Preparation And Properties Of New Types Of Metal-organic And Organic Porous Materials

As a new type of porous materials, metal-organic frameworks have drawn a lot ofattentions in recent years and developed rapidly. These materials have a lot of diversetopological structures and specific high surface areas, at the same time there materialshave a broad of potential applications in the gas adsorption separation, sensors,catalysis, proton conduction, drug delivery, and other fields. Meanwhile, as a newtype of porous material, organic porous materials with the introduction of a variety ofsynthetic methods in recent years have greatly developed. Organic porous materialswith unique stabilities, structure diversities and functions have exhibit potentialapplications in gas adsorption separation, catalysis and other fields.In this dissertation, we focused mainly on three aspects from the structural design,synthesis and function application of these materials. The results show that therematerials can both exhibit good stabilities and gas adsorption abilities, especially CO2adsorption performance. The main research results are as follows:1. In the exploration of porous materials, people have pained their efforts in boththe development of novel structures as well as finding of materials with good stabilityto meet the actual usage conditions. Therefore, we selected here relatively stablezeolite like imidazole ester skeleton as the research object, the synthetic strategy iscared here and a new kind of zeolite like materials with GIS topology, namely,Zn4(2-mbIm)3(bIm)5·4H2O (JUC-160) can be obtained with mixed ligand. This is thefirst report of such zeolite like materials with GIS topology with the application of theimidazole ligand containing2-methyl benzene group as the skeleton of the framework.Here, JUC-160has shown excellent thermal stability, the skeleton of JUC-160canremain its thermal stability under the condition of500oC, JUC-160also exhibits theexcellent chemical stability. The skeleton can be well maintained when the samples ofJUC-160was boiling at100oC in the NaOH solution for7days. JUC-160has shownrelatively good adsorption performance toward CO2in the gas adsorption studies. Theselective adsorption studies found that in the mixed component gas, the CO2 selectivity of CO2/CH4is5.6, CO2/O2is28, CO2/N2is65, respectively. The resultshows that JUC-160is a potential carbon capture materials.2. In the exploration of porous materials, peoples have found that the metal-organicframeworks containing zirconium metal clusters have shown relatively good stabilityand performance. We focused here in the development of zirconium containing MOFwith zirconium metal clusters. Through the topology analysis, a new kind of Zr-MOF,Zr6O4(OH)4(TCPS)3(H2O)4, called compound1here, was obtained here with theusage of four nodes four carboxyl tetraphenyl silane tetrahedron acid ligand(tetrakis(4-carboxyphenyl)silane, or TCPS) with zirconium metal clusters(Zr6O4(OH)4). The relative characterization of this Zr-MOF shows that it has excellentthermal stability, relatively good hydrogen adsorption capacity and carbon adsorptionability. The hydrogen adsorption of the Zr-MOF at77K and an atmospheric pressurehas a value of1.73wt%. The carbon dioxide capture experiment under the conditionof atmospheric pressure at273K shows a value of19.8wt%, these results make it apotential hydrogen storage and CO2capture application material.3. The conjugated organic microporous polymers are a kind of porous skeletonmaterials with good stability and other performance, for the first time, we choose tosynthesis conjugated microporous polymers (called compounds2and3polymers here)containing large conjugated pyrene ring monomer by Suzuki reaction. With thecharacterization of these materials and analyze of conjugated nature of compound2and3, we found that the introduction of the condensed ring may help to increase thegas adsorption ability such as hydrogen and carbon dioxide adsorption. The hydrogenadsorption enthalpy of compound2reached8.07kJ/mol, and compound3is7.5kJ/mol, the carbon dioxide adsorption enthalpy of compound2carbon is also biggerthan compound3. This synthetic strategy has promoted us to further synthesisconjugated organic microporous materials with good gas adsorption abilities.4. The idea of introduction of the amino functional group to promote the selectivitycarbon dioxide adsorption ability of metal-organic skeleton materials have beengreatly researched and reported. Here, we tried to introduce amino functional group inthe synthesis of conjugated organic microporous polymer, and compound4without amino group and amino functioned compound5was synthesized here. Through thecontrast of the CO2adsorption enthalpy of the these two materials, we found that thevalue of compound5is nearly10%higher than that of compound4, which provesthat after amination, the CO2adsorption ability of compound5has a greatenhancement, as a result, the idea functionalization of metal-organic skeletonmaterials can be very also used in the conjugated organic microporous polymers.