Zirconium hydrocarbyl chemisorption on sulfated metal oxides: New supports, chemisorption pathways, and implications for catalysis

Christopher P. Nicholas, Tobin J Marks

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

The sulfated metal oxides (SMOs) sulfated stannia (SnS), sulfated iron oxide (FeS), and sulfated titanium dioxide (TiS) have been synthesized and examined as support materials/cocatalysts/activators for molecule-based olefin polymerization and hydrogenation catalysis. 13C CPMAS NMR spectroscopic analysis of Cp 2Zr( 13CH 3) 2/SMO chemisorption shows that cationic zirconocenium species are formed along with varying amounts of catalytically inactive μ-oxo (Cp 2Zr(CH 3)O-surface) species, depending on the support material. Ethylene polymerization data with the supported catalysts show that polymerization activity is dependent on both precursor ligation [Zr(CH 2Ph) 4 > (Me 5Cp)ZrMe 3] and the nature of the support (SnS > FeS > TiS). Poisoning studies were performed in conjunction with ethylene polymerization, mediated by (Me 5Cp) ZrMe 3 supported on each SMO, and reveal that, for (Me 5Cp)ZrMe 3/SnS, 61 ± 5% of the Zr sites are catalytically significant, while, for (Me 5Cp)ZrMe 3/FeS, this quantity is 22 ± 2%, and for (Me 5Cp)ZrMe 3/TiS, 63 ± 9%. These catalysts are also active for benzene hydrogenation and are separable from liquid-phase products using physical or, in the case of FeS, magnetic techniques.

Original languageEnglish
Pages (from-to)9456-9462
Number of pages7
JournalLangmuir
Volume20
Issue number22
DOIs
Publication statusPublished - Oct 26 2004

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Chemisorption
Catalyst supports
Zirconium
chemisorption
Oxides
Catalysis
catalysis
metal oxides
polymerization
Metals
Polymerization
Hydrogenation
hydrogenation
Ethylene
ethylene
methylidyne
catalysts
Spectroscopic analysis
poisoning
spectroscopic analysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Colloid and Surface Chemistry

Cite this

Zirconium hydrocarbyl chemisorption on sulfated metal oxides : New supports, chemisorption pathways, and implications for catalysis. / Nicholas, Christopher P.; Marks, Tobin J.

In: Langmuir, Vol. 20, No. 22, 26.10.2004, p. 9456-9462.

Research output: Contribution to journalArticle

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abstract = "The sulfated metal oxides (SMOs) sulfated stannia (SnS), sulfated iron oxide (FeS), and sulfated titanium dioxide (TiS) have been synthesized and examined as support materials/cocatalysts/activators for molecule-based olefin polymerization and hydrogenation catalysis. 13C CPMAS NMR spectroscopic analysis of Cp 2Zr( 13CH 3) 2/SMO chemisorption shows that cationic zirconocenium species are formed along with varying amounts of catalytically inactive μ-oxo (Cp 2Zr(CH 3)O-surface) species, depending on the support material. Ethylene polymerization data with the supported catalysts show that polymerization activity is dependent on both precursor ligation [Zr(CH 2Ph) 4 > (Me 5Cp)ZrMe 3] and the nature of the support (SnS > FeS > TiS). Poisoning studies were performed in conjunction with ethylene polymerization, mediated by (Me 5Cp) ZrMe 3 supported on each SMO, and reveal that, for (Me 5Cp)ZrMe 3/SnS, 61 ± 5{\%} of the Zr sites are catalytically significant, while, for (Me 5Cp)ZrMe 3/FeS, this quantity is 22 ± 2{\%}, and for (Me 5Cp)ZrMe 3/TiS, 63 ± 9{\%}. These catalysts are also active for benzene hydrogenation and are separable from liquid-phase products using physical or, in the case of FeS, magnetic techniques.",
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