层状化合物高效制备金属有机框架材料的机理研究

Solving the challenge of scalable production is key to realizing the industrial applications of metal-organic frameworks (MOFs). Traditional solvothermal methods often require high reaction temperature, high pressure, and long reaction time. Consequently, it is still very difficult to develop processes for large production of MOFs. New synthesis routes enabling facile MOF production are therefore highly desired. We have reported for the first time that layered compounds can be rapidly converted to MOFs at room temperature. Recent studies have also shown that this strategy has ultra-high space-time yield (STY), general applicability and low energy requirement. These advantages make it very promising for scalable production and industrial applications of MOF materials. However, current research efforts have not yet systematically explored the mechanism of the conversion reaction from layered compounds to MOFs. Much is still unknown for the critical factors that affect the conversion and the STY. Therefore, we propose to study the mechanism and kinetics of this facile synthesis reaction. We will investigate the mass transfer and reaction process of different organic ligands in the interlaminar space within the layered compounds, and find the key factors for enhancing the conversion and the STY. This proposed research project has great significance in guiding the development of new facile synthesis routes for MOFs and realizing scalable production for MOF materials.

金属有机框架（MOF）材料的宏量制备是实现MOF工业应用所需要解决的核心问题。传统的溶剂热法因其合成时间较长、反应温度和压力较高等缺点，难以实现工艺放大，因此开发高效合成的新方法对实现MOF宏量制备具有十分重要的意义。由申请者首次提出的层状化合物转化法，实现了室温条件下MOF材料的快速制备。近期的多项研究表明该方法具有空时产率高、普适性好、能耗低等优点，有望实现MOF的宏量制备、推动MOF的工业应用。然而目前对该合成反应的机理还缺乏系统的研究，影响其转化率、空时产率的主要因素仍有待确定。因此，申请者拟通过多种原位表征手段，研究层状化合物转化生成MOF的机理及反应动力学；通过研究不同有机配体阴离子在层状化合物中的迁移、反应过程，分析影响该反应转化率及空时产率的关键因素。本项研究对进一步拓展高效制备MOF的方法、实现MOF材料宏量制备有重要的科学意义。

层状化合物转化法可实现室温条件下金属有机框架(MOF)材料的快速制备，具有空时产率高、普适性好、能耗低等优点，能克服传统的溶剂热法合成时间长、反应温度和压力高的缺点，有望推动MOF材料的宏量制备和工业应用。然而目前对层状化合物转化合成MOF的反应机理还缺乏系统的研究，影响其转化率、产物结构与性能的主要因素仍有待确定。本项目借助多技术联用表征方法，研究了层状化合物通过溶液相和气固相反应转化生成MOF材料的机制。以双金属碱式盐(HDS)为层状化合物模型，发展了一系列制备具有混合金属节点的MOF(mmMOF)材料的新方法，获得了多种金属比例可控、晶型可调的双金属类沸石咪唑骨架(ZIF)结构。开发了一系列双金属MOF粉体、薄膜和复合材料，探索了双金属MOF材料在流式质谱细胞术标签材料、气体膜分离材料中的应用。