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Ensemble effects on methanol oxidation to formaldehyde on ferric molybdate catalysts

Ensemble effects on methanol oxidation to formaldehyde on ferric molybdate catalysts
Ensemble effects on methanol oxidation to formaldehyde on ferric molybdate catalysts

The properties of Mo-doped iron oxide are compared with those of the single oxides of Fe and Mo, and with stoichiometric ferric molybdate for the selective oxidation of methanol. It is found that Mo oxide segregates to the surface of the iron oxide at low loadings, while at higher loadings, but below the stoichiometric ratio, presents layers of ferric molybdate at the surface. The relationship between bulk loading and surface Mo is explored, and it is concluded that the reactivity is dominated by ensemble effects. Simple modelling indicates that four or more Fe cation ensembles are required to combust methanol to CO 2, ensembles of two Mo cations are required for selective oxidation to formaldehyde, whereas it seems that isolated single sites of either Fe or Mo produce CO.

Ensemble, formaldehyde, iron molybdate catalysts, methanol, methanol oxidation, Ensembles
1867-3880
Bowker, Michael
c9ab10a5-d144-4533-bf6d-2fa16b669565
House, Matthew
9ede64cb-ebdb-42ee-a628-78de8ca339e9
Brookes, Catherine
fcbf76ed-9e86-4aea-b8f5-174607bae342
Hellier, Pip
c3bd090a-2f8d-45ec-8ee6-781c034eb9b9
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Bowker, Michael
c9ab10a5-d144-4533-bf6d-2fa16b669565
House, Matthew
9ede64cb-ebdb-42ee-a628-78de8ca339e9
Brookes, Catherine
fcbf76ed-9e86-4aea-b8f5-174607bae342
Hellier, Pip
c3bd090a-2f8d-45ec-8ee6-781c034eb9b9
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266

Bowker, Michael, House, Matthew, Brookes, Catherine, Hellier, Pip and Wells, Peter P. (2024) Ensemble effects on methanol oxidation to formaldehyde on ferric molybdate catalysts. ChemCatChem, 16 (6), [e202301464]. (doi:10.1002/cctc.202301464).

Record type: Article

Abstract

The properties of Mo-doped iron oxide are compared with those of the single oxides of Fe and Mo, and with stoichiometric ferric molybdate for the selective oxidation of methanol. It is found that Mo oxide segregates to the surface of the iron oxide at low loadings, while at higher loadings, but below the stoichiometric ratio, presents layers of ferric molybdate at the surface. The relationship between bulk loading and surface Mo is explored, and it is concluded that the reactivity is dominated by ensemble effects. Simple modelling indicates that four or more Fe cation ensembles are required to combust methanol to CO 2, ensembles of two Mo cations are required for selective oxidation to formaldehyde, whereas it seems that isolated single sites of either Fe or Mo produce CO.

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ChemCatChem - 2024 - Bowker - Ensemble Effects on Methanol Oxidation to Formaldehyde on Ferric Molybdate Catalysts - Accepted Manuscript
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ChemCatChem - 2024 - Bowker - Ensemble Effects on Methanol Oxidation to Formaldehyde on Ferric Molybdate Catalysts - Version of Record
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More information

Accepted/In Press date: 22 January 2024
e-pub ahead of print date: 29 January 2024
Published date: 22 March 2024
Additional Information: Funding information: EPSRC. Grant Numbers: EP/R026939/1, EP/R026815/1 Publisher Copyright: © 2024 The Authors. ChemCatChem published by Wiley-VCH GmbH.
Keywords: Ensemble, formaldehyde, iron molybdate catalysts, methanol, methanol oxidation, Ensembles

Identifiers

Local EPrints ID: 487586
URI: http://eprints.soton.ac.uk/id/eprint/487586
ISSN: 1867-3880
PURE UUID: 5696ebaa-4358-4180-9c72-00da1bbc21dd
ORCID for Peter P. Wells: ORCID iD orcid.org/0000-0002-0859-9172

Catalogue record

Date deposited: 27 Feb 2024 20:50
Last modified: 28 Aug 2024 01:40

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Contributors

Author: Michael Bowker
Author: Matthew House
Author: Catherine Brookes
Author: Pip Hellier
Author: Peter P. Wells ORCID iD

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