Active-Site Determination and Mechanistic Insights in a MOF-Supported Polymerization Catalyst

Timothy A. Goetjen, Magali S. Ferrandon, A. Jeremy Kropf, Jessica V. Lamb, Massimiliano Delferro, Joseph T. Hupp*, Omar K. Farha

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


The structural elucidation of catalyst active sites in heterogeneous catalysts when supported by traditional metal oxides remains a challenge despite the advanced characterization techniques that have been developed. The catalyst-deposition-site nonuniformity in metal oxides inhibits clear structural characterization through bulk spectroscopic methods and rules out the use of single-crystal X-ray diffraction. However, for metal-organic framework (MOF)-supported catalysts, the crystallinity and uniform structures of the underlying support enhance our ability to identify the precatalyst and catalytically active sites and open the door to using single-crystal X-ray diffraction coupled with spectroscopy under reaction conditions. The use of in situ X-ray absorption spectroscopy identifies the catalytically active site in diethylaluminum chloride (DEAC)-pretreated Cr-SIM-NU-1000 to be a Cr-ethyl when used for ethylene polymerization. Further kinetic experiments elucidate the effects of ethylene pressure, temperature, catalyst loading, and cocatalyst loading, furthering mechanistic knowledge and helping to deconvolute the structure-function relationship.

Original languageEnglish (US)
Pages (from-to)20388-20394
Number of pages7
JournalJournal of Physical Chemistry C
Issue number48
StatePublished - Dec 8 2022

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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