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The extrusion of noble metal nanoparticle catalysts for sustainable oxidation reactions

The extrusion of noble metal nanoparticle catalysts for sustainable oxidation reactions
The extrusion of noble metal nanoparticle catalysts for sustainable oxidation reactions
Through employing a combination of complimentary structural, spectroscopic and high-resolution microscopy techniques, the superior properties of a [PtCl4]2- precursor to yield well-defined, isolated nanoparticles (predominantly 2-3 nm) upon microporous framework architectures, have been established. These are prepared via a one-step, in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. The catalytic activity of these materials can be intrinsically linked to the degree of nanoparticle formation. The [PtCl4]2- precursor bestows a greater propensity for nanoparticle formation across a range of activation conditions by comparison to [PdCl4]2- and [AuCl4]- precursors. This, in concert with the surrounding microporous architecture, donates superior catalytic performance for the aerobic oxidation of KA oil to cyclohexanone (precursor for adipic acid and ε-caprolactam), under continuous flow conditions. It is able to approach unrivalled yields of >90% by adapting a ‘closed-loop’ system.
Detailed spectroscopic investigations into the nature of the active sites at the molecular level, coupled with high-resolution electron microscopy, reveal that the intricacies of the synthetic methodology and associated activation procedures play a vital role in regulating the locality, morphology and size of the metal nanoparticles produced. Theseinvestigations also offer insights into the potential consequences of prolonged catalytic exposure.
All three (Au, Pt & Pd) nanoparticle systems demonstrate a profound influence on the activation of molecular oxygen and alkyl peroxides for a plethora of selective catalytic oxidations. Furthermore, this design strategy offers adequate scope for the creation of multi-metallic (e.g. Pd-Cu, Au-Cu & Au-Pt), multifunctional heterogeneous catalysts, in the continued quest for the activation of molecular oxygen in sustainable catalytic processes.
University of Southampton
Gill, Arran Michael
db3a2ff8-27f5-4d40-a895-69b3900f7624
Gill, Arran Michael
db3a2ff8-27f5-4d40-a895-69b3900f7624
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b

Gill, Arran Michael (2017) The extrusion of noble metal nanoparticle catalysts for sustainable oxidation reactions. University of Southampton, Doctoral Thesis, 294pp.

Record type: Thesis (Doctoral)

Abstract

Through employing a combination of complimentary structural, spectroscopic and high-resolution microscopy techniques, the superior properties of a [PtCl4]2- precursor to yield well-defined, isolated nanoparticles (predominantly 2-3 nm) upon microporous framework architectures, have been established. These are prepared via a one-step, in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. The catalytic activity of these materials can be intrinsically linked to the degree of nanoparticle formation. The [PtCl4]2- precursor bestows a greater propensity for nanoparticle formation across a range of activation conditions by comparison to [PdCl4]2- and [AuCl4]- precursors. This, in concert with the surrounding microporous architecture, donates superior catalytic performance for the aerobic oxidation of KA oil to cyclohexanone (precursor for adipic acid and ε-caprolactam), under continuous flow conditions. It is able to approach unrivalled yields of >90% by adapting a ‘closed-loop’ system.
Detailed spectroscopic investigations into the nature of the active sites at the molecular level, coupled with high-resolution electron microscopy, reveal that the intricacies of the synthetic methodology and associated activation procedures play a vital role in regulating the locality, morphology and size of the metal nanoparticles produced. Theseinvestigations also offer insights into the potential consequences of prolonged catalytic exposure.
All three (Au, Pt & Pd) nanoparticle systems demonstrate a profound influence on the activation of molecular oxygen and alkyl peroxides for a plethora of selective catalytic oxidations. Furthermore, this design strategy offers adequate scope for the creation of multi-metallic (e.g. Pd-Cu, Au-Cu & Au-Pt), multifunctional heterogeneous catalysts, in the continued quest for the activation of molecular oxygen in sustainable catalytic processes.

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Final Whole Thesis__Arran Gill__Corrections - Version of Record
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Published date: November 2017

Identifiers

Local EPrints ID: 422157
URI: http://eprints.soton.ac.uk/id/eprint/422157
PURE UUID: 704410e5-2434-4202-9567-fdba8ed1e984
ORCID for Robert Raja: ORCID iD orcid.org/0000-0002-4161-7053

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Date deposited: 18 Jul 2018 16:30
Last modified: 28 Jun 2021 04:01

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Contributors

Author: Arran Michael Gill
Thesis advisor: Robert Raja ORCID iD

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