催化碳水化合物“一锅法”转化为高附加值呋喃衍生物的双功能两性材料制备及性能研究

Design and preparation of catalysts or catalytic processes with high efficiency as well as studies on catalytic performance and mechanism are considered to be important basic researches in the selective transformation of biomass, and are also the important direction in current study of comprehensive utilization of biomass. Biomass, especially carbohydrate/sugar, is regarded as one of the most abundant renewable resources in the world. However, it is extremely difficult to find an efficient catalytic system on one-pot transformation of inedible cellulose (six-carbon sugar) and hemicellulose (five-carbon and six-carbon sugars) into biofuels and high value-added chemicals. In our previous studies, we designed and prepared a series of functional heterogeneous catalyst which could effectively catalyze six-carbon sugars into furan derivatives, and studies on reaction mechanisms were also carried out. Hereby, this project will further modify the structure of the previously prepared catalysts by reserving original catalytic active site while introducing a hydrophobic catalyst or a secondary active site, expecting to achieve one-pot conversion of carbohydrates especially natural source biomass to value-added furan-type compounds with the assistance of macroscopic or microscopic two phase system. Through the structure characterization of catalysts and the mechanism research of catalytic processes, we are going to figure out the catalytic performance of bifunctional hydrophilic/hydrophobic materials, so as to provide a scientific basis for the preparation of highly efficient catalysts and the effective conversion of biomass.

高效催化剂或催化体系的创制以及相应催化性能和机理的探讨是生物质定向转化过程中重要的基础研究，也是当前生物质综合利用研究的重要方向。生物质特别是糖类被认为是全球范围内最丰富的可再生资源，但高效催化纤维素（六碳糖）和半纤维素（五碳糖和部分六碳糖）经“一锅法”转化为生物燃料和高附加值化学品仍极其困难。申请者在前期工作中设计和制备出一系列功能化多相催化剂，从中筛选出可将六碳糖高效转化为呋喃衍生物的高效催化剂，并对催化反应机理进行了一定的研究。本申请拟以前期工作为基础，对先前的催化剂进一步结构修饰和改造，在保留原有催化活性位点的基础上，引入二次转化疏水性催化剂或者活性位点，以期在宏观或者微观两相体系的辅助作用下催化碳水化合物特别是天然源生物质“一锅法”转化为高附加值呋喃衍生物。并通过结构表征和机理研究，探讨双功能两性材料的催化性能与结构关系，为高效催化剂的创制与生物质有效转化和利用提供科学依据。

按照研究计划开展了系列研究工作，设计和制备出系列两性功能金属有机框架、双酸沸石/有机-无机杂化材料、磁性酸-碱双功能材料、酸-碱双功能介孔杂化材料等固体催化剂，并成功应用于催化生物质转化中（如碳水化合物催化转化为γ-戊内酯(GVL)或乙酰丙酸酯等高值分子、生物质含氧化合物催化转移加氢或氢化脱氧过程、油料转化为生物燃料等）。研究结果对生物质碳水化合物新型转化路径的开发以及高效两性功能材料的构筑提供了一定的参考。.在宏观两相体系研究的基础上，针对性构建表面亲水、内腔/孔道疏水且分别具备两种不同活性位点的多孔催化剂，进而通过这种单相微催化环境实现两相反应介质同样的辅助作用。此外，开展了上述催化剂应用于直接催化生物质转化为呋喃衍生物的工艺优化研究，探寻合适的加热模式、氢源等。基于上述研究，设计和制备出高效双功能两性材料实现了催化生物质“一锅”多步转化为呋喃衍生物，并运用相应的表征和测试手段探讨催化剂材料结构与催化活性之间的变化规律，提出催化剂活性中心的作用机制、活性调控方法等。所得实验和理论成果可为生物质资源的综合利用提供较好的技术积累和支撑，具有进一步研究的潜力。