Carbonylation of Dimethyl Ether on Solid Rh-Promoted Cs-Salt of Keggin 12-H3PW12O40: A Solid-State NMR Study of the Reaction Mechanism
Full article
| Common |
Language:
Английский,
Genre:
Full article,
Status:
Published,
Source type:
Original
|
| Journal |
Journal of Catalysis
ISSN: 0021-9517
, E-ISSN: 1090-2694
|
| Output data |
Year: 2011,
Volume: 277,
Number: 1,
Pages: 72-79
Pages count
: 8
DOI:
10.1016/j.jcat.2010.10.015
|
| Tags |
12-Tungstophosphoric acid, Carbon monoxide, Carbonylation, Dimethyl ether, Mechanism, Methoxy species, Rhodium carbonyls, Solid-state NMR |
| Authors |
Luzgin Mikhail V.
1,2
,
Kazantsev Maxim S.
1,2
,
Volkova Galina G.
1
,
Wang Wei
3
,
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
|
| 3 |
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000, PR China
|
|
Funding (4)
|
1
|
Russian Foundation for Basic Research
|
08-03-92210
|
|
2
|
National Natural Science Foundation of China
|
20602016
|
|
3
|
Президиум СО РАН
|
111
|
|
4
|
The Ministry of Education and Science of the Russian Federation
|
П253
|
The carbonylation of dimethyl ether (DME) with carbon monoxide on Rh-promoted cesium salt of 12-tungstophosphoric acid, Rh/Cs2HPW12O40 (HPA), has been studied with 13C solid-state NMR. The bi-functional character of Rh/Cs2HPW12O40 catalyst in halide-free carbonylation of DME has been directly demonstrated. The activation of the C–O bond of DME proceeds on Brønsted acid sites of HPA with the formation of the methyl group attached to the surface of HPA (methoxy species), whereas the role of rhodium consists in trapping carbon monoxide from gaseous phase and a transfer of CO to the center of DME activation, acidic OH-group of the catalyst, in the form of rhodium carbonyls. The lattice of Cs2HPW12O40 makes it possible to locate these two different active centers in close proximity to each other, e.g., on two adjacent oxygen atoms, terminal and bridging, of one Keggin anion, thus facilitating the insertion of carbon monoxide from rhodium carbonyl into the C–O bond of methoxy-group to produce the acetate group bound to the Keggin anion. The latter offers finally methyl acetate under the interaction with DME, the intermediate surface methoxy-groups being restored.