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Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites.

Structural characterization of the catalytically significant sites on solid catalyst surfaces is frequently tenuous because their fraction, among all sites, typically is quite low. Here we report the combined application of solid-state (13)C-cross-polarization magic angle spinning nuclear magnetic r... Full description

Journal Title: Proceedings of the National Academy of Sciences of the United States of America January 8, 2013, Vol.110(2), pp.413-418
Main Author: Williams, Linda A
Other Authors: Guo, Neng , Motta, Alessandro , Delferro, Massimiliano , Fragalà, Ignazio L , Miller, Jeffrey T , Marks, Tobin J
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1091-6490 ; DOI: 10.1073/pnas.1220240110
Link: http://search.proquest.com/docview/1273348040/?pq-origsite=primo
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title: Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites.
format: Article
creator:
  • Williams, Linda A
  • Guo, Neng
  • Motta, Alessandro
  • Delferro, Massimiliano
  • Fragalà, Ignazio L
  • Miller, Jeffrey T
  • Marks, Tobin J
subjects:
  • Adsorption–Chemistry
  • Aluminum Oxide–Chemistry
  • Benzene–Chemistry
  • Carbon Isotopes–Methods
  • Catalysis–Chemistry
  • Hydrocarbons, Aromatic–Methods
  • Hydrogenation–Methods
  • Kinetics–Methods
  • Models, Chemical–Methods
  • Models, Molecular–Methods
  • Molecular Structure–Methods
  • Nuclear Magnetic Resonance, Biomolecular–Methods
  • Organometallic Compounds–Methods
  • Static Electricity–Methods
  • Surface Properties–Methods
  • X-Ray Absorption Spectroscopy–Methods
  • Zirconium–Methods
  • Carbon Isotopes
  • Hydrocarbons, Aromatic
  • Organometallic Compounds
ispartof: Proceedings of the National Academy of Sciences of the United States of America, January 8, 2013, Vol.110(2), pp.413-418
description: Structural characterization of the catalytically significant sites on solid catalyst surfaces is frequently tenuous because their fraction, among all sites, typically is quite low. Here we report the combined application of solid-state (13)C-cross-polarization magic angle spinning nuclear magnetic resonance ((13)C-CPMAS-NMR) spectroscopy, density functional theory (DFT), and Zr X-ray absorption spectroscopy (XAS) to characterize the adsorption products and surface chemistry of the precatalysts (η(5)-C(5)H(5))(2)ZrR(2) (R = H, CH(3)) and [η(5)-C(5)(CH(3))(5)]Zr(CH(3))(3) adsorbed on Brønsted superacidic sulfated alumina (AlS). The latter complex is exceptionally active for benzene hydrogenation, with ~100% of the Zr sites catalytically significant as determined by kinetic poisoning experiments. The (13)C-CPMAS-NMR, DFT, and XAS data indicate formation of organozirconium cations having a largely electrostatic [η(5)-C(5)(CH(3))(5)]Zr(CH(3))(2)(+)· · · AlS(-) interaction with greatly elongated Zr · · · O(AlS) distances of ~2.35(2) Å. The catalytic benzene hydrogenation cycle is stepwise understandable by DFT, and proceeds via turnover-limiting H(2) delivery to surface [η(5)-C(5)(CH(3))(5)]ZrH(2)(benzene)(+)· · · AlS(-) species, observable by solid-state NMR and XAS.
language: eng
source:
identifier: E-ISSN: 1091-6490 ; DOI: 10.1073/pnas.1220240110
fulltext: fulltext
issn:
  • 10916490
  • 1091-6490
url: Link


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titleSurface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites.
creatorWilliams, Linda A ; Guo, Neng ; Motta, Alessandro ; Delferro, Massimiliano ; Fragalà, Ignazio L ; Miller, Jeffrey T ; Marks, Tobin J
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ispartofProceedings of the National Academy of Sciences of the United States of America, January 8, 2013, Vol.110(2), pp.413-418
identifierE-ISSN: 1091-6490 ; DOI: 10.1073/pnas.1220240110
subjectAdsorption–Chemistry ; Aluminum Oxide–Chemistry ; Benzene–Chemistry ; Carbon Isotopes–Methods ; Catalysis–Chemistry ; Hydrocarbons, Aromatic–Methods ; Hydrogenation–Methods ; Kinetics–Methods ; Models, Chemical–Methods ; Models, Molecular–Methods ; Molecular Structure–Methods ; Nuclear Magnetic Resonance, Biomolecular–Methods ; Organometallic Compounds–Methods ; Static Electricity–Methods ; Surface Properties–Methods ; X-Ray Absorption Spectroscopy–Methods ; Zirconium–Methods ; Carbon Isotopes ; Hydrocarbons, Aromatic ; Organometallic Compounds
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descriptionStructural characterization of the catalytically significant sites on solid catalyst surfaces is frequently tenuous because their fraction, among all sites, typically is quite low. Here we report the combined application of solid-state (13)C-cross-polarization magic angle spinning nuclear magnetic resonance ((13)C-CPMAS-NMR) spectroscopy, density functional theory (DFT), and Zr X-ray absorption spectroscopy (XAS) to characterize the adsorption products and surface chemistry of the precatalysts (η(5)-C(5)H(5))(2)ZrR(2) (R = H, CH(3)) and [η(5)-C(5)(CH(3))(5)]Zr(CH(3))(3) adsorbed on Brønsted superacidic sulfated alumina (AlS). The latter complex is exceptionally active for benzene hydrogenation, with ~100% of the Zr sites catalytically significant as determined by kinetic poisoning experiments. The (13)C-CPMAS-NMR, DFT, and XAS data indicate formation of organozirconium cations having a largely electrostatic [η(5)-C(5)(CH(3))(5)]Zr(CH(3))(2)(+)· · · AlS(-) interaction with greatly elongated Zr · · · O(AlS) distances of ~2.35(2) Å. The catalytic benzene hydrogenation cycle is stepwise understandable by DFT, and proceeds via turnover-limiting H(2) delivery to surface [η(5)-C(5)(CH(3))(5)]ZrH(2)(benzene)(+)· · · AlS(-) species, observable by solid-state NMR and XAS.
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10Molecular Structure–Methods
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12Organometallic Compounds–Methods
13Static Electricity–Methods
14Surface Properties–Methods
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19Organometallic Compounds
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titleSurface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites.
authorWilliams, Linda A ; Guo, Neng ; Motta, Alessandro ; Delferro, Massimiliano ; Fragalà, Ignazio L ; Miller, Jeffrey T ; Marks, Tobin J
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