Ligand-aided glycolysis of PET using functionalized silica-supported Fe2O3 nanoparticles

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dc.contributor.authorRimola, Albert
dc.contributor.authorHolmes, Justin D.
dc.contributor.authorCollins, Gillian
dc.contributor.authorCasey, Éadaoin
dc.contributor.authorBreen, Rachel
dc.contributor.authorGómez, Jennifer S.
dc.contributor.authorKentgens, Arno P. M.
dc.contributor.authorPareras, Gerard
dc.contributor.funderScience Foundation Ireland
dc.contributor.funderHorizon 2020
dc.contributor.funderFundación Margarita Salas
dc.contributor.funderMinisterio de Economía y Competitividad
dc.date.accessioned2023-11-15T15:35:15Z
dc.date.available2023-11-09T11:36:36Zen
dc.date.available2023-11-15T15:35:15Z
dc.date.issued2023-10-18
dc.date.updated2023-11-09T11:36:38Zen
dc.description.abstractThe development of efficient catalysts for the chemical recycling of poly(ethylene terephthalate) (PET) is essential to tackling the global issue of plastic waste. There has been intense interest in heterogeneous catalysts as a sustainable catalyst system for PET depolymerization, having the advantage of easy separation and reuse after the reaction. In this work, we explore heterogeneous catalyst design by comparing metal-ion (Fe3+) and metal-oxide nanoparticle (Fe2O3 NP) catalysts immobilized on mesoporous silica (SiO2) functionalized with different N-containing amine ligands. Quantitative solid-state nuclear magnetic resonance (NMR) spectroscopy confirms successful grafting and elucidates the bonding mode of the organic ligands on the SiO2 surface. The surface amine ligands act as organocatalysts, enhancing the catalytic activity of the active metal species. The Fe2O3 NP catalysts in the presence of organic ligands outperform bare Fe2O3 NPs, Fe3+-ion-immobilized catalysts and homogeneous FeCl3 salts, with equivalent Fe loading. X-ray photoelectron spectroscopy analysis indicates charge transfer between the amine ligands and Fe2O3 NPs and the electron-donating ability of the N groups and hydrogen bonding may also play a role in the higher performance of the amine-ligand-assisted Fe2O3 NP catalysts. Density functional theory (DFT) calculations also reveal that the reactivity of the ion-immobilized catalysts is strongly correlated to the ligand-metal binding energy and that the products in the glycolysis reaction catalyzed by the NP catalysts are stabilized, showing a significant exergonic character compared to single ion-immobilized Fe3+ ions.en
dc.description.sponsorshipScience Foundation Ireland (AMBER Grant No: 12/RC2278_P2); Ministerio de Economía y Competitividad (project PID2021-126427NB-I00)
dc.description.statusPeer revieweden
dc.description.versionPublished Version
dc.format.mimetypeapplication/pdfen
dc.identifier.citationCasey, É., Breen, R., Gómez, J. S., Kentgens, A. P., Pareras, G., Rimola, A., Holmes, J. D. and Collins, G. (2023) 'Ligand-aided glycolysis of PET using functionalized silica-supported Fe2O3 nanoparticles', ACS Sustainable Chemistry and Engineering, 11(43), pp. 15544-15555. doi: 10.1021/acssuschemeng.3c03585
dc.identifier.doi10.1021/acssuschemeng.3c03585en
dc.identifier.eissn2168-0485
dc.identifier.endpage15555
dc.identifier.issued43
dc.identifier.journaltitleACS Sustainable Chemistry and Engineering
dc.identifier.startpage15544
dc.identifier.urihttps://hdl.handle.net/10468/15232
dc.identifier.volume11
dc.language.isoenen
dc.publisherACS Publications
dc.relation.projectinfo:eu-repo/grantAgreement/EC/H2020::RIA/101008500/EU/A Pan-European Solid-State NMR Infrastructure for Chemistry-Enabling Access/PANACEA
dc.rights© 2023, the Authors. Published by the American Chemical Society. This article is licensed under CC BY 4.0
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectHeterogeneous catalysts
dc.subjectGlycolysis
dc.subjectSiO2
dc.subjectNanoparticles
dc.subjectPolyethylene terephthalate
dc.subjectDFT
dc.subjectSolid-state NMR
dc.titleLigand-aided glycolysis of PET using functionalized silica-supported Fe2O3 nanoparticles
dc.typeArticle (peer-reviewed)
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