生物质氢解制α,ω-二醇催化剂设计及催化机理研究

The conversion of biomass into high value-added chemicals is an important frontier research topic. In this project, we conducted research on two key scientific issues in the hydrogenolysis of biomass to versatile α,ω-diol reactions: 1) Exploring the precise hydrodeoxygenation and C-O bond cleavage control mechanisms of biomass 2) Explaining the synergistic effect in the multi-component catalyst and the structure-catalytic performance relationship. It is intended to start with the controlling of catalyst acidity, defects, metal active components, and oxygen-philic additives to reveal the origin of metal-metal, metal-support, and metal-defect interactions in the catalytic system, and to investigate the nature of their interactions with substrates and intermediates in dehydration, hydration, hydrogenation, rearrangement, dehydrogenation and other reactions. The establishment of the relationship among hydrogen transfer, hydrogen heterolytic cleavage, carbocation intermediates, solvent effects and reaction pathways, and the clarification of related catalytic mechanisms will be extremely useful. By optimizing the catalyst design and reaction parameters, high-efficiency conversion of biomass feedstock to α,ω-diols is expected to be achieved. The implementation of this project will provide useful reference for the in-depth development and utilization of biomass.

将生物质转化成大宗、高附加值化学品是重要的前沿课题。本项目中针对甘油、四氢呋喃甲醇等生物质氢解制大宗、用途广泛的α，ω-二醇反应中的两个关键科学问题开展研究：1）探究生物质原料的精准加氢脱氧和C-O键裂解控制机制，2）阐述多组分催化剂中的协同效应及与催化性能之间的构效关系。拟通过对催化剂酸性、缺陷、金属活性组分、亲氧助剂的调控入手，揭示催化体系中金属-金属，金属-载体，金属-缺陷相互作用的本质，考察其及对底物和中间产物在催化剂表面的脱水、水合、加氢、重排、脱氢等反应的影响。建立氢转移、氢异裂、碳正离子中间体、以及溶剂效应与反应路径的关联，并阐明相关催化机理。通过优化催化剂设计和反应工艺参数，实现生物质原料高效转化制α，ω-二醇。本项目的实施将为生物质的深度开发利用提供有益参考。

生物质高效氢解制大宗、高附加值化学品是多相催化和绿色化学领域的重要课题。本项目研究了生物质内酯、四氢糠醇等氢解制α，ω-二醇催化反应中和生物质C-O键裂解反应中的关键科学问题和瓶颈技术问题。重点研究了生物质氢解催化剂中金属-酸/碱位点、金属-可还原氧化物之间的协同作用；生物质底物在催化剂表面的吸附构型及调控策略；非贵金属氢解催化剂的稳定策略；氢气的异裂活化等。其中主要研究成果包括：（1）开发了多种基于非贵金属的氢解催化剂，高效氢解生物质原料制1，5-戊二醇，1，4-丁二醇，1，4-戊二醇，1，6-己二醇等。（2）研究了各类生物质C-O键活化裂解策略及并提出相应催化剂设计原理。（3）对生物质氢解反应中的金属-酸中心、金属-缺陷中心的协同催化作用形成新认识。（4）对催化剂表面的竞争吸附及氢气的异裂活化提出新理解、新思路。本项目取得的相关成果将为生物质资源催化转化利用提供有益的理论依据和技术支撑。