Ultra-Dilute SnCl4-Catalyzed Conversion of Concentrated Glucose to 5-Hydroxymethylfurfural in Aqueous Deep Eutectic Solvent.

IF 7.5 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
ChemSusChem Pub Date : 2025-01-14 Epub Date: 2024-12-03 DOI:10.1002/cssc.202401105
Guo Xusheng, Qin Chuan, Si Yuxi, Lyu Xilei, Cheng Youwei
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Abstract

5-Hydroxymethylfurfural(HMF) is a versatile chemical synthesized from glucose dehydration catalyzed by metal chloride (MClx) in deep eutectic solvents (DESs). However, the low glucose concentration and high catalyst dosage hinder large-scale HMF production. Herein, we report an aqueous DES of tetraethylammonium bromide(TEAB)-glucose for converting concentrated glucose (40 wt %, relative to TEAB) using ultra-dilute SnCl4 (0.25 mol %), achieving a 62 % yield of HMF. Ultra-dilute MClx-catalyzed selective conversion of glucose is feasible only when combining SnCl4 with Br-based DES, which is elucidated by density functional theory and molecular dynamic calculations. Using SnCl4 is essential due to its higher glucose isomerization activity than AlCl3 and CrCl3, which can be attributed to its low-barrier coordination with glucose and its barrier-free separation from fructose. Halide anions in DESs strongly interact with glucose, hindering the MClx-glucose coordination and thereby reducing MClx's activity for glucose isomerization. Consequently, Br-based DESs facilitate higher activity of MClx than Cl-based DESs, due to the weaker interaction between halide anion and glucose. In addition, we elucidated the side reactions including condensation, polymerization, and isomerization, and proposed a reaction network. Our findings clarify the differential activity of MClx and the impact of halide anions in DESs on MClx's activity.

在水性深共晶溶剂中,超稀释 SnCl4 催化浓缩葡萄糖转化为 5-羟甲基糠醛。
5-Hydroxymethylfurfural (HMF) 是一种多功能化学品,由葡萄糖在深共晶溶剂(DES)中经氯化金属(MClx)催化脱水合成。然而,低葡萄糖浓度和高催化剂用量阻碍了 HMF 的大规模生产。在此,我们报告了一种四乙基溴化铵(TEAB)-葡萄糖水溶液 DES,利用超稀释 SnCl4(0.25 摩尔%)转化浓缩葡萄糖(相对于 TEAB 为 40 wt%),实现了 62% 的 HMF 收率。超稀释 MClx 催化的葡萄糖选择性转化只有在将 SnCl4 与基于溴的 DES 结合使用时才可行,密度泛函理论和分子动力学计算阐明了这一点。与 AlCl3 和 CrCl3 相比,SnCl4 具有更高的葡萄糖异构化活性,因此必须使用 SnCl4。DESs 中的卤化物阴离子与葡萄糖有强烈的相互作用,阻碍了 MClx 与葡萄糖的配位,从而降低了 MClx 的葡萄糖异构化活性。因此,由于卤化物阴离子与葡萄糖之间的相互作用较弱,Br 基 DESs 比 Cl 基 DESs 有助于提高 MClx 的活性。此外,我们还阐明了包括缩合、聚合和异构化在内的副反应,并提出了反应网络。我们的研究结果阐明了 MClx 的不同活性以及 DES 中卤化物阴离子对 MClx 活性的影响。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
ChemSusChem
ChemSusChem 化学-化学综合
CiteScore
15.80
自引率
4.80%
发文量
555
审稿时长
1.8 months
期刊介绍: ChemSusChem Impact Factor (2016): 7.226 Scope: Interdisciplinary journal Focuses on research at the interface of chemistry and sustainability Features the best research on sustainability and energy Areas Covered: Chemistry Materials Science Chemical Engineering Biotechnology
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