Sulfated Zirconium Metal-Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis.

Autor:	Syed ZH; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States.; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Mian MR; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States., Patel R; Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, United States., Xie H; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States., Pengmei Z; Department of Chemistry, Chicago Center for Theoretical Chemistry, University of Chicago, Chicago, Illinois 60637, United States., Chen Z; Department of Chemistry, Stony Brook University, Stony Brook, New York 11794, United States., Son FA; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States., Goetjen TA; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States.; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Chapovetsky A; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Fahy KM; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States., Sha F; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States., Wang X; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States., Alayoglu S; Center for Catalysis and Surface Science, Northwestern University, Evanston, Illinois 60208, United States., Kaphan DM; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States., Chapman KW; Department of Chemistry, Stony Brook University, Stony Brook, New York 11794, United States., Neurock M; Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, United States., Gagliardi L; Department of Chemistry, Chicago Center for Theoretical Chemistry, University of Chicago, Chicago, Illinois 60637, United States.; Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States., Delferro M; Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.; Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States., Farha OK; Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, Illinois 60208, United States.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2022 Sep 21; Vol. 144 (37), pp. 16883-16897. Date of Electronic Publication: 2022 Sep 11.
DOI:	10.1021/jacs.2c05290
Abstrakt:	Understanding heterogeneous catalysts is a challenging pursuit due to surface site nonuniformity and aperiodicity in traditionally used materials. One example is sulfated metal oxides, which function as highly active catalysts and as supports for organometallic complexes. These applications are due to traits such as acidity, ability to act as a weakly coordinating ligand, and aptitude for promoting transformations via radical cation intermediates. Research is ongoing about the structural features of sulfated metal oxides that imbue the aforementioned properties, such as sulfate geometry and coordination. To better understand these materials, metal-organic frameworks (MOFs) have been targeted as structurally defined analogues. Composed of inorganic nodes and organic linkers, MOFs possess features such as high porosity and crystallinity, which make them attractive for mechanistic studies of heterogeneous catalysts. In this work, Zr 6 -based MOF NU-1000 is sulfated and characterized using techniques such as single crystal X-ray diffraction in addition to diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The dynamic nature of the sulfate binding motif is found to transition from monodentate, to bidentate, to tridentate depending on the degree of hydration, as supported by density functional theory (DFT) calculations. Heightened Brønsted acidity compared to the parent MOF was observed upon sulfation and probed through trimethylphosphine oxide physisorption, ammonia sorption, in situ ammonia DRIFTS, and DFT studies. With the support structure benchmarked, an organoiridium complex was chemisorbed onto the sulfated MOF node, and the efficacy of this supported catalyst was demonstrated for stoichiometric and catalytic activation of benzene- d 6 and toluene with structure-activity relationships derived.
Databáze:	MEDLINE
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