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Toward understanding the catalytic synergy in the design of bimetallic molecular sieves for selective aerobic oxidations

Toward understanding the catalytic synergy in the design of bimetallic molecular sieves for selective aerobic oxidations
Toward understanding the catalytic synergy in the design of bimetallic molecular sieves for selective aerobic oxidations
Structure–property correlations and mechanistic implications are important in the design of single-site catalysts for the activation of molecular oxygen. In this study we rationalize trends in catalytic synergy to elucidate the nature of the active site through structural and spectroscopic correlations. In particular, the redox behavior and coordination geometry in isomorphously substituted, bimetallic VTiAlPO-5 catalysts are investigated with a view to specifically engineering and enhancing their reactivity and selectivity in aerobic oxidations. By using a combination of HYSCORE EPR and in situ FTIR studies, we show that the well-defined and isolated oxophilic tetrahedral titanium centers coupled with redox-active VO2+ ions at proximal framework positions provide the loci for the activation of oxidant that leads to a concomitant increase in catalytic activity compared to analogous monometallic systems.
0002-7863
2915-2918
Leithall, Rebecca M.
01550709-ef72-44f1-8c73-eec71dc3a6b6
Shetti, Vasudev N.
a928ca6f-6cae-4fdc-aff4-43463be2c4db
Maurelli, Sara
a7b261b6-6687-4a5b-b2f3-7d6bbeebdc2d
Chiesa, Mario
848d9140-8756-4e2c-b15b-8f54d6ebab05
Gianotti, Enrica
2496d8d3-780f-4fe0-a43e-147e68331078
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b
Leithall, Rebecca M.
01550709-ef72-44f1-8c73-eec71dc3a6b6
Shetti, Vasudev N.
a928ca6f-6cae-4fdc-aff4-43463be2c4db
Maurelli, Sara
a7b261b6-6687-4a5b-b2f3-7d6bbeebdc2d
Chiesa, Mario
848d9140-8756-4e2c-b15b-8f54d6ebab05
Gianotti, Enrica
2496d8d3-780f-4fe0-a43e-147e68331078
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b

Leithall, Rebecca M., Shetti, Vasudev N., Maurelli, Sara, Chiesa, Mario, Gianotti, Enrica and Raja, Robert (2013) Toward understanding the catalytic synergy in the design of bimetallic molecular sieves for selective aerobic oxidations. Journal of the American Chemical Society, 135 (8), 2915-2918. (doi:10.1021/ja3119064).

Record type: Article

Abstract

Structure–property correlations and mechanistic implications are important in the design of single-site catalysts for the activation of molecular oxygen. In this study we rationalize trends in catalytic synergy to elucidate the nature of the active site through structural and spectroscopic correlations. In particular, the redox behavior and coordination geometry in isomorphously substituted, bimetallic VTiAlPO-5 catalysts are investigated with a view to specifically engineering and enhancing their reactivity and selectivity in aerobic oxidations. By using a combination of HYSCORE EPR and in situ FTIR studies, we show that the well-defined and isolated oxophilic tetrahedral titanium centers coupled with redox-active VO2+ ions at proximal framework positions provide the loci for the activation of oxidant that leads to a concomitant increase in catalytic activity compared to analogous monometallic systems.

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e-pub ahead of print date: 7 February 2013
Published date: 27 February 2013
Organisations: Chemistry

Identifiers

Local EPrints ID: 348354
URI: http://eprints.soton.ac.uk/id/eprint/348354
ISSN: 0002-7863
PURE UUID: c823ab39-847d-4e81-adac-960d53f3d6bb
ORCID for Robert Raja: ORCID iD orcid.org/0000-0002-4161-7053

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Date deposited: 12 Feb 2013 14:12
Last modified: 18 Feb 2021 17:07

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