Design,Synthesis And Application Of Novel Porous Organic Polymers

Porous organic polymers（POPs）are a class of products formed by covalent bonding of organic structural units,which produce pores（cavities,channels or gaps）during the formation process.The POPs have the characteristics of small density and good stability,because the skeleton of the POPs are mainly composed by light elements such as C,H,N,O,B,etc.,which are connected by covalent bonds.In addition,the large number of pore structures formed by the material provides a wide range of contact interfaces for the interaction of the material with external compound.Therefore,these materials have broad application prospects in adsorption,catalysis,optoelectronics and other fields.This topic was started from the structural design of new POPs and guided by functional applications,through screening appropriate chemical reactions and adjusting reaction conditions,three new types of porous organic polymers with novel structures were successfully synthesized in this study.In order to obtain functional POPs,metal ions were loaded on the second and third application platforms through"post modification"strategy,and thus three functional POPs were obtained:AHCP-1;PTBP-1（Fe）,PTBP-2（Fe）,PTBP-3（Fe）;PPOP-3（Ni）,PPOP-4（Ni）.The main research contents of this topic are as follows:1.One of the challenges in water remediation is adsorbent designing,aiming at low cost and ultrafast contaminant adsorption.In the second chapter,we developed a simple and scalable one-pot synthesis method to achieve a cost-effective anionic hypercrosslinked polymer（AHCP-1）through Friedel-Crafts reaction with sodium tetraphenylboron as the monomer.AHCP-1 possessed a high speficic surface area of 939 m²·g^-1 with a micro/mesoporous structure.Owing to the high surfae area,the abundant phenyl groups and the built-in ionic charges,AHCP-1 displayed ultrafast adsorption towards dyes and phenolic derivatives,and a high adsorption capacity of 229.89 mg·g^-1 for RhB and 540.5 mg·g^-1 for BPA.It is also found that the adsorption behavior is dependent on the pollutant concentration,the pH value,and the structure and charge states of the pollutant moecules.2.Efficient and sustainable energy conversion and storage technologies can alleviate the current energy shortages.The design and synthesis of low-cost,high activity and stable electrocatalysts is necessary to break through the bottleneck if we want to achieve this technology.In the third chapter,we injected the porphyrin ring as catalytic sites through the Tr?ger’s base folding structure,and obtained three kinds of expandable PIMs（PTBP-1,PTBP-2,and PTBP-3）.The three materials have excellent structural stability and rich microporous structure.Then,they are modified as catalytic carriers to obtain abundant Fe-porphyrin active sites.The doping of nitrogen atoms can enhance the electrical conductivity of the material,and the abundant micropores formed by the distortion of the structure can serve as an effective channel for small molecule diffusion,so that the catalytic process can be kept uninterrupted.These characteristics give the PTBPs（Fe）excellent OER catalytic performance,especially PTBP-1（Fe）at a current density of 10 mA·cm^-2,the overpotential is 433 mV,and the Tafel slope is only 52.0 mV·dec^-1.At the same time,all three materials exhibit excellent stability and durability.These advantages make PTBPs（Fe）a promising electrocatalyst.3.Two-dimensional（2-D）PPOPs have great potential for energy storage applications because they have not only heteroatom doping,but also abundant pore and layered structure,which can provide abundant redox active sites and ion diffusion paths through 2-D planes and1-D channels.In the fourth chapter,by using phenolic resin synthesis method,TFPP was reacted with two-dimensional phenol to successfully obtain two kinds of two-dimensional functional polymers（PPOP-3 and PPOP-4）with porphyrin ring and phenolic hydroxyl structure.Ni²⁺was then loaded into the porphyrin ring by a"post-modification"strategy to obtain materials with supercapacitor potential（PPOP-3（Ni）and PPOP-4（Ni））.The specific surface areas of the two materials were 194.06 m²·g^-1 and 356.76 m²·g^-1,respectively.Supercapacitor performance studies on two materials show that PPOP-4（Ni）has better performance.When applied as an supercapacitor,it delivers a specific capacitance of 390F·g^-1 at a current density of 1.0 A·g^-1,and both materials exhibited a reversible redox process and excellent stability in 10,000 charge and discharge cycles.