Porphyrin-Containing Porous Aromatic Frameworks: Design,Synthesis And Characterization

In rencent years,Porous Organic Frameworks?POFs?as a new class of porous materials,which are constructed by pure organic building blocks through covalent bond,have been rapidly developed.Lots of advantages have been found in these materials,such as high surface area,high stability,tunable pore size and controllable functional groups.Furthuremore,POFs have been widely applied in a variety of fields such as gas storage and separation,organic catalysis,energy storage and transmission because of their excellent properties.As a class of important bionic materials,Porphyrins with excellent properties have been studied by researchers with great interest in the fields of bionic and optoelectronics.This paper is focus on the design and synthesis of porphyrin-contained aromatic porous materials.The properties and potential applications of these materials in gas storage and separation,organic catalysis and electrochemical oxygen evolution electrocatalytic hydrogen production are comprehensive studied.Firstly,PAF-40 was synthesized based on tetraphenylporphyrin via Schrall reaction catalyzed by AlCl₃.PAF-40-Fe and PAF-40-Mn were synthesized based on tetraphenylporphyrin-Fe and tetraphenylporphyrin-Mn via the same polymerization.The effects on the surface area and gas adsorption separation properties of the materials coused by the introduction of different metal ions were investigated.The small alkanes gas adsorption tests of C2 and C3 were carried out on these materials,and the separation ratios of C2 and C3 to CH4 were calculated by IAST.The results show that the PAF-40 s have a high gas adsorption capacity and an excellent gas separation ratios.Secondly,PAF-76 was synthesized based on tetrabenzyltetraboron and tetrabromotetraphenylporphyrin via Suzuki coupling reaction.The same method was used to synthesize PAF-76-Mn,PAF-76-Mn and PAF-76-Zn with tetrabromotetraphenylporphyrin-Fe,tetrabromotetraphenylporphyrin-Mn and tetrabromotetraphenylporphyrin-Zn.Due to the enrichment of single and highly dense metal sites in the microporous skeleton,PAF-76 s show excellent catalytic properties including the high conversion rates of styrene and the high selectivity to the product of phenylacetaldehy.The PAF-76 s exhibit high thermal stability,good recyclability and excellent durability of the solvent,further demonstrating their excellent heterogeneous catalytic abilities.Finally,PAF-77 and PAF-78 were synthesized based on tetramethyltetraphenylporphyrin,5,10-bis?4-aminophenyl?-10,20-diphenylporphyrin and 1,3,5-terephthalo-phloroglucinoluse via Schiff base reaction,and then PAF-77-Co and PAF-78-Co were synthesized by introducing Co ion complexation with porphyrin skeleton.Due to the different skeleton in pore volume,pore size and the introduction of metal ions,PAF-77 and PAF-78 show excellent electrochemical catalytic properties.A trend of PAF-78-Co> PAF-77-Co> PAF-78> PAF-77 were found by comparing the results of electrochemical test of LSV and Tafel slope effect.These materials show excellent oxygen evolution stabilities in 0.5 M H2SO4?pH = 1?solution and 1M NaOH?pH = 14?solution.