Catalysis by framework zinc in silica-based molecular sieves

Orazov, Marat; Davis, Mark E.

doi:10.1039/c5sc03889h

Title: Catalysis by framework zinc in silica-based molecular sieves

Journal Article · Mon Jan 04 00:00:00 EST 2016 · Chemical Science

DOI:https://doi.org/10.1039/c5sc03889h· OSTI ID:1387609

Orazov, Marat ^[1]; Davis, Mark E. ^[1]

California Inst. of Technology (CalTech), Pasadena, CA (United States)

Microporous and mesoporous zincosilicates (e.g., CIT-6, VPI-8, Zn-MFI, and Zn-MCM-41) synthesized in the presence of alkali cations contain two broad types of Zn sites: one that is a dication analog of the monocation ion-exchangeable Al-site in aluminosilicates, while the other resembles isolated Zn sites on amorphous silica. The ratio of these sites varies, depending on the synthesis conditions of the zincosilicate. Post-synthetic strategies based on ion-exchange can alter the site distribution towards either population. Furthermore, post-synthetic introduction of isolated Zn sites of the latter type is possible for materials possessing silanol nests. Both types of sites behave as Lewis acid centers in probe-molecule IR spectroscopy, but have very different catalytic properties. Due to the unusually high adsorption energies of Lewis bases on such materials, Lewis acid catalysis is difficult at low temperatures and in solvents bearing Lewis basic functionality. However, at high temperatures, in hydrocarbon solvents, CIT-6 (Zn-beta) is able to selectively catalyze the Lewis-acid-catalyzed Diels–Alder cycloaddition–dehydration reactions of ethylene with methyl 5-(methoxymethyl)furan-2-carboxylate, a furan that can be derived quantitatively by partial oxidation of biomass-based 5-hydroxymethylfurfural. Additionally, zinc in silica-based molecular sieves is shown here to enable chemistries previously not accessible with framework Sn-, Ti- and Zr-based Lewis acid sites, e.g., the direct production of dimethyl terephthalate by Diels–Alder cycloaddition–dehydration reactions of ethylene and the dimethyl ester of furan-2,5-dicarboxilic acid.

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Research Organization:: Univ. of Delaware, Newark, DE (United States). Energy Frontier Research Center (EFRC) Catalysis Center for Energy Innovation (CCEI)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0001004; DGE-1144469

OSTI ID:: 1387609

Journal Information:: Chemical Science, Vol. 7, Issue 3; Related Information: CCEI partners with the University of Delaware (lead); Brookhaven National Laboratory; California Institute of Technology; Columbia University; University of Delaware; Lehigh University; University of Massachusetts, Amherst; Massachusetts Institute of Technology; University of Minnesota; Pacific Northwest National Laboratory; University of Pennsylvania; Princeton University; Rutgers University; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 58 works

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