| The main chain of polymers of intrinsic microporosity（PIMs）combines a rigid and twisted conformation that makes it difficult to stack molecular chains in a regular manner and thus has a high specific surface area and interconnected micropores,while the non-cross-linked structure makes them more soluble in common organic solvents.Although these materials have been widely used in gas separation membranes and ion conduction membranes and have shown excellent performance,the single material morphology and pore structure have limited their functions and applications.Hence,in this research,we propose to functionalize polymers of intrinsic microporosity（PIM-1）with specific morphology and functional groups,and apply them to dye adsorption,supercapacitor and photothermal energy storage according to their characteristics,and analyze the relationship between structure and performance in detail.The main contents of this research are as follows.（1）A facile electrospray technique combining breath figure（BF）or nonsolvent induced phase separation（NIPS）was developed to prepare hierarchically porous microparticles with various morphologies based on polymers of intrinsic microporosity（PIM-1）.The relationship between the ternary system composition of the electrospraying（PIM-1 and cosolvent）and the microparticle architectures（morphology and pore structure）was carefully investigated.The as-prepared PIM-1 microparticles possess predominant micropores and abundant macropores with high surface areas in range from 548 m2 g-1 to 747 m2 g-1.Their adsorption capacities for CO2 and organic dye were facilitated by the generation of macropores,owing to the increased accessibility of isolated micro-mesopores.More importantly,they perform enhanced selective adsorption abilities towards malachite green（MG）for the methyl orange/MG mixture pairs.（2）Concave-belly-bowl-like carbons（CBCs）with micro-meso-macroporous structures were fabricated by direct carbonization of the electrosprayed polymer microparticles without any assistant reagents.Those microparticles were prepared by the electrospraying of polymers of intrinsic microporosity（PIM-1）.The morphologies of CBCs were maintained under different carbonization conditions,and the graphitization degrees and specific surface areas（SSAs）of CBCs enhance with the increase of the carbonization temperature.Specially,CBC-900 obtained at the carbonization temperature of 900 oC possesses the highest graphitization degree of 2.38and the largest SSAs of 1618.0 m2 g-1.CBC-900 also shows high specific capacitance of 174.8 F g-1 at 0.5 A g-1 in 1 M H2SO4 electrolyte and robust cycling property with almost 100%capacitance efficiency at 10 A g-1 under 5000 cycles.Moreover,CBC-900 performs an energy density of 5.08 W h kg-1 at the power density is 250.00 W kg-1.（3）Small molecules of azo-benzene were designed and synthesized,and then the small molecules of azo-benzene were used as synthetic monomers to synthesize azo-benzene polymers using polymers of intrinsic microporosity PIM-1 as a template.The chemical structures of the small molecule azo-benzene,azo-benzene polymers azo-PIM-1/9 and azo-PIM-1/3 were characterized by FT-IR and 1H NMR,which proved the successful synthesis of the corresponding azo-benzene molecules.The photoisomerization properties of the small molecules azo-benzene,azo-benzene polymers azo-PIM-1/9 and azo-PIM-1/3 were investigated by UV-vis absorption spectroscopy under solvent assistance.Finally,the energy densities of small molecule azo-benzene,azo-benzene polymers azo-PIM-1/9 and azo-PIM-1/3 after charging were measured by differential scanning calorimetry as 140.50 J g-1,13.39 J g-1 and 36.75 J g-1,respectively.Subsequently,in order to improve the utilization of photons during the photoisomerization of azobenzene to increase the energy storage density of azobenzene polymers,hierarchical pore azobenzene particles were considered to be prepared by electrospraying of azobenzene polymers. |
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