生物质基呋喃二甲醛的绿色合成

2,5-Diformylfuran (DFF) has received particular attention due to the various applications in pharmaceuticals, functional polymers and energy-materials etc. This project aims to carry out study on one-pot aproach to DFF from cheap fructose over the novel acid-metal bifunctional catalysts through dehydratic oxidation pathway. The bifunctional catalysts are metalloporphyrin based acidic porous organic polymers. DFF will therefore be produced by the acid (H+)-catalyzed dehydration of fructose, followed by the metalloporphyrin M(Por)-catalyzed aerobic oxidation of 5-hydroxymethylfurfural (HMF). The porous properties such as pore diameters and surface areas of the catalyst will be tuned by the size of linker molecules. The catalytic performance of the bi-functional catalyst on dehydration and oxidation reactions will be tuned by the controllable tuning the acid density and metal content, respectively. The mechanism on dehydration of fructose and oxidation of HMF will be investigated, and highly selective conversion of fructose to DFF will be relalized. The ratio of acid density to the transition metal density (nH+/nM) of the catalyst is used to monitor the balance between the dehydration and oxidation functions in this research, which will provide theoretical guidance for the construction of high efficient bifunctional catalysts. The goal of this project is to enhance understanding of the roles of construction for bifunctional catalytic system, to provide a theoretical basis for the high-value utilization of biomass resource. The research thus has great theoretical significance and potential application values.

2,5-呋喃二甲醛（DFF）在药物、高分子、能源材料制备等方面均有重要用途。本项目拟构建新型酸－金属双功能催化剂多孔酸性聚金属卟啉，以氧气为氧化剂，完成廉价的可再生生物质基果糖一步、高效、绿色、经济地定向转化为高附加值的DFF。项目拟通过调变催化剂骨架链接基团的体积来调节其孔径、比表面积等孔结构参数，通过调变催化剂酸密度和金属种类/含量来调节其催化脱水和催化氧化反应性能，研究催化剂中酸组分与金属组分在催化反应过程中的协同作用与平衡机制，揭示果糖脱水与5-羟甲基呋喃甲醛氧化反应的归并与耦合机制。项目的实施将加深对双功能催化体系构筑规律的认识，将为用于生物质能转化的多功能催化剂的可控合成提供新思路，也将为生物质能源高值化利用、可再生资源的绿色转化与规模化利用提供理论依据和技术支撑。因此，本项目的开展既具有科学理论价值又有经济效益、社会意义。

5-羟甲基糠醛（HMF）和糠醛是可再生的、重要的生物质基平台化合物，通过构建高效的催化体系，实现其绿色、定向转化为高附加值化学品具有重要意义。.2,5-二羟甲基四氢呋喃 (DHMTHF) 是重要溶剂和高分子单体。以胺基功能化的铝基有机金属框架化合物（MOFs）为载体负载金属钯，实现了HMF的选择性加氢制备DHMTHF。载体上的胺基增强了其与中间产物2,5-二羟甲基呋喃 (DHMF) 的相互作用，促进了其连续加氢，提高了目标产物DHMTHF的选择性。HMF加氢的转化率达100%，DHMTHF收率高达96%。该研究利用载体与底物、中间产物相互作用的差异，通过催化剂中多元组分之间的协同作用，来调控目标产物的选择性，并成功揭示了生物质基精细化学品定向合成的选择性调控规律。.以氨基功能化的铁基MOFs为载体负载金属钯，构建了可见光催化剂，以三乙胺为牺牲性供电子剂、甲酸为质子源、可见光为光源，实现了HMF的选择性光催化转移加氢制备DHMF，其收率高达27%。该光催化反应体系同样适用于糠醛的光催化转移加氢制备糠醇，其收率高达29%。该研究提供了一条绿色、可持续的以太阳能为驱动力催化生物质转化的新途径。.糠醇是一种有机化工原料，而2-甲基呋喃（MF）和2,5-二甲基呋喃（DMF）是一种生物液体燃料。以类水滑石为前驱体构建了铜基催化剂，以甲醇为溶剂和氢源，通过转移加氢反应实现了糠醛高效转化制备糠醇，其收率高达94%。进一步通过调变催化活性中心铜组分的价态、以及催化剂载体的Lewis 酸性还可以实现了糠醛在甲醇介质中一步转移加氢/氢解制备MF，其收率高达94.1%。铜基催化体系同样适用于HMF的一步转移加氢/氢解制备DMF，其收率高达96.7%。该研究发展了无需外加氢气、高效/廉价的铜-甲醇催化体系用生物质分子的转移加氢，还提出了催化活性组分的价态、载体酸性对产物选择性的协同调控机制。