Trivalent Metal Organic Frameworks And Microporous Organic Polymers: Synthesis,catalysis And Absorption

The development and synthesis of microporous material are hot topic in the field of material science.As important components of microporous materials,metal organic frameworks（MOFs）and microporous organic polymer have attracted more and more attention due to their large specific surface area,the diversity of the synthetic method and easy to introduce the functional groups,and exhibited potential or actual applications in the field of the gas adsorption and separation,catalysis and sensor.In this work,the design and synthesis of trivalent metal organic frameworks have been studied along with their properties in catalysis and luminescence.Moreover,through the rational design of functional monomers,new super-crosslinked organic polymers were synthesized and their adsorption properties for CO₂ and organic dye molecules in water phase were studied,respectively.The important contents of this article are as follows:1.We studied the catalytic activities of the In-MOF and MIL-53 series catalysts in the Strecker reaction between imines and TMSCN,and investigated the effects of metal centers,frameworks and substituted groups on the catalytic reactions.The experimental results showed that the catalyst In-MOF could efficiently catalyzed the Strecker reaction between N-Bn imines and TMSCN.Moreover,catalyst In-MOF could be isolated from the reaction system with simple filtering method,and it could be reused three times without the loss of the activity.The MIL-53 series showed moderate to excellent catalytic activity on the Strecker reactions between N-Bn protected imines and TMSCN.Among them,NH₂-MIL-53（Sc）with the Lewis acid-base bifunctional centers showed higher conversions than other catalysts.2.2D layered In-MOF 1 and 3D Ln-MOFs 2-Ln（Ln=Eu,Tb,Er）were synthesized based on semi-rigid H₂L under hydrothermal conditions.It is worth noting that H₂L showed different coordination modes in the resulting frameworks.In In-MOF 1,hydrogen-bond interactions between the layer and free H₂O,for instance,O–H…Cl and O–H…O,link 2D entities to 3D frameworks.By adjusting the co-doping ratio of Eu³⁺and Tb³⁺ions into the same framework as that of 2,we successfully designed and constructed a series of 2-Eu_1-xTb_x（x=0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1）,the photoluminescence color of that can be tuned from green to yellow and red by varying the doping concentration of the Eu³⁺ion.3.Using two big rigid monomers M3 and M4 as building units,FDA as crosslinking agent,three hyper-crosslinked polymers（HCPs）have been synthesized via Friedel-Crafts alkylation reaction promoted by anhydrous FeCl₃.HCPs 1 and 2showed good CO₂ capture capacity which coould be attributed to the introduction of polar hydroxyl and lactam groups into the sekelton of the polymer which provided effective adsorption sites for CO₂.Moreover,HCP 3 also showed good CO₂absorportion capacity.In addition,they all exhibited good adsorption capacity for organic dyes in water.Thus,combined with their advantages,such as low cost,easy avialability,good thermal stability and water resistance,these HCPs could be considered as potenitial absorbants for applications in the field of clean energy and environmental issues.