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Capping agent, solvent, and nanoparticle interactions: driving selectivity for biomass transformations

Capping agent, solvent, and nanoparticle interactions: driving selectivity for biomass transformations
Capping agent, solvent, and nanoparticle interactions: driving selectivity for biomass transformations
It is well-established that tailoring the structural properties of nanoparticles, for example, their size, shape, available active surface, and interaction with metal oxide supports, imparts significant control on catalytic transformations. However, this often relies on the use of stabilizing (capping) agents. These capping agents, predominantly long chain, or bulky polymers, are not benign and also influence the catalytic performance. In this study, we expand on the use of surfactant-controlled reaction pathways for the hydrogenation of furfural on Pd/TiO2. In particular, the presence of polyvinyl alcohol (PVA) on the methanol prepared catalysts, shifts product selectivity for furfural hydrogenation to tetrahydrofurfuryl alcohol (THFA), resulting from restricted diffusion away from the Pd nanoparticle surface. Furthermore, we demonstrate how solid-state NMR is able to study the surfactant-catalyst interaction and how these can be correlated to the selectivity profile for furfural hydrogenation.
Furfural hydrogenation, Pd nanoparticles, Sol-immobilization, Solid-state nuclear magnetic resonance spectroscopy, X-ray absorption spectroscopy
1867-3880
Tierney, George F.
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Banks, Daniel
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Carravetta, Marina
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Oakley, Alice E.
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Alijani, Shahram
667987aa-3ee6-4c4f-8922-80bebe3bd5b9
Barlocco, Ilaria
34b2c770-a1b5-4ede-ab12-03df8d48d8ea
Dimitratos, Nikolaos
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Villa, Alberto
d1f6646b-f0d4-420c-8a52-c09663f46e5f
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266
Tierney, George F.
5a1b1e97-5868-4933-a321-9b2cdfb69c5a
Banks, Daniel
8a78adb9-cc68-4526-86f7-1855a49e068f
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Oakley, Alice E.
78ad819d-33bb-4c77-af90-9dcc96ed52e0
Alijani, Shahram
667987aa-3ee6-4c4f-8922-80bebe3bd5b9
Barlocco, Ilaria
34b2c770-a1b5-4ede-ab12-03df8d48d8ea
Dimitratos, Nikolaos
a4385576-4a05-478b-8389-460bfb43412b
Villa, Alberto
d1f6646b-f0d4-420c-8a52-c09663f46e5f
Wells, Peter P.
bc4fdc2d-a490-41bf-86cc-400edecf2266

Tierney, George F., Banks, Daniel, Carravetta, Marina, Oakley, Alice E., Alijani, Shahram, Barlocco, Ilaria, Dimitratos, Nikolaos, Villa, Alberto and Wells, Peter P. (2025) Capping agent, solvent, and nanoparticle interactions: driving selectivity for biomass transformations. ChemCatChem, 17 (13), [e202401892]. (doi:10.1002/cctc.202401892).

Record type: Article

Abstract

It is well-established that tailoring the structural properties of nanoparticles, for example, their size, shape, available active surface, and interaction with metal oxide supports, imparts significant control on catalytic transformations. However, this often relies on the use of stabilizing (capping) agents. These capping agents, predominantly long chain, or bulky polymers, are not benign and also influence the catalytic performance. In this study, we expand on the use of surfactant-controlled reaction pathways for the hydrogenation of furfural on Pd/TiO2. In particular, the presence of polyvinyl alcohol (PVA) on the methanol prepared catalysts, shifts product selectivity for furfural hydrogenation to tetrahydrofurfuryl alcohol (THFA), resulting from restricted diffusion away from the Pd nanoparticle surface. Furthermore, we demonstrate how solid-state NMR is able to study the surfactant-catalyst interaction and how these can be correlated to the selectivity profile for furfural hydrogenation.

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ChemCatChem - 2025 - Tierney - Capping Agent Solvent and Nanoparticle Interactions Driving Selectivity for Biomass - Version of Record
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Accepted/In Press date: 24 April 2025
e-pub ahead of print date: 25 April 2025
Published date: 8 July 2025
Additional Information: Publisher Copyright: © 2025 The Author(s). ChemCatChem published by Wiley-VCH GmbH.
Keywords: Furfural hydrogenation, Pd nanoparticles, Sol-immobilization, Solid-state nuclear magnetic resonance spectroscopy, X-ray absorption spectroscopy

Identifiers

Local EPrints ID: 502300
URI: http://eprints.soton.ac.uk/id/eprint/502300
ISSN: 1867-3880
PURE UUID: 6b4f920a-3c72-4936-9ba5-42524d171356
ORCID for Marina Carravetta: ORCID iD orcid.org/0000-0002-6296-2104
ORCID for Alice E. Oakley: ORCID iD orcid.org/0000-0002-5489-9424
ORCID for Peter P. Wells: ORCID iD orcid.org/0000-0002-0859-9172

Catalogue record

Date deposited: 20 Jun 2025 16:43
Last modified: 04 Sep 2025 02:08

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Contributors

Author: George F. Tierney
Author: Daniel Banks
Author: Alice E. Oakley ORCID iD
Author: Shahram Alijani
Author: Ilaria Barlocco
Author: Nikolaos Dimitratos
Author: Alberto Villa
Author: Peter P. Wells ORCID iD

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