【摘要】：金屬-有機(jī)骨架材料(Metal-Organic Frameworks,MOFs)作為一種新型的功能材料,因具有高的比表面積、豐富的拓?fù)浣Y(jié)構(gòu)、持久性的孔道結(jié)構(gòu)以及可修飾的孔道表面等特點(diǎn),在氣體儲(chǔ)存、催化劑、吸附分離、傳感等許多領(lǐng)域具有廣闊的應(yīng)用前景。多重穿插結(jié)構(gòu)的MOFs是金屬-有機(jī)骨架材料的重要分支,由于具有穿插結(jié)構(gòu)增強(qiáng)了結(jié)構(gòu)穩(wěn)定性,同時(shí)具有高的熱穩(wěn)定性等特點(diǎn)引起人們廣泛關(guān)注。目前,將穿插結(jié)構(gòu)的MOFs用于色譜固定相分離的例子很少。本文合成四種穿插結(jié)構(gòu)的MOFs,制備成毛細(xì)管柱作為固定相用于氣相色譜分離肉桂、薄荷等香料。1通過(guò)溶劑熱法成功合成一種新型四重穿插金屬-有機(jī)骨架材料[Ni(pybz)2]·DMF(1),這是一個(gè)四重穿插、具有金剛石拓?fù)浣Y(jié)構(gòu)的MOF,在c方向有一個(gè)尺寸為7.6?′7.6?的一維通道。采用動(dòng)態(tài)涂覆法將其制備成毛細(xì)管氣相色譜柱,在氣相色譜上成功分離了包含醇、醛、酮、酸、酯、醚等的六組香料,對(duì)分離機(jī)理進(jìn)行探討并模擬計(jì)算MOF與香料間的范德華力大小。結(jié)果顯示:這種固定相對(duì)這些香料具有很好分離能力,模擬計(jì)算結(jié)果與色譜分離結(jié)果吻合。這是第一例將四重穿插的MOF做固定相在氣相色譜上分離香料。2通過(guò)水熱法成功合成出兩種四重穿插結(jié)構(gòu)的金屬-有機(jī)骨架材料,[Zn(D.Cam)(tmdpy)]·H_2O(2)和[Cd(D.Cam)(tmdpy)](3),它們有相同的手性金剛石拓?fù)浣Y(jié)構(gòu)。這兩個(gè)MOFs都是由一個(gè)可伸縮的手性“Z”橋連鏈狀配體tmdpy形成3D結(jié)構(gòu),再自組裝成四重穿插的3D手性MOFs。將它制備成毛細(xì)管柱在氣相色譜上成功分離了六組香料。實(shí)驗(yàn)結(jié)果表明:這兩種固定相都能將六組香料較好的分離開,但3涂覆的毛細(xì)管柱的分離能力比2好。3通過(guò)水熱法成功合成出了三重穿插結(jié)構(gòu)的金屬-有機(jī)骨架材料[Ni(D.Cam)(tmdpy)](4),它具有一種罕見的4-連接雙層的單元,它與相鄰的配體tmdpy連接形成三重穿插的三維超分子結(jié)構(gòu)。采用動(dòng)態(tài)涂覆法將它制備成毛細(xì)管柱在氣相色譜上成功分離了五組香料。實(shí)驗(yàn)結(jié)果表明,該MOF涂覆的毛細(xì)管柱對(duì)五組不同官能團(tuán)(R-OH,H-C(R)=O,C(RR’)=O,HO-(R)C=O,R-O-(R’)C=O,R-O-R’)取代的直鏈、芳香結(jié)構(gòu)化合物以及環(huán)烷烴具有良好的分離能力。
[Abstract]:Metal-organic skeleton material (Metal-Organic Frameworks,MOFs), as a new functional material, is stored in gas because of its high specific surface area, rich topological structure, persistent pore structure and modifiable pore surface. Catalysts, adsorption separation, sensing and many other fields have broad application prospects. MOFs with multiple interlaced structures is an important branch of metal-organic skeleton materials. Because of its interlaced structure, it enhances the structural stability and has high thermal stability. At present, there are few examples of using interlaced MOFs for chromatographic stationary phase separation. In this paper, four kinds of interlaced MOFs, were synthesized to prepare capillary column as stationary phase for the separation of cinnamon by gas chromatography. A new type of metal-organic skeleton material [Ni (pybz) 2] DMF (1) was successfully synthesized by solvothermal method, which is a quadruple intercalated MOF, with diamond topological structure. 1. A new type of metal-organic skeleton material [DMF 2] DMF (1) has been successfully synthesized by solvothermal method. There is a size of 7.6 鈮，

本文編號(hào)：2491406