Please use this identifier to cite or link to this item: http://hdl.handle.net/10773/34326
Title: A silicododecamolybdate/pyridinium-tetrazole hybrid molecular salt as a catalyst for the epoxidation of bio-derived olefins
Author: Nunes, Martinique S.
Neves, Patrícia
Gomes, Ana C.
Cunha-Silva, Luís
Lopes, André D.
Valente, Anabela A.
Pillinger, Martyn
Gonçalves, Isabel S.
Keywords: Polyoxometalate
Inorganic-organic hybrid
Pyridinium
Hydrogen bonds
Epoxidation
Bio-olefins
Issue Date: Feb-2021
Publisher: Elsevier
Abstract: The hybrid polyoxometalate (POM) salt (Hptz)4[SiMo12O40]∙nH2O (1) (ptz = 5-(2-pyridyl)tetrazole) has been prepared, characterized by X-ray crystallography, and examined as a catalyst for the epoxidation of cis-cyclooctene (Cy) and bio-derived olefins, namely dl-limonene (Lim; a naturally occurring monoterpene found in the rinds of citrus fruits), methyl oleate and methyl linoleate (fatty acid methyl esters (FAMEs) obtained by transesterification of vegetable oils). The crystal structure of 1 consists of α-Keggin-type heteropolyanions, [SiMo12O40]4-, surrounded by space-filling and charge-balancing 2-(tetrazol-5-yl)pyridinium (Hptz+) cations, as well as by a large number of water molecules of crystallization (n = 9). The water molecules mediate an extensive three-dimensional (3D) hydrogen-bonding network involving the inorganic anions and organic cations. For the epoxidation of the model substrate Cy in a nonaqueous system (tert-butylhydroperoxide as oxidant), the catalytic performance of 1 (100% epoxide yield at 24 h, 70 ◦C) was superior to that of the tetrabutylammonium salt (Bu4N)4[SiMo12O40] (2) (63% epoxide yield at 24 h), illustrating the role of the counterion Hptz+ in enhancing catalytic activity. The hybrid salt 1 was effective for the epoxidation of Lim (69%/85% conversion at 6 h/24 h) and the FAMEs (87–88%/100% conversion at 6 h/24 h), leading to useful bio-based products (epoxides, diepoxides and diol products).
Peer review: yes
URI: http://hdl.handle.net/10773/34326
DOI: 10.1016/j.ica.2020.120129
ISSN: 0020-1693
Appears in Collections:CICECO - Artigos

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