Study On Synthesis And Characteristics Of Novel Porphyrin-based Conjugated Microporous Polymer Materials

Over the past two decades, microporous materials have attracted considerableattention from both the academic and the industrial communities due to their widerange of potential applications in storage, separation, and catalysis. Primarily duringthe past decade, a variety of newer classes of metal-organic frameworks (MOFs),crystalline covalent-organic frameworks (COFs), and amorphous porous organicpolymers (POPs) have been constructed and used in many applications. While POPsarguably are the easiest to make among the three aforementioned classes of materials,they are noncrystalline and have nonuniform pores. Generally speaking, porousorganic polymers have extremely good chemical stability and thermal stability.Herein we demonstrated two novel conjugated microporous polymer frameworkswhich structures were fully characterized and properties were systematicallyresearched.A new porphyrin-based conjugated microporous polymer with rich nitrogen sitesin the skeleton has been synthesized by alkyne-alkyne homocoupling reaction. TheBrunauer-Emmett-Teller specific surface area up to662m2g-1was obtained for thenew polymer framework with a pore volume of0.55cm3g-1. The polymer networkdisplays high carbon dioxide uptake capacity (up to3.58mmol g-1) at273K and1bar, with good selectivity towards CO2over N2and CH4. Furthermore, thisframework also acts as solid organocatalyst towards Knoevenagel reaction ofmalononitrile with aromatic, heterocyclic aldehydes, and cyclic ketone. The reactionafforded the corresponding products in excellent yields (up to99%) with short times.Moreover, the heterogeneous catalyst was also found to exhibit an excellentrecyclability (up to10times) without loss of efficiency.A new metalloporphyrin-based conjugated microporous polymer, NiP-CMP, was constructed via homo-coupling polymerization reaction. NiP-CMP possesses highBET surface area of over2600m2g-1, large pore volume of2.288cm3g-1and as wellas good stability, and display excellent guest uptake of202%in iodine vapour. Wealso highlight that the polymer exhibits outstanding performance in the reversibleadsorption of iodine in solution.