新型硼酸盐及硼钒酸盐的合成、表征与性质研究

发布时间：2018-10-08 21:38

【摘要】：无机-有机杂化材料因具有既能避免无机材料难以修饰的缺陷,也能改善有机材料稳定性和坚固性差的特点,在不同领域得到广泛的关注和应用。硼酸盐是无机微孔材料的分支之一,到目前为止有大量金属硼酸盐被合成出来,一般多用于非线性光学材料和发光材料。与之相比,无机-有机杂化硼酸盐的研究却很少,把有机功能组分引入到硼酸盐体系中,不仅能修饰无机骨架丰富其结构化学,还能得到集无机和有机优良特性于一体的新型材料。近些年,硼钒酸盐因丰富的结构变化和其钒价态的多样性,其在磁学、光学、吸附和催化等方面都有着潜在的应用,受到了人们的广泛关注。硼钒酸盐同时包含B-O基团和V-O基团,预示着更加丰富多彩的结构化学及潜在的应用前景,因此研究者们积极地合成和研究,硼钒酸盐的阴离子结构也已经从分立的零维簇扩展到链、层、网状和三维骨架。虽然多聚硼钒酸盐材料的合成取得了很多进步,但是关于其性质的研究报道的却很少,所以开发此类化合物材料的潜在应用价值也具有非常重要的意义。本论文的主要研究工作为将有机功能组分引入到硼酸盐和硼钒酸盐体系中,合成出具有新颖结构的无机-有机杂化硼酸盐及硼钒酸盐化合物,同时对其结构、稳定性、磁性、荧光和质子传导性质进行了研究。(1)我们采用溶剂热法合成了一种新颖的三维超分子开放骨架结构[Cu_2(bipy)3(B5O7(OH)3)2]?2bipy?4H2O(1)。我们首次将双核铜配合物引入到硼酸盐骨架中,并根据结构特点研究了其性质,变温磁化率结果表明双核铜之间存在弱的反铁磁相互作用;在波长360nm的紫外光激发下,化合物1能发射出紫色的光,最佳发射波长为387nm,并且对爆炸物三硝基苯酚有一定识别效果;结构中存在广泛的氢键,具有一定的质子传导能力。(2)通过水热法成功制备了一个具有新颖结构的硼钒酸盐(enH_2)_4Na_2[V12B18O54(OH)6(H2O)]?7(H2O)(2),其硼钒氧簇通过钠离子连接成二维的层状结构,并在ab面上形成多元孔道,孔道及层和层之间填充着游离的乙二胺和水分子,乙二胺通过氢键将二维层连接起来形成三维超分子骨架结构。通过变温磁化率的测试,发现钒原子之间存在强的反铁磁相互作用,并首次测试了这类材料的质子电导性能,结果表明,其具有与HZSM-5分子筛相当的质子电导能力,为同类材料的性质研究奠定了基础。
[Abstract]:Inorganic-organic hybrid materials have been widely concerned and applied in different fields because they can not only avoid the defects of inorganic materials which are difficult to modify, but also improve the stability and robustness of organic materials. Borate is one of the branches of inorganic microporous materials. Up to now, a large number of metal borates have been synthesized, which are generally used in nonlinear optical materials and luminescent materials. In contrast, there are few studies on inorganic organic hybrid borates. The introduction of organic functional components into borate systems can not only modify the inorganic skeleton to enrich its structural chemistry. A new type of material with excellent inorganic and organic properties can also be obtained. In recent years, boron vanadate has been widely used in magnetism, optics, adsorption and catalysis due to its rich structural changes and the variety of vanadium valence states. Boron vanadates contain both B-O and V-O groups, indicating a more colorful structural chemistry and potential applications, so researchers actively synthesize and study. The anionic structure of boronovanadate has also been extended from discrete zero-dimensional clusters to chain, layer, mesh and three-dimensional skeleton. Although much progress has been made in the synthesis of polyboron vanadate materials, there have been few reports on their properties. Therefore, the potential application value of polyboron vanadate materials is also very important. The main work of this thesis is to introduce organic functional components into borate and borovanadate systems to synthesize inorganic-organic hybrid borates and boron vanadate compounds with novel structure. Fluorescence and proton conduction properties were studied. (1) A novel three-dimensional supramolecular open skeleton structure [Cu_2 (bipy) _ 3 (B5O7 (OH) _ 3) _ 2] was synthesized by solvothermal method. 2bipy? 4H2O (1). The binuclear copper complex was introduced into the borate skeleton for the first time, and its properties were studied according to its structural characteristics. The variable-temperature magnetization results show that there is a weak antiferromagnetic interaction between the binuclear copper complexes, which is excited by ultraviolet light at wavelength 360nm. Compound 1 can emit purple light, the best emission wavelength is 387 nm, and it has a certain recognition effect to the explosive trinitrophenol; there are a wide range of hydrogen bonds in the structure, (2) A novel boron vanadate (enH_2) 4NaSP 2 [V12B18O54 (OH) 6 (H2O)] was successfully prepared by hydrothermal method. 7 (H2O) (2), in which boron vanadium oxide clusters are connected by sodium ions to form a two-dimensional layered structure, and a multicomponent pore is formed on the surface of the ab, filled with free ethylenediamine and water molecules between the pore channels and the layers and layers. Ethylenediamine connects the two-dimensional layers by hydrogen bonding to form a three-dimensional supramolecular skeleton. The strong antiferromagnetic interaction between vanadium atoms was found by the measurement of magnetic susceptibility at variable temperature. The proton conductivity of this kind of materials was tested for the first time. The results show that it has the same proton conductivity as HZSM-5 molecular sieve. It lays a foundation for the study of the properties of similar materials.
【学位授予单位】：吉林大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O613.81

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