Carbonylation of Dimethyl Ether with CO on Solid 12-Tungstophosphoric Acid: In Situ Magic Angle Spinning NMR Monitoring of the Reaction Kinetics Full article
Journal |
The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455 |
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Output data | Year: 2013, Volume: 117, Number: 21, Pages: 11168-11175 Pages count : 8 DOI: 10.1021/jp401604r | ||
Tags | Carbon monoxide; Fuels; Magic angle spinning; Nuclear magnetic resonance spectroscopy; Reaction kinetics; Surface reactions | ||
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Abstract:
Knowledge of the elementary steps of the reaction on the surface of a heterogeneous catalyst is crucial for understanding the reaction mechanism. This valuable information could be provided by in situ monitoring of the reaction with solid-state NMR spectroscopy. In this paper, the kinetics of the dimethyl ether (DME) carbonylation on 12-tungstophosphoric acid has been followed with high temperature H-1 magic angle spinning (MAS) NMR. The equilibrium of the initial ether activation toward the intermediate surface methoxy species has been examined with C-13 MAS NMR as well. The energy profile of DME carbonylation with CO to the Keggin acetate on H3PW12O40 has been established. The apparent activation energy of the carbonylation, 95 +/- 10 kJ mol(-1), represents a sum (within experimental error) of the standard enthalpy of the methoxy group formation, 57 +/- 4 kJ mol(-1), and the activation barrier of the rate-determining step of the process, the interaction between methoxy group and carbon monoxide, 50 +/- 4 kJ mol(-1).
Cite:
Kazantsev M.S.
, Luzgin M.V.
, Stepanov A.G.
Carbonylation of Dimethyl Ether with CO on Solid 12-Tungstophosphoric Acid: In Situ Magic Angle Spinning NMR Monitoring of the Reaction Kinetics
The Journal of Physical Chemistry C. 2013. V.117. N21. P.11168-11175. DOI: 10.1021/jp401604r WOS Scopus РИНЦ
Carbonylation of Dimethyl Ether with CO on Solid 12-Tungstophosphoric Acid: In Situ Magic Angle Spinning NMR Monitoring of the Reaction Kinetics
The Journal of Physical Chemistry C. 2013. V.117. N21. P.11168-11175. DOI: 10.1021/jp401604r WOS Scopus РИНЦ
Dates:
Submitted: | Feb 14, 2013 |
Accepted: | Apr 23, 2013 |
Published online: | May 16, 2013 |
Published print: | May 30, 2013 |
Identifiers:
Web of science | WOS:000319896700033 |
Scopus | 2-s2.0-84878376656 |
Elibrary | 20436282 |
Chemical Abstracts | 2013:633940 |
Chemical Abstracts (print) | 158:650858 |
OpenAlex | W2326256266 |