糠醛制γ-戊内酯的高选择性Cu-Ni/铌固体酸多功能催化剂的制备及协同效应研究

由糠醛催化转化制高附加值的γ-戊内酯是一条极具前景的生物质利用途径，包含糠醛选择性加氢到糠醇，糠醇醇解制乙酰丙酸酯以及乙酰丙酸酯加氢脱水至γ-戊内酯三步反应。本项目结合前期研究结果及文献调研，得出铌固体酸上的糠醇催化醇解在三步反应中尤显重要。因此，通过反应动力学研究、原位反应表征设计及DFT理论计算，深入探讨醇解催化反应机理，同时对各反应间的相互影响进行研究；在此基础上，通过对铌固体酸表面酸中心的种类和强度的调节、Cu-Ni加氢组分的纳米化制备，利用二者之间的协同作用，设计制备出多功能的铌固体酸负载纳米Cu-Ni的复合催化剂，实现糠醛一釜制备γ-戊内酯的高效催化过程；并通过Cu-Ni/铌固体酸复合催化剂上糠醛制γ-戊内酯反应的动力学研究及DFT理论计算，确定整个反应过程的速控步骤，揭示多步反应间的耦合效应，为高效、绿色、低成本合成γ-戊内酯提供新思路。

Catalytic conversion of furfural to the high value-added γ-valerolactone (GVL) is one of the most promising pathways in the highly efficient utilization of biomass, including hydrogenation of furfural, alcoholysis of furfuryl alcohol, hydrogenation and dehydration of levulinate ester. in the project the alcoholysis of furfuryl alcohol on niobic solid acid is important among three above reactions by our recently studies and references. Therefore, we intend to explore catalytic alcoholysis mechanism in-depth by kinetics studies of the reaction, in situ characterization and DFT theoretical calculation, and study the interaction between the various reactions; On this basis, design and prepare niobic solid acid supported Cu-Ni bimetallic multifunctional catalyst through regulating the surface acid sites and intensity of niobic solid acid, preparation of Cu-Ni nano hydrogenation component and taking advantage of the synergetic effects between the two active sites; Integrate all the intermediate reaction steps of hydrogenation, alcoholysis, hydrogenation and dehydration in the furfural conversion by virtue of designing and preparing niobic solid acid supported Cu-Ni bimetallic multifunctional catalyst, and finally realize the highly efficient one-pot synthesis of GVL; Determine the rate-determining step of the process through kinetic studies and DFT theoretical calculation on Cu-Ni/Nb solid acid composite catalyst; Understand the coupling effects among different steps in whole the reactions. On the whole, the development of Cu-Ni/niobic solid acid multi-functional catalysts in this project would be believed to provide a novel idea for the highly efficient, low-cost and green synthesization of GVL.