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dc.contributor.authorArora, Jyotsna Sudhiren_US
dc.contributor.authorAnsari, Khursheed Badruddinen_US
dc.contributor.authorChew, Jia Weien_US
dc.contributor.authorDauenhauer, Paul J.en_US
dc.contributor.authorMushrif, Samir H.en_US
dc.identifier.citationArora, J. S., Ansari, K. B., Chew, J. W., Dauenhauer, P. J. & Mushrif, S. H. (2019). Unravelling the catalytic influence of naturally occurring salts on biomass pyrolysis chemistry using glucose as a model compound : a combined experimental and DFT study. Catalysis Science & Technology, 9(13), 3504-3524.
dc.description.abstractFast pyrolysis is an efficient thermochemical decomposition process to produce bio-oil and renewable chemicals from lignocellulosic biomass. It has been suggested that alkali- and alkaline-earth metal (AAEM) ions in biomass alter the yield and composition of bio-oil, but little is known about the intrinsic chemistry of metal-catalyzed biomass pyrolysis. In this study, we combined thin-film pyrolysis experiments and density functional theory (DFT) calculations to obtain insights into AAEM-catalyzed glucose decomposition reactions, especially forming major bio-oil components and char. Experiments reveal the difference in the yield and composition of bio-oil of metal-free and AAEM complexed glucose. Metal-free glucose produced 2,3-dihydro-3,5-dihydroxy-6-methyl-4H-pyran-4-one (DHMDHP) as the predominant compound in bio-oil, while 1,6-anhydroglucofuranose (AGF) was dominant in Na(I)/glucose, levoglucosan (LGA) in K(I)/glucose, levoglucosenone (LGO) in Ca(II)/glucose and furfural in Mg(II)/glucose. To evaluate the stereoelectronic basis of metal ions in altering pyrolysis reaction kinetics, the reaction mechanisms of AGF, LGA, 5-hydroxymethylfurfural (5-HMF), furfural, 1,5-anhydro-4-deoxy-D-glycerohex-1-en-3-ulose (ADGH), LGO, and char formation were investigated using DFT calculations. DFT results showed that the presence of Ca(II) and Mg(II) ions catalyzed furfural and LGO formation, while alkali ions decatalyzed the formation of these products. Conversely, Na(I) and K(I) ions catalyzed the concerted dehydrative ring closure of glucofuranose during AGF formation. For ADGH, AAEMs showed an anti-catalytic effect. We also described a novel route for char formation via coupling between 1,2-anhydroglucopyranose and a carbonyl compound. The presence of alkali ions catalyzed char formation. Thus, the atomistic insights obtained from DFT calculations assist in understanding the observed change in experimental yields of individual bio-oil compounds governing their composition.en_US
dc.description.sponsorshipMinistry of Education (MOE)en_US
dc.relation.ispartofCatalysis Science & Technologyen_US
dc.rights© 2019 The Royal Society of Chemistry. All rights reserved.en_US
dc.subjectEngineering::Chemical engineeringen_US
dc.titleUnravelling the catalytic influence of naturally occurring salts on biomass pyrolysis chemistry using glucose as a model compound : a combined experimental and DFT studyen_US
dc.typeJournal Articleen
dc.contributor.schoolSchool of Chemical and Biomedical Engineeringen_US
dc.subject.keywordsCellulose Pyrolysisen_US
dc.description.acknowledgementThis research is supported by the Ministry of Education, Singapore, under the Academic Research Fund (AcRF) Tier-2 grant (Grant no. T2-1-082). Computational resources were provided by National Supercomputing Centre Singapore and Compute Canada.en_US
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