2011

Other

Other242nd ACS National Meeting and Exposition
CountryUnited States
CityDenver, CO
Period8/28/119/1/11

Fingerprint

Benzene
Catalysis
Hydrogenation
Metals
Catalysts
Kinetics
Precipitates
Nanoparticles

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

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; Finke, Richard G.; Fulton, John; Roberts, John; Smurthwaite, Tricia D.; Ozkar, Saim; Szymczak, Nathaniel K.

ACS National Meeting Book of Abstracts. 2011.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Bayram, E, Linehan, J, Finke, RG, Fulton, J, Roberts, J, 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. in ACS National Meeting Book of Abstracts. 242nd ACS National Meeting and Exposition, Denver, CO, United States, 8/28/11.
@inproceedings{9abf0d153e8f49eb85a4a0d254b30ff9,
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 John Linehan and Finke, {Richard G.} and John Fulton and John Roberts and Smurthwaite, {Tricia D.} and Saim Ozkar and Szymczak, {Nathaniel K.}",
year = "2011",
language = "English",
booktitle = "ACS National Meeting Book of Abstracts",

}

TY - GEN

T1 - 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

AU - Bayram, Ercan

AU - Linehan, John

AU - Finke, Richard G.

AU - Fulton, John

AU - Roberts, John

AU - Smurthwaite, Tricia D.

AU - Ozkar, Saim

AU - Szymczak, Nathaniel K.

PY - 2011

Y1 - 2011

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.

UR - http://www.scopus.com/inward/record.url?scp=84861015817&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84861015817&partnerID=8YFLogxK

M3 - Conference contribution

BT - ACS National Meeting Book of Abstracts

ER -