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

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

doi:10.1021/acs.jpcc.2c06643

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

Journal Article · Mon Nov 28 00:00:00 EST 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c06643· OSTI ID:2283550

^[1]; Ferrandon, Magali S. ^[2]; Kropf, A. Jeremy ^[2];

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Northwestern University, Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States); University of Chicago, IL (United States)
Northwestern University, Evanston, IL (United States)

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. Additionally, 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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Ames Laboratory (AMES), Ames, IA (United States); Oak Ridge Institute for Science and Education (ORISE), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; SC0012702; AC02-07CH11358; SC0014664; ECCS-1542205

OSTI ID:: 2283550

Journal Information:: Journal of Physical Chemistry. C, Vol. 126, Issue 48; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
metal-organic frameworks
heterogeneous catalysis
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