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Understanding the role of molecular diffusion and catalytic selectivity in liquid-phase Beckmann rearrangement

Understanding the role of molecular diffusion and catalytic selectivity in liquid-phase Beckmann rearrangement
Understanding the role of molecular diffusion and catalytic selectivity in liquid-phase Beckmann rearrangement
Understanding the role of diffusion in catalysis is essential in the design of highly active, selective and stable industrial heterogeneous catalysts. By using a combination of advanced in situ spectroscopic characterisation tools, particularly quasi-elastic and inelastic neutron scattering, we outline the crucial differences in diffusion modes and molecular interactions of active sites within solid-acid catalysts. This, coupled with 2D solid-state NMR and probe-based FTIR spectroscopy, reveals the nature of the active site in our SAPO-37 catalyst and affords detailed information on the evolution of solid-acid catalysts that can operate at temperatures as low as 130 °C, for the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam (precursor for Nylon-6). The versatility of this approach leads to structure-property correlations that contrast the dynamics of the diffusion process in the different materials studied. Our results illustrate the power of these techniques in unravelling the interplay between active site and molecular diffusion in single-site heterogeneous catalysts, which can play a vital role in designing low-temperature, sustainable catalytic processes.
Neutron scattering, catalytic diffusion, Beckmann rearrangement, heterogeneous catalysts, nylon-6, operando spectroscopy
2155-5435
2926-2934
Potter, Matthew
34dee7dc-2f62-4022-bb65-fc7b7fb526d2
O'Malley, Alexander J.
9a7506b9-31f7-4ec5-aa95-b8d4cbbba477
Chapman, Stephanie
02fa6ac4-c0e7-4cd3-8ffb-bf1c88cbfd45
Kezina, Julija
e4207217-45a7-4b24-a1b2-2436ce4a80fd
Newland, Stephanie
dc459841-89d5-4b96-b862-526b03f30e03
Silverwood, Ian P.
82866f8b-db54-4b52-ae0e-20ac70e21b9e
Mukhopadhyay, Sanghamitra
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Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Mezza, Thomas M.
a77c484c-a79f-4283-90c3-b049b63bdb1c
Parker, Stewart F.
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Catlow, C. Richard A.
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Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b
Potter, Matthew
34dee7dc-2f62-4022-bb65-fc7b7fb526d2
O'Malley, Alexander J.
9a7506b9-31f7-4ec5-aa95-b8d4cbbba477
Chapman, Stephanie
02fa6ac4-c0e7-4cd3-8ffb-bf1c88cbfd45
Kezina, Julija
e4207217-45a7-4b24-a1b2-2436ce4a80fd
Newland, Stephanie
dc459841-89d5-4b96-b862-526b03f30e03
Silverwood, Ian P.
82866f8b-db54-4b52-ae0e-20ac70e21b9e
Mukhopadhyay, Sanghamitra
15eb08b0-d556-45f1-8808-2fad9c9f4be5
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Mezza, Thomas M.
a77c484c-a79f-4283-90c3-b049b63bdb1c
Parker, Stewart F.
8752cd59-1b63-4399-859d-78e11a37c6d4
Catlow, C. Richard A.
50b88125-9415-4b37-9146-af6783e42510
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b

Potter, Matthew, O'Malley, Alexander J., Chapman, Stephanie, Kezina, Julija, Newland, Stephanie, Silverwood, Ian P., Mukhopadhyay, Sanghamitra, Carravetta, Marina, Mezza, Thomas M., Parker, Stewart F., Catlow, C. Richard A. and Raja, Robert (2017) Understanding the role of molecular diffusion and catalytic selectivity in liquid-phase Beckmann rearrangement. ACS Catalysis, 7, 2926-2934. (doi:10.1021/acscatal.6b03641).

Record type: Article

Abstract

Understanding the role of diffusion in catalysis is essential in the design of highly active, selective and stable industrial heterogeneous catalysts. By using a combination of advanced in situ spectroscopic characterisation tools, particularly quasi-elastic and inelastic neutron scattering, we outline the crucial differences in diffusion modes and molecular interactions of active sites within solid-acid catalysts. This, coupled with 2D solid-state NMR and probe-based FTIR spectroscopy, reveals the nature of the active site in our SAPO-37 catalyst and affords detailed information on the evolution of solid-acid catalysts that can operate at temperatures as low as 130 °C, for the Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam (precursor for Nylon-6). The versatility of this approach leads to structure-property correlations that contrast the dynamics of the diffusion process in the different materials studied. Our results illustrate the power of these techniques in unravelling the interplay between active site and molecular diffusion in single-site heterogeneous catalysts, which can play a vital role in designing low-temperature, sustainable catalytic processes.

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More information

Accepted/In Press date: 13 March 2017
e-pub ahead of print date: 13 March 2017
Keywords: Neutron scattering, catalytic diffusion, Beckmann rearrangement, heterogeneous catalysts, nylon-6, operando spectroscopy
Organisations: Chemistry, Magnetic Resonance, FIMS

Identifiers

Local EPrints ID: 406724
URI: https://eprints.soton.ac.uk/id/eprint/406724
ISSN: 2155-5435
PURE UUID: 82be7dfc-cca2-4cf1-ac7b-33b280898a14
ORCID for Matthew Potter: ORCID iD orcid.org/0000-0001-9849-3306
ORCID for Marina Carravetta: ORCID iD orcid.org/0000-0002-6296-2104
ORCID for Robert Raja: ORCID iD orcid.org/0000-0002-4161-7053

Catalogue record

Date deposited: 21 Mar 2017 02:03
Last modified: 17 Sep 2019 04:58

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