【摘要】：金屬-有機骨架材料(Metal-Organic Frameworks,MOFs)作為一種新型的功能材料,因具有高的比表面積、豐富的拓撲結構、持久性的孔道結構以及可修飾的孔道表面等特點,在氣體儲存、催化劑、吸附分離、傳感等許多領域具有廣闊的應用前景。多重穿插結構的MOFs是金屬-有機骨架材料的重要分支,由于具有穿插結構增強了結構穩(wěn)定性,同時具有高的熱穩(wěn)定性等特點引起人們廣泛關注。目前,將穿插結構的MOFs用于色譜固定相分離的例子很少。本文合成四種穿插結構的MOFs,制備成毛細管柱作為固定相用于氣相色譜分離肉桂、薄荷等香料。1通過溶劑熱法成功合成一種新型四重穿插金屬-有機骨架材料[Ni(pybz)2]·DMF(1),這是一個四重穿插、具有金剛石拓撲結構的MOF,在c方向有一個尺寸為7.6?′7.6?的一維通道。采用動態(tài)涂覆法將其制備成毛細管氣相色譜柱,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,對分離機理進行探討并模擬計算MOF與香料間的范德華力大小。結果顯示:這種固定相對這些香料具有很好分離能力,模擬計算結果與色譜分離結果吻合。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通過水熱法成功合成出兩種四重穿插結構的金屬-有機骨架材料,[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撲結構。這兩個MOFs都是由一個可伸縮的手性“Z”橋連鏈狀配體tmdpy形成3D結構,再自組裝成四重穿插的3D手性MOFs。將它制備成毛細管柱在氣相色譜上成功分離了六組香料。實驗結果表明:這兩種固定相都能將六組香料較好的分離開,但3涂覆的毛細管柱的分離能力比2好。3通過水熱法成功合成出了三重穿插結構的金屬-有機骨架材料[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構。采用動態(tài)涂覆法將它制備成毛細管柱在氣相色譜上成功分離了五組香料。實驗結果表明,該MOF涂覆的毛細管柱對五組不同官能團(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、芳香結構化合物以及環(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：2491406