Design,Synthesis And Properties Of Azo And Triazine Based Porous Organic Frameworks

Porous organic polymers materials have been intensively investigated during the last few decades due to their exceptionally high BET surface area,good stability and structure adjustability,feasibility of grafting reactive functional groups at the pore surface and a wide diversity of framework compositions.They have found a huge potential for application in selective gas adsorption,heterogeneous catalysis,electrochemistry,sensors,biochemistry and so on.Herein,two novel porous organic frameworks of azo and triazine have been designed and synthesized.We aim to investigate the porosity properties,selective gas adsorption,supercapacitor performance and exploration of CO₂ conversion.First,We use the 2,6,14-Triaminotriptycene with three-dimensional structure and tri/diphenols to obtain two three-dimensional structures of azo frameworks?HAzo-TB-1and HAzo-TB-2?.The frameworks with hierarchical porous structures were synthesized via a simple diazo-coupling reaction in aqueous solution under mild conditions.The surface areas of HAzo-TB-1and HAzo-TB-2 are 800.41m²g^-11 and 788.4 m²g^-1,displaying excellent CO₂uptake abilities and good adsorption selectivity for CO₂ over N₂.The value of CO₂ storage are14.05 wt%and 13.585wt%for HAzo-TB-1 and HAzo-TB-2 at 273 K and 1 bar,respectively.Moreover,the IAST of the frameworks toward CO₂ over N₂ are 108 and 55.The integration of azo and phenolic-OH can give frameworks the ability to chelate with metal ions.These frameworks complexed with Zn show excellent performance for catalyzing the reaction of CO₂ with epoxide,affording a TOF of 3100 h^-1.Second,a serious of novel covalent thiazine frameworks?CTFs?were prepared by trimerization of di?4-cyanophenyl?ethyne?DCPE?in molten ZnCl₂ under ionothermal conditions.The influence of several parameters such as the ZnCl₂/monomer ratio and reaction temperature on the structure and porosity of the resulting frameworks was systematically examined.Notably,the CTF-DCE-5-600 has the highest BET and pore volume(2125.7 m²/g and 1.14 cm³ g^-1).Besides,we systematically study the relationship between the BET,pore structure,and the adsorption of CO₂ and H₂.Compared with others CTF-DCEs,the CTF-DCE-5-400 has the highest adsorption for CO₂ and H₂ in 1 bar,the value of CO₂ storage can reach up to 103 and 64 cc/g at 273 K and 298 K;the H₂ adsorption capacities is 211cm³g^-1 and 155 cm³g^-1 at 77K and 87K,respectively.Based on its good adsorption performance,we study the adsorption of dyes.The studies show that the adsorption amount of CTF-DCE-5-600 for dye MO is 1270 mg/g.Besides,the materials also perform good supercapacitor performance.The researches show that CTF-DCE-5-600 has the largest specific capacitance?303F/g?,indicating good application in supercapacitors.