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dc.contributor.authorYue, Chaochao
dc.contributor.authorLi, Guanna
dc.contributor.authorPidko, Evgeny A.
dc.contributor.authorWiesfeld, Jan J.
dc.contributor.authorRigutto, Marcello
dc.contributor.authorHensen, Emiel J. M.
dc.date.accessioned2016-12-29T13:20:20Z
dc.date.available2016-12-29T13:20:20Z
dc.date.issued2016-08-05
dc.identifier.citationYue C, Li G, Pidko EA, Wiesfeld JJ, Rigutto M, et al. (2016) Dehydration of Glucose to 5-Hydroxymethylfurfural Using Nb-doped Tungstite. ChemSusChem 9: 2421–2429. Available: http://dx.doi.org/10.1002/cssc.201600649.
dc.identifier.issn1864-5631
dc.identifier.pmid27493127
dc.identifier.doi10.1002/cssc.201600649
dc.identifier.urihttp://hdl.handle.net/10754/622083
dc.description.abstractDehydration of glucose to 5-hydroxymethylfurfural (HMF) remains a significant problem in the context of the valorization of lignocellulosic biomass. Hydrolysis of WCl6 and NbCl5 leads to precipitation of Nb-containing tungstite (WO3H2O) at low Nb content and mixtures of tungstite and niobic acid at higher Nb content. Tungstite is a promising catalyst for the dehydration of glucose to HMF. Compared with Nb2O5, fewer by-products are formed because of the low BrOnsted acidity of the (mixed) oxides. In water, an optimum yield of HMF was obtained for Nb-W oxides with low Nb content owing to balanced Lewis and BrOnsted acidity. In THF/water, the strong Lewis acidity and weak BrOnsted acidity caused the reaction to proceed through isomerization to fructose and dehydration of fructose to a partially dehydrated intermediate, which was identified by LC-ESI-MS. The addition of HCl to the reaction mixture resulted in rapid dehydration of this intermediate to HMF. The HMF yield obtained in this way was approximately 56% for all tungstite catalysts. Density functional theory calculations show that the Lewis acid centers on the tungstite surface can isomerize glucose into fructose. Substitution of W by Nb lowers the overall activation barrier for glucose isomerization by stabilizing the deprotonated glucose adsorbate.
dc.description.sponsorshipThe authors acknowledge financial support by Shell Global Solutions International. This work was partly supported by the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), an NWO Gravitation program funded by the Ministry of Education, Culture and Science of the government of the Netherlands.
dc.publisherWiley-Blackwell
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/cssc.201600649/full
dc.rightsThis is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subject5-hydroxylmethylfurfural
dc.subjectdehydration
dc.subjectglucose
dc.subjectniobium oxide
dc.subjecttungsten oxide
dc.titleDehydration of Glucose to 5-Hydroxymethylfurfural Using Nb-doped Tungstite
dc.typeArticle
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalChemSusChem
dc.eprint.versionPublisher's Version/PDF
dc.contributor.institutionInorganic Materials Chemistry; Eindhoven University of Technology; P.O. Box 513 5600 MB Eindhoven The Netherlands
dc.contributor.institutionShell Global Solutions International B.V.; P.O. Box 38000 1030 BN Amsterdam The Netherlands
kaust.personYue, Chaochao
refterms.dateFOA2018-06-14T04:38:51Z


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This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Except where otherwise noted, this item's license is described as This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.