Design,Synthesis And Properties Of Hyper-Cross-Linked Metal-Organic Polyhedra Membranes

Metal–Organic Cage,also known as Metal–Organic Polyhedra?MOPs?,as one of the most popular porous materials in current research,have the traditional properties of porous materials?ordered structure,adjustable pore size,high porosity,good stability,and customizable functionality?.More importantly,the unique solution processability of MOPs makes it easy to react or interact with other materials?such as polymers?to produce high-performance composite materials.Thus MOPs have become the bridge to achieve cooperation between different scientific fields,and play the irreplaceable important role in many applications,such as gas storage or separation,smart sensors,biomedicine,energy conversion,catalysis and so on.Based on the research hotspots of solution chemistry of MOPs,this paper summarizes recent developments of MOPs in the polymer field through pre-synthesis or post-modification.We introduced a new class of hybrid membrane:Hyper-Cross-linked Metal–Organic Polyhedra?HCMOPs?.These membranes are based upon soluble MOPs that can serve as high-connectivity nodes in hyper-cross-linked polymer networks.HCMOPs can spontaneously form macro-scale,defect-free,freestanding membranes with multiple functionalities.This study introduces a new concept for the design and fabrication of multi-functional membranes and also broadens the applications of MOPs.The main contributions in this thesis are as below:1.A series of MOPs with-NH₂ functional groups were designed and synthesized,and their structures were analyzed by single crystal X-ray diffraction.The structures and properties of materials were characterized using PXRD,gas adsorption,UPLC-Q-TOF-MS,UV-vis spectra,¹H NMR and so on.2.A series of HCMOP membranes were fabricated using MOP-1 and MOP-2,the structures and mechanical properties of the membranes were characterized by FT-IR,SEM,EDX,stress-strain testing,and other means.According to its structural characteristics,further researches on the functionality of HCMOP membranes were carried out.Thanks to the positively charged nature of MOPs and the presence of dynamic imine bonds,we found that HCMOP membranes possess excellent selective separation property,self-healing property,shape remodeling property,and antimicrobial activity.We have carried out detailed studies on these properties and proved that the versatile membranes have potential application value in sewage treatment and other aspects.