National-Local Joint Engineering Laboratory for Energy Conservation in Chemical Process Integration and Resources Utilization, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin, China.
The School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China.
Carbohydr Polym. 2022 Feb 15;278:118936. doi: 10.1016/j.carbpol.2021.118936. Epub 2021 Nov 26.
Cellulose conversion into 5-hydroxymethylfurfural (5-HMF) is difficult because of the strong hydrogen bonding existed in cellulose chains. Brønsted/Lewis (B/L) biacidic functionalized ionic liquids (ILs) have great advantages in acid-catalyzed tandem reactions, but the catalytic effect of ILs differs considerably depending on B/L acid ratios. Therefore, this work designed a series of reactions with different proportions of biacidic ILs for the preparation of 5-HMF from cellulose. The tandem reaction is often performed in the presence of a solvent, and the activity of the catalyst is also affected by the solvent. Therefore, in this work, the solvation model density(SMD) model was introduced into the quantum chemical calculation method for molecular design to predict the catalytic effect and explore the catalytic mechanism. The calculation results and experiments jointly showed that [(HSO-P)im]Cl·ZnCl had the highest efficiency, with a 5-HMF yield of 65.66%. This study facilitates the directional optimization design of the catalyst.
纤维素转化为 5-羟甲基糠醛（5-HMF）比较困难，因为纤维素链中存在很强的氢键。布朗斯特/路易斯（B/L）双酸性功能化离子液体（ILs）在酸催化串联反应中具有很大的优势，但 ILs 的催化效果因 B/L 酸比而异。因此，这项工作设计了一系列具有不同 B/L 双酸性 ILs 比例的反应，用于从纤维素制备 5-HMF。串联反应通常在溶剂存在的情况下进行，而催化剂的活性也受到溶剂的影响。因此，在这项工作中，引入了溶剂化模型密度（SMD）模型到量子化学计算方法的分子设计中，以预测催化效果并探索催化机制。计算结果和实验共同表明，[(HSO-P)im]Cl·ZnCl 具有最高的效率，5-HMF 的产率为 65.66%。这项研究有助于对催化剂进行定向优化设计。
