朱廣山+卜顯和+孫福興+常澤+景曉飛
摘 要:目前,性能優(yōu)異的有機多孔材料已經(jīng)成為多孔材料研究領(lǐng)域的熱點及前沿問題。多孔共價有機框架材料作為一種新型的多孔材料,在結(jié)構(gòu)和性質(zhì)調(diào)控方面比傳統(tǒng)的分子篩和MOFs材料更加靈活?,F(xiàn)階段,國內(nèi)外關(guān)于有機多孔材料方面的研究集中在實驗合成方法、材料在氣體儲存及作為催化劑載體等方面。雖然有機多孔材料具有高穩(wěn)定性(熱穩(wěn)定性及化學(xué)穩(wěn)定性)、較大的比表面積,但是在氣體吸附(特別是在氫氣儲存方面)并沒有表現(xiàn)出優(yōu)異的性能。該課題組報道的PAF-1在77 K,48 bar下氫氣儲存質(zhì)量百分?jǐn)?shù)7 wt%,是有機多孔材料在氫氣儲存上最高的,同樣也處于一系列多孔材料在氫氣儲存方面的前列。目前有機多孔材料的構(gòu)筑基元多為具有剛性結(jié)構(gòu)的多節(jié)點單體。由于材料的結(jié)構(gòu)特點影響其性能,在已知報道的基礎(chǔ)上,可以利用有機單體的多樣性特點,在特定的聚合反應(yīng)中引入可官能化的單體,這樣就可以豐富有機多孔材料的結(jié)構(gòu),引入的官能團也可以有效地改變材料的性能,同時也利于材料在后修飾方面的開發(fā)應(yīng)用。目前,雖然有機多孔材料在局部結(jié)構(gòu)上具有一定的有序性,但是它們長程無序?qū)е逻@類材料大多是無定形的,制備可以分析結(jié)構(gòu)的結(jié)晶有機多孔材料也是研究的熱點及前沿性問題。該課題將在已有積累的基礎(chǔ)上,探索共價有機多孔材料的設(shè)計合成、結(jié)構(gòu)調(diào)控以及與儲氣、分離、純化等功能性之間的關(guān)聯(lián)規(guī)律,尋找提高儲氣、分離材料各項性能指標(biāo)的關(guān)鍵因素,以期獲得新型高性能的多孔有機固體儲氣材料、分離材料。具體研究內(nèi)容包括:(1)計算機理論模擬作為開展有機框架多孔材料研究的指導(dǎo);(2)有機結(jié)構(gòu)基元的設(shè)計與合成;(3)選擇合適的制備有機框架多孔材料的聚合反應(yīng)類型;(4)有機框架多孔材料的功能化探索。期望通過5年的研究,可以通過對材料的官能化,改變材料的性能,使材料在與能源及環(huán)境息息相關(guān)的領(lǐng)域,包括氫氣、二氧化碳、甲烷儲存及有機分子污染物吸附方面產(chǎn)生很好的應(yīng)用前景。
關(guān)鍵詞:有機多孔材料 氣體吸附 孔框架化合物
Abstract:Currently, porous organic frameworks (POFs) has become a hot research field of porous materials. As a new type of porous material, their structure and nature of regulation are more modifiable than zeolites and metal-organic frameworks. At present, researches is concentrated in the experimental synthesis methods, their gas storage and catalysis properties. Although porous organic material have a high stability (thermal and chemical stability) and large specific surface area, they did not exhibit superior performance in the gas adsorption. Our research group reported PAF-1 at 77 K, 48 bar with a hydrogen storage of 7 wt%, the highest hydrogen storage among the porous organic materials, also at the forefront of the whole porous materials. Current organic monomers to construct the porous organic materials are mostly rigid. On the basis of the known report, we can use the characteristics of the diversity of organic monomers, in particular those may be introduced functional groups in the polymerization. And the introduction of functional groups can effectively change their gas adsorption properties. On the other hand, currently, although some of the porous organic materials have a partial order on the structure, they lead to long-range disorder. Crystalline porous organic materials whose structures can be analyzed are also the hot research frontier issues. This project will be on the basis of the existing accumulated results, and explore the design and synthesis of porous organic frameworks, study the association between the structural features and the properties of gas storage, separation and purification, look to the key factors to improve the gas storage and separation properties of various materials, and obtain porous organic materials with high performance of gas storage and separations. Specific studies will include: (1)computer simulation as the guiding to carry out organic porous materials research; (2)design and synthesis of organic monomers as building blocks; (4)select the type of polymerization reaction which are suitable for preparing the targeted organic porous materials; (4)explore the functions of these porous materials. It is expected, through five-year research, we can obtain a series of porous organic frameworks which have good potential applications in the energy and environmental fields, including the storage of hydrogen, carbon dioxide, and methane and the adsorption of pollutants products through the structure modification.
Key Words:Porous organic frameworks; Gas storage; Structure modification
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