TY - JOUR
T1 - Microkinetic modeling of cis-cyclooctene oxidation on heterogeneous Mn-tmtacn complexes
AU - Bjorkman, Kathryn R.
AU - Schoenfeldt, Nicholas J.
AU - Notestein, Justin M.
AU - Broadbelt, Linda J.
N1 - Funding Information:
The authors would like to thank The Dow Chemical Company and The Dow Methane Challenge for financial support, and Andrew Korinda for useful discussions.
PY - 2012/7
Y1 - 2012/7
N2 - 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.
AB - 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.
KW - Heterogeneous
KW - Hydrogen peroxide
KW - Microkinetic modeling
KW - Mn-tmtacn
KW - Oxidation
KW - Reaction mechanism
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U2 - 10.1016/j.jcat.2012.03.026
DO - 10.1016/j.jcat.2012.03.026
M3 - Article
AN - SCOPUS:84862001860
SN - 0021-9517
VL - 291
SP - 17
EP - 25
JO - Journal of Catalysis
JF - Journal of Catalysis
ER -