一种可循环利用的催化薄膜材料的合成与催化性能研究

In this project, MOFs with high thermal and chemical stabilities are prepared by reactions of carboxylate or imidazole ligands with amino- or phosphorus- group and copper, zinc and zirconium salts under proper conditions to solve the recycle problems of the catalysts. Subsequently, three major approaches, exfoliation and deposition, in situ growth method on the self-assembled organic monolayers (SAMs) and layer by layer growth method (LBL), would be tried to obtain the uniform oriented MOF membranes to improve the efficiency and recyclability of the catalysts for the catalytic condensation, esterification, and dehydrogenation reactions. Particularly internal and external structure information would be gathered by XRD, SEM and AFM, etc. Factors like solvents, temperature and additives would be screened for the standard condition, which would be applied to different substrates. In addition, post-modification can be performed to the MOF membranes to achieve higher selectivity and reactivity of the catalytic reactions, for example, the olefination of the inert C-H bonds. This project has great significance in understanding the role of the MOF membranes in promoting the efficiency and recyclability of the catalysts.

本项目为解决催化剂的回收利用问题，拟通过选择带有氨基、磷基基团的羧酸或咪唑配体与铜、锌、锆等金属盐反应，合成具有高热稳定性、化学稳定性的MOFs材料；在此基础上进一步通过开层-沉积法、SAMs原位生长法和LBL法等方法获得具有高质量、高渗透通量的MOF薄膜材料，以实现缩合、酯化、脱氢等反应过程中催化剂的催化效率的提高和催化剂的回收与循环利用。所获材料的结构和表面特征将通过XRD、SEM、AFM等设备进行表征。通过溶剂、温度、反应时间等因素的调节获得最优反应条件，努力拓展催化剂的应用范围。随后，对MOF薄膜材料进行功能后修饰，以研究催化剂在惰性碳-氢键官能化（如烯烃化等）领域的催化效果和循环利用情况。本项目的研究工作对深入了解MOF薄膜材料在提高催化反应产率，回收催化剂等方面的作用具有重要意义。

在本项目中，我们通过设计合成多种带有多个氨基的咪唑/三氮唑配体，尝试多种合成方法，将其与金属盐结合，合成了一系列具有高热稳定性、化学稳定性的MOFs催化材料，并成功将其应用于气体吸附、有机分子识别、以及惰性二氧化碳气体的固定转化反应等方面。该类催化剂对二氧化碳分子的转化表现出较好的催化活性且反应结束后可回收使用，循环使用五次后催化效率没有明显下降。同时，我们发展了一系列配体促进的三价铑催化的选择性碳-氢键官能化（如芳基化、胺化、硫化等）反应。在本项目的支持下，已发表SCI论文14篇。