Continuous flow (Sulfated) Zirconia Catalysed Cascade Conversion of Levulinic Acid to γ-Valerolactone

Merenda, A; Orr, SA; Liu, Y; Hernández Garcia, B; Osatiashtiani, A; Morales, G; Paniagua, M; Melero, JA; Lee, AF; Wilson, K

Continuous flow (Sulfated) Zirconia Catalysed Cascade Conversion of Levulinic Acid to γ-Valerolactone

Merenda, A

Orr, SA Liu, Y Hernández Garcia, B Osatiashtiani, A Morales, G Paniagua, M Melero, JA Lee, AF Wilson, K

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Publisher:: WILEY-V C H VERLAG GMBH
Publication Type:: Journal Article
Citation:: ChemCatChem, 2023, 15, (3)
Issue Date:: 2023-02-08

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Field	Value	Language
dc.contributor.author	Merenda, A https://orcid.org/0000-0002-9998-0330
dc.contributor.author	Orr, SA
dc.contributor.author	Liu, Y
dc.contributor.author	Hernández Garcia, B
dc.contributor.author	Osatiashtiani, A
dc.contributor.author	Morales, G
dc.contributor.author	Paniagua, M
dc.contributor.author	Melero, JA
dc.contributor.author	Lee, AF
dc.contributor.author	Wilson, K
dc.date.accessioned	2023-10-09T04:59:12Z
dc.date.available	2023-10-09T04:59:12Z
dc.date.issued	2023-02-08
dc.identifier.citation	ChemCatChem, 2023, 15, (3)
dc.identifier.issn	1867-3880
dc.identifier.issn	1867-3899
dc.identifier.uri	http://hdl.handle.net/10453/172595
dc.description.abstract	γ-Valerolactone (GVL) is a renewable and versatile platform chemical derived from sustainable carbon feedstocks. The cascade conversion of levulinic acid into GVL requires Brønsted and Lewis acid catalysed reactions. Here, a dual-catalyst bed configuration is demonstrated that promotes synergy between Brønsted acid sites in sulfated zirconia (SZ) and Lewis acid sites in ZrO2/SBA-15 for the liquid phase, continuous flow esterification and subsequent catalytic transfer hydrogenation (CTH) of levulinic acid to GVL. A saturated surface sulfate monolayer, possessing a high density of strong Brønsted acid sites, was optimal for levulinic acid esterification to isopropyl levulinate over SZ (>80 % conversion). A conformal ZrO2 bilayer, deposited over a SBA-15 mesoporous silica and possessing mixed Brønsted:Lewis acidity, catalysed CTH of the levulinate ester and subsequent dealcoholisation/cyclisation to GVL (>60 % selectivity). Maximum stable productivity for the dual-bed was 2.2 mmolGVL.gcat.h−1 at 150 °C, significantly outperforming either catalyst alone or a physical mixture of both. Flow chemistry is a versatile approach to achieve spatial control over cascade transformations involving distinct catalytically active sites.
dc.language	English
dc.publisher	WILEY-V C H VERLAG GMBH
dc.relation.ispartof	ChemCatChem
dc.relation.isbasedon	10.1002/cctc.202201224
dc.rights	info:eu-repo/semantics/closedAccess
dc.subject	0302 Inorganic Chemistry, 0306 Physical Chemistry (incl. Structural), 0904 Chemical Engineering
dc.subject.classification	Organic Chemistry
dc.subject.classification	4004 Chemical engineering
dc.title	Continuous flow (Sulfated) Zirconia Catalysed Cascade Conversion of Levulinic Acid to γ-Valerolactone
dc.type	Journal Article
utslib.citation.volume	15
utslib.for	0302 Inorganic Chemistry
utslib.for	0306 Physical Chemistry (incl. Structural)
utslib.for	0904 Chemical Engineering
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology/School of Civil and Environmental Engineering
utslib.copyright.status	closed_access	*
dc.date.updated	2023-10-09T04:59:11Z
pubs.issue	3
pubs.publication-status	Published
pubs.volume	15
utslib.citation.issue	3

Abstract:

γ-Valerolactone (GVL) is a renewable and versatile platform chemical derived from sustainable carbon feedstocks. The cascade conversion of levulinic acid into GVL requires Brønsted and Lewis acid catalysed reactions. Here, a dual-catalyst bed configuration is demonstrated that promotes synergy between Brønsted acid sites in sulfated zirconia (SZ) and Lewis acid sites in ZrO2/SBA-15 for the liquid phase, continuous flow esterification and subsequent catalytic transfer hydrogenation (CTH) of levulinic acid to GVL. A saturated surface sulfate monolayer, possessing a high density of strong Brønsted acid sites, was optimal for levulinic acid esterification to isopropyl levulinate over SZ (>80 % conversion). A conformal ZrO2 bilayer, deposited over a SBA-15 mesoporous silica and possessing mixed Brønsted:Lewis acidity, catalysed CTH of the levulinate ester and subsequent dealcoholisation/cyclisation to GVL (>60 % selectivity). Maximum stable productivity for the dual-bed was 2.2 mmolGVL.gcat.h−1 at 150 °C, significantly outperforming either catalyst alone or a physical mixture of both. Flow chemistry is a versatile approach to achieve spatial control over cascade transformations involving distinct catalytically active sites.

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http://hdl.handle.net/10453/172595