基于柔性芳香羧酸配体的铝基-有机框架物缓控释合成及选择性气体吸附

The porous aluminium-organic frameworks (Al-PMOFs) with super low framework density have very important potential application in the field of gas absorption and separation. However, there is no suitable assembly strategies for the synthesis of Al-PMOFs and lack of systematic design of the organic ligands, hence its research is still in its starting stage. Our project intends to choose the organic aluminium as the source of aluminium, from which the aluminium ions are released from midbody by slowly control method, and design the modified flexible carboxylate ligands combining with mixed ligand strategy, by using hydrothermal, solvent thermal or microwave techniques to strategically construct Al-PMOFs with high efficiency. Meanwhile, the selective absorption properties of Al-PMOFs will be investigated by the indent of ligand's size and the modified groups's affinity. This research can partially achieve the strategic control in the assembly process of the Al-PMOFs and improve our competitiveness in the designs and synthesis of functional Al-PMOFs keeping of selective gas adsorption function, endowing it a great meaning.

超低框架密度多孔铝基-有机框架物（Al-PMOFs）在气体吸附与分离方面具有重要的潜在应用价值，但当前国内外对其的研究还处于起步阶段，对Al-PMOFs的合成没有合适的组装策略，并缺少对有机配体的系统性开发。本项目拟选用有机铝作为金属铝源，通过中间体缓控释法释放铝离子，设计合成含修饰基团的系列柔性芳香羧酸配体（融合混合配体策略），借助水热、溶剂热与微波辐射技术，避免沉淀实现高效结晶，策略性的构筑Al-PMOFs。同时利用Al-PMOFs中柔性芳香羧酸配体的特性，如修饰基团的亲和力、柔性键的微观可调性以及柔性基团的尺寸等，开发Al-PMOFs的选择性气体吸附性能。本课题研究的展开可以部分实现对Al-PMOFs组装过程的策略性控制，提高我国在设计合成以选择性气体吸附功能为导向的Al-PMOFs的竞争力。

对已报到的MIL系列铝基金属-有机框架物(Al-MOFs)优化合成及衍生氧化铝研究，通过变化有机配体和选择不同的铝源（无机铝源和有机铝源）较大量的合成了铝基-有机框架结构MIL-96，MIL-53，MIL-100和MIL-101等，并且以其为前驱体通过一步热分解制备的多孔Al2O3氧化铝，对MIL-96，MIL-53，MIL-100和MIL-101等前驱体及其产物氧化铝性能表征及比对，研究结果表明产物氧化铝可以较好地保持前驱体的晶态和形貌，但是内部的孔径和气体吸附能力发生了明显的下降。合成了系列具有不同对称性、不同骨架和不同配位官能团的有机配体，使其与过度系列金属离子自组装，得到了11例新型金属-有机配合物，通过合理的表征手段详细表征了其晶体结构，并且对相关结构的拓扑结构、荧光性质，磁性，溶剂识别性能及气体吸附能力进行了测试与表征。本课题研究的展开部分实现了对 Al-MOFs 组装过程的策略性控制，丰富了金属-有机框架物结构的结构类型与性质挖掘，培养了具有配位化学知识能力与经验的研究人才。