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Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe2O3 surface doped with Mo oxide

Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe2O3 surface doped with Mo oxide
Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe2O3 surface doped with Mo oxide
Iron molybdate catalysts are used for the selective oxidation of methanol to formaldehyde. In this paper we have attempted to understand what determines high selectivity in this reaction system by doping haematite with surface layers of Mo by incipient wetness impregnation. This works well and the Mo appears to form finely dispersed layers. Even very low loadings of Mo have a marked effect on improving the selectivity to formaldehyde. Haematite itself is a very poor catalyst with high selectivity to combustion products, whereas, when only 0.25 monolayers of Mo are deposited on the surface, formaldehyde and CO selectivities are greatly enhanced and CO2 production is greatly diminished. However, even with as much as seven monolayers of Mo dosed on to the surface, these materials achieve much less selectivity to formaldehyde at high conversion than do the industrial catalysts. The reason for this is that the Mo forms a 'skin' of ferric molybdate on a core of iron oxide, but does not produce a pure Mo oxide monolayer on the surface, a situation which is essential for very high yields of formaldehyde.
1463-9076
12056-12067
Bowker, M.
8e99ffe0-6f5e-442e-a30a-158afaa3f85c
Brookes, C.
485540de-a96e-4c26-9324-291b8cdcc80f
Carley, A.F.
37c86ec4-3338-40c0-a1bd-b3f82011d372
House, M.P.
d56fedf6-db6f-4d7f-a263-a3c3cf213b29
Kosif, M.
b31277fe-7cff-4521-8731-7ff2f855197a
Sankar, G.
38b9039e-7899-467b-887a-60397cd25a5e
Wawata, I.
64ef125c-77bf-443c-bd63-1526534130fd
Wells, P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Yaseneva, P.
19f2a427-9e57-440f-ae58-1edeeccef42a
Bowker, M.
8e99ffe0-6f5e-442e-a30a-158afaa3f85c
Brookes, C.
485540de-a96e-4c26-9324-291b8cdcc80f
Carley, A.F.
37c86ec4-3338-40c0-a1bd-b3f82011d372
House, M.P.
d56fedf6-db6f-4d7f-a263-a3c3cf213b29
Kosif, M.
b31277fe-7cff-4521-8731-7ff2f855197a
Sankar, G.
38b9039e-7899-467b-887a-60397cd25a5e
Wawata, I.
64ef125c-77bf-443c-bd63-1526534130fd
Wells, P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Yaseneva, P.
19f2a427-9e57-440f-ae58-1edeeccef42a

Bowker, M., Brookes, C., Carley, A.F., House, M.P., Kosif, M., Sankar, G., Wawata, I., Wells, P. and Yaseneva, P. (2013) Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe2O3 surface doped with Mo oxide. Physical Chemistry Chemical Physics, 15 (29), 12056-12067. (doi:10.1039/c3cp50399b). (PMID:23552323)

Record type: Article

Abstract

Iron molybdate catalysts are used for the selective oxidation of methanol to formaldehyde. In this paper we have attempted to understand what determines high selectivity in this reaction system by doping haematite with surface layers of Mo by incipient wetness impregnation. This works well and the Mo appears to form finely dispersed layers. Even very low loadings of Mo have a marked effect on improving the selectivity to formaldehyde. Haematite itself is a very poor catalyst with high selectivity to combustion products, whereas, when only 0.25 monolayers of Mo are deposited on the surface, formaldehyde and CO selectivities are greatly enhanced and CO2 production is greatly diminished. However, even with as much as seven monolayers of Mo dosed on to the surface, these materials achieve much less selectivity to formaldehyde at high conversion than do the industrial catalysts. The reason for this is that the Mo forms a 'skin' of ferric molybdate on a core of iron oxide, but does not produce a pure Mo oxide monolayer on the surface, a situation which is essential for very high yields of formaldehyde.

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Accepted/In Press date: 22 March 2013
e-pub ahead of print date: 2 April 2013
Published date: 7 August 2013
Organisations: Organic Chemistry: SCF

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Local EPrints ID: 400613
URI: http://eprints.soton.ac.uk/id/eprint/400613
ISSN: 1463-9076
PURE UUID: 3eb31ad4-96ce-4ef8-b943-fd1ff6f307de
ORCID for P. Wells: ORCID iD orcid.org/0000-0002-0859-9172

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Date deposited: 21 Sep 2016 15:41
Last modified: 15 Mar 2024 03:24

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Contributors

Author: M. Bowker
Author: C. Brookes
Author: A.F. Carley
Author: M.P. House
Author: M. Kosif
Author: G. Sankar
Author: I. Wawata
Author: P. Wells ORCID iD
Author: P. Yaseneva

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