Preparation And Properties Of Novel Organic Microporous Polymers/carbon Materials

Energy and environment is a main problem in today's society. On the one hand, traditional energy storage is not energy to satisfy with the increasing need of people. We need to develop the new energy resources. On the other hand, in the modern industry, extensive using of coal, oil, natural gas and other fossil fuels can produce a large number of exhaust gas which cause the greenhouse effect is the main gas carbon dioxide. A large number of research results show that the porous material is beneficial to absorb the carbon dioxide, the microporous material become a new material of capturing CO₂, and the porous materials especially the porous carbon, due to its large specific surface area and pore volume, plays an important role in clean energy such as energy storge and supercapacitor. The microporous materials have high specific surface area, excellent physical and chemical stability, low skeleton density, diversity of synthetic methods has a wide range of application in gas adsorption. In recent years, the microporous polymer caused more and more concern of researchers. The past decade has witnessed a rapid development of a wide range of MOPs, such as polymers of intrinsic microporosity ?PIMs?, covalent organic frameworks ?COFs?, conjugated microporous polymers ?CMPs?, and hypercrosslinked porous polymers ?HCPs?.?1? A series of conjugated microporous polymers ?CMPs? based on tetraphenylethylene has been synthesized via Pd-catalyzed Sonogashira-Hagihara reaction. It was found that the homo-coupled polymer network of TPE-CMP1 from 1,1,2,2-tetrakis?4-ethynylphenyl?ethene shows the highest Brunauer-Emmet-Teller specific surface area up to 1096 m2 g^-1 among the resulting polymer networks. TPE-CMP1 exhibits a CO₂ uptake ability of 2.36 mmol g^-1 at 1.13 bar and 273 K with a H2 uptake capacity of 1.35 wt% at 1.13 bar and 77.3 K. All of the polymer networks show high CO₂/N2 selectivity around 30:1 and high isosteric heat of adsorption for CO₂ up to 27.6 kJ mol^-1. Given the facile preparation strategy, the high physicochemical and thermal stability, the high surface area, and the outstanding CO₂ sorption performances, these polymer networks are promising candidates for potential applications in post-combustion CO₂ capture and sequestration technology.?2? A series of isoindigo-based microporous organic polymers from nitrogen- and oxygen-rich 6,6'-dibromoisoindigo and its alkylated derivatives has been synthesized via palladium-catalyzed Sonogashira-Hagihara cross-coupling reaction. The pore properties ?pore size & surface area? of these kinds of microporous polymers could be tuned by the alkyl groups connected with 6,6'-dibromoisoindigo unit. Owing to the incorporation of nitrogen atoms and ketonic groups from the isoindigo unit into the skeleton of the microporous polymers enhanced the interaction between the pore wall and CO₂ molecules, the polymers show high isosteric heats of CO₂ adsorption of 27.4?33.5 kJ mol^-1, which are higher than those of many reported porous aromatic frameworks. Compared with the alkylated polymers of TBMIDM and TBMIDE, TBMID without alkyl group exhibits a high CO₂ uptake ability of 3.30 mmol g^-1?1.13 bar/273 K? with a CO₂/N2 sorption selectivity of 58.8:1. It shows that we choosing the suitable monomer, when we introducing the heteroatomic groups into the polymer skeleton.?3? A series of carbonized materials was obtained using the pyrene-based conjugated microporous polymer as the precursor by high-temperature treatment with potassium hydroxide activation. The material SDBPy-800 shows the highest gravimetric capacitance of 300 F g^-1 at a current density of 1.0 A g^-1 in 3-electrode cell, high rate capability and excellent cycling stability with a capacitance retention of 92.6% after 10000 cycles in 6 M KOH electrolyte. Gas sorption study confirms that these carbon show remarkably high capacities for the adsorption of both H2 and CO₂ up to2.71 wt% for H2 adsorption at 77 K and 1 bar; up to 5.57 and 4.08 mmol g^-1 at 1 bar for CO₂ adsorption at 273 K and 298 K. Given the high surface areas, such high performance as supercapacitor electrode materials and the outstanding gas sorption performances, and the facile preparation strategy, these novel carbon materials show great potential for the development of high capacity carbon-based sorbents for the energy storage applications.