Synthesis-Structure-Function Relationships of Silica-Supported Niobium(V) Catalysts for Alkene Epoxidation with H2O2

Nicholas E. Thornburg, Scott L. Nauert, Anthony B. Thompson, Justin M Notestein

Research output: Contribution to journalArticle

31 Citations (Scopus)

Abstract

Many industrially significant selective oxidation reactions are catalyzed by supported and bulk transition metal oxides. Catalysts for the synthesis of oxygenates, and especially for epoxidation, have predominantly focused on TiOx supported on or co-condensed with SiO2, whereas much of the rest of Groups 4 and 5 have been less studied. We have recently demonstrated through periodic trends using a uniform molecular precursor that niobium(V)-silica catalysts reveal the highest activity and selectivity for efficient utilization of H2O2 for epoxidation across all of Groups 4 and 5. In this work, we graft a wide range of Nb(V) precursors, spanning surface densities of 0.07-1.6 Nb groups nm-2 on mesoporous silica, and we characterize these materials with UV-visible spectroscopy and Nb K-edge XANES. Further, we apply in situ chemical titration with phenylphosphonic acid (PPA) in the epoxidation of cis-cyclooctene by H2O2 to probe the numbers and nature of the active sites across this series and in a set of related Ti-, Zr-, Hf-, and Ta-SiO2 catalysts. By this method, the fraction of kinetically relevant NbOx species ranges from ∼15% to ∼65%, which correlates with spectroscopic evaluation of the NbOx sites. This titration leads to a single value for the average turnover frequency, on a per active site basis rather than a per Nb atom basis, of 1.4 ± 0.52 min-1 across the 21 materials in the series. These quantitative maps of structural properties and kinetic consequences link key catalyst descriptors of supported Nb-SiO2 to enable rational design for next-generation oxidation catalysts.

Original languageEnglish
Pages (from-to)6124-6134
Number of pages11
JournalACS Catalysis
Volume6
Issue number9
DOIs
Publication statusPublished - Sep 2 2016

Fingerprint

Niobium
Epoxidation
Alkenes
Silicon Dioxide
Olefins
Silica
Catalysts
Titration
Oxidation
Catalyst selectivity
Grafts
Oxides
Transition metals
Structural properties
Catalyst activity
Spectroscopy
Atoms
Kinetics
Acids

Keywords

  • active site
  • calixarene
  • epoxidation
  • heterogeneous catalysis
  • hydrogen peroxide
  • niobium
  • supported catalyst
  • supported oxide

ASJC Scopus subject areas

  • Catalysis

Cite this

Synthesis-Structure-Function Relationships of Silica-Supported Niobium(V) Catalysts for Alkene Epoxidation with H2O2 . / Thornburg, Nicholas E.; Nauert, Scott L.; Thompson, Anthony B.; Notestein, Justin M.

In: ACS Catalysis, Vol. 6, No. 9, 02.09.2016, p. 6124-6134.

Research output: Contribution to journalArticle

Thornburg, Nicholas E. ; Nauert, Scott L. ; Thompson, Anthony B. ; Notestein, Justin M. / Synthesis-Structure-Function Relationships of Silica-Supported Niobium(V) Catalysts for Alkene Epoxidation with H2O2 In: ACS Catalysis. 2016 ; Vol. 6, No. 9. pp. 6124-6134.
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abstract = "Many industrially significant selective oxidation reactions are catalyzed by supported and bulk transition metal oxides. Catalysts for the synthesis of oxygenates, and especially for epoxidation, have predominantly focused on TiOx supported on or co-condensed with SiO2, whereas much of the rest of Groups 4 and 5 have been less studied. We have recently demonstrated through periodic trends using a uniform molecular precursor that niobium(V)-silica catalysts reveal the highest activity and selectivity for efficient utilization of H2O2 for epoxidation across all of Groups 4 and 5. In this work, we graft a wide range of Nb(V) precursors, spanning surface densities of 0.07-1.6 Nb groups nm-2 on mesoporous silica, and we characterize these materials with UV-visible spectroscopy and Nb K-edge XANES. Further, we apply in situ chemical titration with phenylphosphonic acid (PPA) in the epoxidation of cis-cyclooctene by H2O2 to probe the numbers and nature of the active sites across this series and in a set of related Ti-, Zr-, Hf-, and Ta-SiO2 catalysts. By this method, the fraction of kinetically relevant NbOx species ranges from ∼15{\%} to ∼65{\%}, which correlates with spectroscopic evaluation of the NbOx sites. This titration leads to a single value for the average turnover frequency, on a per active site basis rather than a per Nb atom basis, of 1.4 ± 0.52 min-1 across the 21 materials in the series. These quantitative maps of structural properties and kinetic consequences link key catalyst descriptors of supported Nb-SiO2 to enable rational design for next-generation oxidation catalysts.",
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KW - active site

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KW - hydrogen peroxide

KW - niobium

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KW - supported oxide

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