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Issue 3, 2016
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Catalysis by framework zinc in silica-based molecular sieves

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Abstract

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.

Graphical abstract: Catalysis by framework zinc in silica-based molecular sieves

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Supplementary files

Article information


Submitted
14 Oct 2015
Accepted
04 Jan 2016
First published
04 Jan 2016

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 2264-2274
Article type
Edge Article
Author version available

Catalysis by framework zinc in silica-based molecular sieves

M. Orazov and M. E. Davis, Chem. Sci., 2016, 7, 2264
DOI: 10.1039/C5SC03889H

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