Solid-State NMR Study of the Kinetics and Mechanism of Dimethyl Ether Carbonylation on Cesium Salt of 12-Tungstophosphoric Acid Modified with Ag, Pt, and Rh | Sciact - CRIS-system of Boreskov Institute of Catalysis

Solid-State NMR Study of the Kinetics and Mechanism of Dimethyl Ether Carbonylation on Cesium Salt of 12-Tungstophosphoric Acid Modified with Ag, Pt, and Rh Full article

Journal

Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694

Output data

Year: 2013, Volume: 308, Pages: 250-257 Pages count : 8 DOI: 10.1016/j.jcat.2013.08.024

Tags

12-Tungstophosphoric acid, Carbon monoxide, Carbonylation, Dimethyl ether, Kinetics, Mechanism, Metal-carbonyls, Solid-state NMR

Authors

Luzgin Mikhail V. ^1,2 , Kazantsev Maxim S. ¹ , Volkova Galina G. ¹ , Stepanov Alexander G. ^1,2

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Department of Natural Sciences, Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia

By using C-13 magic angle spinning (MAS) NMR, the mechanism of dimethyl ether (DME) carbonylation with carbon monoxide has been studied on solid metal-containing acidic cesium salt of 12-tungstophosphoric acid, M/Cs2HPW12O40 (M/HPA, M = Ag, Pt, and Rh). The kinetics of the reaction has been monitored with H-1 MAS NMR in situ. Activation of DME occurs on acidic OH groups of M/HPA and gives rise to the surface methoxy groups at 293-473 K. Carbon monoxide forms the surface metal-carbonyl complexes on M/HPA at 293-473 K. The insertion of CO from the carbonyl into the CH3-O bond of surface methoxide results in the acetate group attached to the Keggin anion, from which the target product, methyl acetate, is produced under the interaction with dimethyl ether. The reaction rate decreases in the following order: Rh/Cs2HPW12O40 Pt/Cs2HPW/O-12(40) > AB/Cs2HPW12O40, which correlates well with concentration of the reaction intermediates, methoxy groups, and metal-carbonyls. The higher concentration of these intermediates detected on Rh/Cs2HPW12O40 is in charge of the higher carbonylation rate on this catalyst with respect to M/HPA (M = Ag, Pt) catalysts.

Luzgin M.V. , Kazantsev M.S. , Volkova G.G. , Stepanov A.G.
Solid-State NMR Study of the Kinetics and Mechanism of Dimethyl Ether Carbonylation on Cesium Salt of 12-Tungstophosphoric Acid Modified with Ag, Pt, and Rh
Journal of Catalysis. 2013. V.308. P.250-257. DOI: 10.1016/j.jcat.2013.08.024 WOS Scopus РИНЦ

Submitted:	Feb 26, 2013
Accepted:	Aug 18, 2013
Published online:	Sep 23, 2013
Published print:	Dec 1, 2013

Web of science	WOS:000329881700023
Scopus	2-s2.0-84889093250
Elibrary	21464741
Chemical Abstracts	2013:1527375
Chemical Abstracts (print)	160:13964
OpenAlex	W2019793116