Counting active sites on titanium oxide-silica catalysts for hydrogen peroxide activation through in situ poisoning with phenylphosphonic acid

Todd R. Eaton, Andrew M. Boston, Anthony B. Thompson, Kimberly A. Gray, Justin M. Notestein

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Quantifying specific active sites in supported catalysts improves our understanding and assists in rational design. Supported oxides can undergo significant structural changes as surface densities increase from site-isolated cations to monolayers and crystallites, which changes the number of kinetically relevant sites. Herein, TiOx domains are titrated on TiOx-SiO2 selectively with phenylphosphonic acid (PPA). An ex situ method quantifies all fluid-accessible TiOx, whereas an in situ titration during cis-cyclooctene epoxidation provides previously unavailable values for the number of tetrahedral Ti sites on which H2O2activation occurs. We use this method to determine the active site densities of 22 different catalysts with different synthesis methods, loadings, and characteristic spectra and find a single intrinsic turnover frequency for cis-cyclooctene epoxidation of (40± 7) h-1. This simple method gives molecular-level insight into catalyst structure that is otherwise hidden when bulk techniques are used.

Original languageEnglish
Pages (from-to)3215-3222
Number of pages8
JournalChemCatChem
Volume6
Issue number11
DOIs
Publication statusPublished - Nov 2014

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Keywords

  • Epoxidation
  • Heterogeneous catalysis
  • Structure-activity relationships
  • Supported catalysts
  • Titanium

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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