葡萄糖“一锅法”合成2,5-二甲基呋喃磁性双功能催化剂的构建及催化机理

2,5-Dimethylfuran is an important biomass fuel.At present, the conversion from glucose to synthesize 2,5-dimethylfuran (DMF) mainly employ two-step approach. There are some problems, eg, difficulity to separate and recycle, as well as poor efficiency, to be resolved. Therefore, this program proposes a kind of magnetic bifunctional catalysts which the loading acid (B acid & L acid) and noble (or transition) metal nanoparticles simultaneously are applied in one-pot synthesis of 2,5-dimethylfuran from glucose. We will also explore the structure-activity relationship of catalysts, and the mechanism of the catalytic reactions. Morover, we will mainly study the basic scientific problems which are the synergy catalysis of B acid and L acid, the stabilisation model for noble (or transition) metal nanoparticles (NPs) in poly (ionic liquid), and the relevance among the reactions of one-pot synthesis. It is estimated that the implementation of this program should increase the reaction efficiency and the yield of DMF, providing new ideas for biomass catalytic conversion and catalysts design.

2,5-二甲基呋喃（DMF）是一种重要的生物质燃料，其可由葡萄糖通过脱水、脱氧还原两步法转化而来，但两步法存在分离难、不易回收、效率低等问题。为此，本项目提出用一种同时载有酸（B酸&L酸）与贵（过渡）金属纳米粒子（NPs）的磁性双功能催化剂，"一锅法"直接由葡萄糖合成DMF。揭示了催化剂的构效关系，以及催化作用的机理。重点研究B酸与L酸协同催化作用，聚离子液体稳定贵（过渡）NPs，以及"一锅法"中反应间的关联等基础科学问题。预计本项目的实施能够提高反应的效率及DMF的收率，并为生物质催化转化以及催化剂的设计提供了新思路。

以含不饱和键硅偶联剂、磁性纳米粒子、含不饱和键的功能化离子液体等出发制备纳米催化剂，用于生物质单糖葡萄糖与果糖合成液体燃料2,5-二甲基呋喃反应，目前能获取高产率的得到中间体5-羟甲基糠醛，并对相关机理进行了研究；接着借助自己合成的三氯氢硅为前体，经水解自组装得到两亲性硅球，然后负载Pd等贵金属得到负载型催化剂，该催化剂能高效5-羟甲基糠醛脱氢还原合成2,5-二甲基呋喃，相对于已报道的我们的催化活性高，反应温度低，且催化剂可回收。2. 双酸性催化剂高效催化纤维素一步转化为5-羟甲基糠醛：从三甲基硅基咪唑出发合成了一系列双酸性催化剂，组合不同的低粘度离子液体，催化纤维素高效转化为5-羟甲基糠醛，目前产率高达92%以上，比目前报道的要高20个百分点以上，催化剂相对绿色，且用量少。