Direct Bronsted Acid-Catalyzed Dehydration of Glucose to HMF in Methyl Isobutyl Ketone

被引:24
作者
Quiroz, Natalia Rodriguez [1 ]
Chen, Tso-Hsuan [1 ]
Caratzoulas, Stavros [2 ]
Vlachos, Dionisios G. [1 ,2 ]
机构
[1] Univ Delaware, Dept Chem & Biomol Engn, Newark, DE 19716 USA
[2] Univ Delaware, Catalysis Ctr Energy Innovat, Newark, DE 19716 USA
关键词
biomass conversion; glucose; solvent; reaction kinetics; acid catalysts; molecular dynamics; QM/MM; D-FRUCTOSE; BIPHASIC DEHYDRATION; DIMETHYL-SULFOXIDE; METAL CHLORIDES; FORCE-FIELD; ISOMERIZATION; BIOMASS; CONVERSION; MECHANISM; SUGARS;
D O I
10.1021/acscatal.3c03153
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We report the direct Bronsted acid-catalyzed glucose dehydration in methyl isobutyl ketone solvent doped with small fractions of water to a high yield of 5-hydroxymethylfurfural (HMF) (74%) at low temperatures without using a Lewis acid catalyst, but the mechanistic understanding remains unclear. We combine fast experimental reaction kinetics, quantum mechanics/molecular mechanics molecular dynamics (QM/MM MD) simulations, IR and C-13 NMR spectroscopy, and kinetic isotope effects to elucidate the solvent effects and infer the potential reaction mechanism for glucose dehydration. Our results indicate that the direct conversion of glucose to HMF proceeds via acyclic isomerization to fructose, initiated by protonation of the ring oxygen followed by the opening of the pyranose ring. We found that ketone-based organic solvents promote the selective dehydration of glucose by enhancing the catalyst-substrate interactions at the ring oxygen, which facilitates dehydration. In contrast, alcohol-based organic solvents promote protonation of secondary hydroxyl groups, leading to reversion products and humins. Our findings highlight the importance of solvent selection in facilitating the protonation of the target glucose oxygen while minimizing protonation of the hydroxyl groups, which leads to undesired byproducts.
引用
收藏
页码:14221 / 14232
页数:12
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