Mechanisms and Energetics for Acid Catalyzed β-D-Glucose Conversion to 5-Hydroxymethylfurfurl

被引：55

作者：

Qian, Xianghong ^{[1
]}

机构：

[1] Univ Arkansas, Dept Chem Engn, Fayetteville, AR 72701 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2011年 / 115卷 / 42期

基金：

美国国家科学基金会;

关键词：

MOLECULAR-DYNAMICS SIMULATIONS; D-FRUCTOSE; D-XYLOSE; CONDENSATION-REACTIONS; HIGH-TEMPERATURE; LIQUID ALKANES; WATER; DEHYDRATION; 5-HYDROXYMETHYL-2-FURALDEHYDE; DENSITY;

D O I：

10.1021/jp2041982

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：

Car-Parrinello based ab initio molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations were carried out to investigate the mechanism and energetics for acid-catalyzed beta-D-glucose conversion to 5-hydroxymethylfurfurl (HMF) in water. HMF is a critical intermediate for biomass conversion to biofuels. It was found that protonation of the C2-OH on glucose, the breakage of the C2-O2 bond, and the formation of the C2-O5 bond is the critical rate-limiting step for the direct glucose conversion to HMF without converting to fructose first, contrary to the wide-spread assumption in literature that fructose is the main intermediate for glucose conversion to HMF. The calculated reaction barrier of 30-35 kcal/mol appears to be solvent-induced and is in excellent agreement with experimental observations.

引用

页码：11740 / 11748

页数：9

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