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Integrated theoretical and empirical studies for probing substrate-framework interactions in hierarchical catalysts

Integrated theoretical and empirical studies for probing substrate-framework interactions in hierarchical catalysts
Integrated theoretical and empirical studies for probing substrate-framework interactions in hierarchical catalysts
Soft‐templating with siliceous surfactant is an established protocol for the synthesis of hierarchically‐porous aluminophosphates (HP AlPOs) with improved mass transport properties. Motivated by the enhanced performance of HP (Si)AlPOs in the Beckmann rearrangement of cyclohexanone oxime to the nylon‐6 precursor, ε‐caprolactam, we have undertaken an integrated theoretical and empirical study to investigate the catalytic potential of the siliceous mesopore network. Neutron scattering studies, in particular, have provided unique insight into substrate‐framework interactions in HP AlPOs, allowing reactive species to be studied, independent of the catalyst matrix. Reinforced by probe‐based FT‐IR, solid‐state NMR and computational modelling, neutron spectroscopy has revealed ambient‐temperature interactions between cyclohexanone oxime and the HP catalysts, vindicating substrate activation by silanol sites in the mesoporous network. These investigations highlight the power of integrative studies in achieving a molecular‐level understanding of catalyst mechanism, and demonstrate how synthetic methodology can be used maximize catalyst productivity.
hierarchical architectures, solid-acid catalysts, Beckmann rearrangement, advanced characterization, Neutron spectroscopy, probe-based FTIR, solid-state NMR, computational modelling
0947-6539
9938-9947
Chapman, Stephanie
02fa6ac4-c0e7-4cd3-8ffb-bf1c88cbfd45
O'Malley, Alexander J.
9a7506b9-31f7-4ec5-aa95-b8d4cbbba477
Miletto, Ivana
9a3fe0ee-6afd-4e72-abff-8e83a9114ae9
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Cox, Paul
1ee9fac0-c2d7-4269-bb19-b6f7b7f4836f
Gianotti, Enrica
2496d8d3-780f-4fe0-a43e-147e68331078
Marchese, Leonardo
684a36ec-9847-4604-82e7-71234cd44090
Parker, Stewart F.
8752cd59-1b63-4399-859d-78e11a37c6d4
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b
Chapman, Stephanie
02fa6ac4-c0e7-4cd3-8ffb-bf1c88cbfd45
O'Malley, Alexander J.
9a7506b9-31f7-4ec5-aa95-b8d4cbbba477
Miletto, Ivana
9a3fe0ee-6afd-4e72-abff-8e83a9114ae9
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Cox, Paul
1ee9fac0-c2d7-4269-bb19-b6f7b7f4836f
Gianotti, Enrica
2496d8d3-780f-4fe0-a43e-147e68331078
Marchese, Leonardo
684a36ec-9847-4604-82e7-71234cd44090
Parker, Stewart F.
8752cd59-1b63-4399-859d-78e11a37c6d4
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b

Chapman, Stephanie, O'Malley, Alexander J., Miletto, Ivana, Carravetta, Marina, Cox, Paul, Gianotti, Enrica, Marchese, Leonardo, Parker, Stewart F. and Raja, Robert (2019) Integrated theoretical and empirical studies for probing substrate-framework interactions in hierarchical catalysts. Chemistry - A European Journal, 25 (42), 9938-9947. (doi:10.1002/chem.201901188).

Record type: Article

Abstract

Soft‐templating with siliceous surfactant is an established protocol for the synthesis of hierarchically‐porous aluminophosphates (HP AlPOs) with improved mass transport properties. Motivated by the enhanced performance of HP (Si)AlPOs in the Beckmann rearrangement of cyclohexanone oxime to the nylon‐6 precursor, ε‐caprolactam, we have undertaken an integrated theoretical and empirical study to investigate the catalytic potential of the siliceous mesopore network. Neutron scattering studies, in particular, have provided unique insight into substrate‐framework interactions in HP AlPOs, allowing reactive species to be studied, independent of the catalyst matrix. Reinforced by probe‐based FT‐IR, solid‐state NMR and computational modelling, neutron spectroscopy has revealed ambient‐temperature interactions between cyclohexanone oxime and the HP catalysts, vindicating substrate activation by silanol sites in the mesoporous network. These investigations highlight the power of integrative studies in achieving a molecular‐level understanding of catalyst mechanism, and demonstrate how synthetic methodology can be used maximize catalyst productivity.

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Accepted/In Press date: 26 April 2019
e-pub ahead of print date: 29 April 2019
Published date: July 2019
Keywords: hierarchical architectures, solid-acid catalysts, Beckmann rearrangement, advanced characterization, Neutron spectroscopy, probe-based FTIR, solid-state NMR, computational modelling

Identifiers

Local EPrints ID: 430638
URI: https://eprints.soton.ac.uk/id/eprint/430638
ISSN: 0947-6539
PURE UUID: 63610499-b0e4-4a9d-8cd0-a38faa7ab25f
ORCID for Marina Carravetta: ORCID iD orcid.org/0000-0002-6296-2104
ORCID for Robert Raja: ORCID iD orcid.org/0000-0002-4161-7053

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Date deposited: 07 May 2019 16:30
Last modified: 15 Aug 2019 00:46

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