Preparation And Application Of Organosilicon Porous Materials Based On BODIPY And Its Analogues

As an important new type of porous materials,organosilicon porous materials have found promising applications such as aerospace,sensors,and pharmaceuticals.In comparison with other porous materials,organosilicon based porous materials have unique advantages.For example,using polyhedral oligomeric sesquisiloxane(POSS)as the monomers,it is easy to construct organosilicon porous materials with high specific surface area and excellent fluorescence property.Using tetrahedral silanes as the monomers,it is easy to build porous materials with ultra-high specific surface area.Although research on organosilicon porous materials has advanced recently,it still lags behind organocarbon porous materials in terms of variety and application range.The exploitation of organosilicon porous materials with new structures and functions remains an important research direction in this field.Therefore,in this thesis,we introduce fluoroboron dipyrrole compounds(BODIPY)unit and its analogue,bifluoroboron dipyrrole compound(BOPHY)into the organosilicon porous network and two new kinds of organosilicon porous materials were prepared.Their applications in dye adsorption and iodine adsorption were explored.The main works are as follows.1.The organosilicon porous polymer BIPOP-1 containing BODIPY units was prepared by Sonogashira reaction using tetrakis(4-ethynylphenyl)silane and dibromo-substituted BODIPY as monomers.BIPOP-1 exhibits high thermal stability and moderate porosity.It was shown that BIPOP-1 exhibited high adsorption performance for various dyes,especially for rhodamine B up to 2207 mg/g,which was higher than most of the dye adsorbents reported so far.The adsorption process of BIPOP-1 for dyes corresponded to the Sips isothermal model as well as the quasi-secondary kinetic model,showing that chemisorption and monolayer and multilayer mixed adsorption were the predominant modes of adsorption.In order to disclose the effects of the organosilicon unit and BODIPY unit,sil icon-free organic porous material BIPOP-2 was prepared using 2,2’,7,7’-tetraethynyl-9,9’-spirobifluorene and dibromo BODIPY and organosilicon porous material CPOP without the BODIPY unit was also prepared using 1,4diethynylbenzene and tetrakis(4-bromophenyl)silane as monomers.The adsorption performance comparison of these polymers reveals that the BODIPY unit was essential for the high adsorption of rhodamine B.The adsorption mechanism was examined using X-ray photoelectron spectroscopy(XPS)and nuclear magnetization techniques.The results showed that the high adsorption performance of BIPOP-1 towards rhodamine B was mainly led by the electrostatic interaction,hydrogen bonding interaction,and pore size fitting of the porous material.BIPOP-1 can also efficiently capture iodine in vapor and organic solutions.These results demonstrated that BODIPY-based porous organosilicon materials can be promisingly utilized as efficient adsorbents for the removal of dye from wastewater or radioactive iodine capture from nuclear contamination.2.The organosilicon porous material BPOP containing BOPHY unit was prepared by the Sonogashira reaction using bis(difluoroboron)-1,2-bis((1H-pyrrol-2-yl)methylene)hydrazine(BOPHY)and tetrakis(4-alkynylphenyl)silane as monomers.BPOP exhibits high thermal stability and high porosity with the specific surface area of 768 m2 g-1.By virtue of the high content of heteroatoms and micropores in the polymers,they can efficiently adsorb and store CO2,with a maximum adsorption capacity of 1.53 mmol g-1(6.73 wt%)at 273 K/101 KPa and a high isosteric heat of adsorption up to 35 kJ mol-1.BPOP can also exhibit high adsorption ability towards various dyes(rhodamine B,congo red,methylene blue,and methyl orange).The adsorption process follows the Langmuir model as well as the quasi-secondary kinetic model,so the adsorption process of dyes by BPOP is mainly monolayer adsorption and chemisorption.These findings imply that BOPHY-based organosilicon porous materials have some promising applications for CO2 capture and dye wastewater treatment.