Microkinetic modeling of cis-cyclooctene oxidation on heterogeneous Mn-tmtacn complexes

Kathryn R. Bjorkman, Nicholas J. Schoenfeldt, Justin M. Notestein, Linda J. Broadbelt*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


Experiments and microkinetic modeling were used to investigate the reaction mechanism of cis-cyclooctene oxidation with H 2O 2 on heterogeneous manganese 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn-tmtacn) catalysts. A mechanism based on literature reports and model discrimination was identified that captured experimental data well, including data at reaction conditions that were not used for parameter estimation. H 2O 2 activation on the heterogeneous catalytic complex was identified as the rate-determining step (RDS), and a simple analytical rate expression was derived using the RDS and the pseudo-steady-state approximation for all intermediates. Predicted reaction orders for cis-cyclooctene, water, H 2O 2, catalyst, and diol and epoxide products are also consistent with experimental observations and can be rationalized according to the derived rate expression. In addition, the ratio of productive to unproductive H 2O 2 use is analyzed, and catalyst deactivation is found to be an important step in the reaction mechanism that is highly sensitive to temperature.

Original languageEnglish (US)
Pages (from-to)17-25
Number of pages9
JournalJournal of Catalysis
StatePublished - Jul 2012


  • Heterogeneous
  • Hydrogen peroxide
  • Microkinetic modeling
  • Mn-tmtacn
  • Oxidation
  • Reaction mechanism

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry


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