多酸基金属—有机骨架复合材料的构筑及其光催化产氢性能研究

发布时间：2018-05-27 15:38

本文选题：多金属氧酸盐 + 金属有机骨架材料　；参考：《东北师范大学》2017年硕士论文

【摘要】：化石燃料被广泛应用于工业生产及日常生活中。但因其不可再生、燃烧会产生许多毒害物质对环境造成污染等诸多弊端,使得人们越来越多的关注太阳能这一新型能源。多金属氧酸盐(POMs)具有优良的结构,可以在化学反应中进行快速的,可逆的,逐步的多电子转移而不改变其结构。因此,越来越多的多金属氧酸盐被应用于光催化水分解领域中。金属有机骨架材料(MOF)是一类有机配体-无机金属/金属簇配位的三维多孔分子材料,因其结构的多孔性和稳定性常作为载体应用于各种光催化反应中。POMs本身具有较高的负电荷,通过将POMs装入稳定的MOF材料中可以对阳离子型MOF材料进行电荷调控,从而得到局部过阴离子化的POMs@MOF复合材料。利用该复合材料吸附阳离子型光敏剂如{Ru(bpy)32+},从而获得具有光催化水分解活性的复合材料。因此,本文结合多金属氧酸盐和金属有机骨架材料二者的优良特性,构筑了一系列阴离子型的Wells-Dawson多酸基金属有机骨架复合材料(WDPOM@MIL-101),并研究了它们的光催化水分解产氢性能。此外,为了证明该方法的有效性和普适性,我们采用金属有机骨架复合材料连续吸附阴离子簇与阳离子的光敏剂{Ru(bpy)32+}进而构筑了具有光催化产氢性能的复合材料(光敏剂@Mo2S12@MIL-101)。该类材料在水溶液中均具有很好的稳定性,可以回收并循环使用,具有广阔的应用前景。主要成果如下:1.设计与合成了一系列WDPOM@MOF复合材料及分子簇基金属有机骨架复合材料,进一步通过ICP,TG,XRD,FTIR,EDX和N2吸附-脱附测试证明不同复合材料的成功合成。(1)P2W17(CoH2O)O61@MIL-101(PW17Co@MIL-101),通过调节不同的多酸担载量,分别获得了多例POM@MOF复合材料:Co-1,Co-2,......Co-7。(2)P2W17(NiH2O)O61@MIL-101(PW17Ni@MIL-101),通过调节不同的多酸担载量,分别获得了多例POM@MOF复合材料:Ni-1,Ni-2,......Ni-7。(3)P2W15V3O62@MIL-101(P2W15V3@MIL-101),通过调节不同的多酸担载量,分别获得了多例POM@MOF复合材料:V-1,V-2,......V-7。(4)Mo2(S2)6@MIL-101(Mo2S12@MIL-101)2.WDPOM@MIL-101复合材料选择性吸附阳离子染料及光敏剂性能的研究对不同染料分子的吸附性能研究表明,WDPOM@MIL-101复合材料可以选择性的吸附阳离子燃料分子,如:亚甲蓝(MB);同时也可以吸附阳离子的光敏剂如:{Ru(bpy)32+}。3.WDPOM@MIL-101与Mo2S12@MIL-101复合材料光催化水分解产氢性能的研究。(1)WDPOM@MIL-101复合材料与WDPOMs光催化水分解产氢性能的比较。在可见光照射8h的条件下,PW17Co@MIL-101(Co-1),PW17Ni@MIL-101(Ni-1),P2W15V3@MIL-101(V-1)复合材料的产氢量是其相应PW17Co,PW17Ni,P2W15V3均相光催化水分解体系提高1.5倍左右,且产氢效果V-1Ni-1Co-1P2W15V3PW17NiPW17Co。(2)Mo2S12@MIL-101复合材料与Mo2S12光催化水分解产氢性能的比较将Mo2S12封装进MIL-101中得到的Mo2S12@MIL-101复合材料,在可见光照射下8 h的产氢的速率高达25578μmol·h-1·g-1,光催化水分解产氢量比均相催化提高约一倍。
[Abstract]:Fossil fuels are widely used in industrial production and daily life. However, because of its non-renewable, combustion will produce a lot of toxic substances to pollute the environment and many other drawbacks, people pay more and more attention to solar energy, a new type of energy. Polyoxometalates (POMs) have excellent structure, which can be used in chemical reactions to carry out rapid, reversible, stepwise multi-electron transfer without changing its structure. Therefore, more and more polyoxometalates are used in the field of photocatalytic water decomposition. Organometallic skeleton material (MOF) is a kind of three-dimensional porous molecular materials coordinated by organic ligands, inorganic metals / metal clusters. Due to its porous structure and stability, it is often used as a carrier in various photocatalytic reactions. By loading POMs into stable MOF material, the cationic MOF material can be controlled by charge, and then the locally over-anionic POMs@MOF composite can be obtained. The composite was used to adsorb cationic Guang Min such as {Ru(bpy)32}, thus the composite with photocatalytic water decomposition activity was obtained. Therefore, a series of anionic Wells-Dawson polyacid-base metal-organic matrix composites (WDPOMMIL-101) have been constructed based on the excellent properties of polyoxometalates and organometallic matrix materials, and their photocatalytic properties for hydrogen production by water decomposition have been studied. In addition, in order to prove the effectiveness and universality of the method, we have constructed a composite with photocatalytic hydrogen production (Guang Min) (Guang Min Mo2S12) MIL-101 by using the metal-organic matrix composite to continuously adsorb anionic clusters and cationic Guang Min agent {Ru(bpy)32}. This kind of material has good stability in aqueous solution, can be recovered and recycled, and has a broad application prospect. The main results are as follows: 1. A series of WDPOM@MOF composites and molecular cluster matrix organometallic matrix composites were designed and synthesized. Further, the successful synthesis of different composites was proved by means of the adsorption and desorption tests of WDPOM@MOF TGN XRDX edX and N2. The successful synthesis of different composites was obtained by adjusting the loading capacity of different polyacids. A number of POM@MOF composite materials: Co-1C Co-2N. Co-7.2U P2W17NiH H 2O O61MIL-101N PW17NiR MIL-101N have been obtained. By adjusting the loading capacity of different kinds of multi-acid, several POM@MOF composite materials, Ni-1T Ni-2N, Ni-7.3P2W15V3O62MIL-101m, P2W15V3MIL-101m, have been obtained, and by adjusting the loading of different polyacids, we have obtained a number of samples of POM@MOF composite materials Ni-1U Ni-2U, Ni-7.3P2W15V3O62MIL-101U, P2W15V3MIL-101M, respectively. The selective adsorption of cationic dyes and Guang Min agents on POM@MOF composites was studied. The results showed that WDPOMERMIL-101 composites could selectively adsorb cationic fuel molecules. The results showed that WDPOMR MIL-101 composites could selectively adsorb cationic fuel molecules. The results showed that WDPOMPLA-MIL-101 composites could selectively adsorb cationic fuel molecules. For example, methylene blue MBF, and also adsorbed cationic Guang Min agents such as: {Ru(bpy)32}. 3.WDPOMMIL-101 and Mo2S12@MIL-101 composite materials for photocatalytic water decomposition of hydrogen production. Comparison between WDPOMMIL-101 composite and WDPOMs in photocatalytic water decomposition of hydrogen production. Under the condition of visible light irradiation for 8 h, the hydrogen production of PW17CoR MIL-101C Co-1C PW17NiNiPOL MIL-101Ni-1OU P2W15V3POL-1) composite is about 1.5 times higher than that of its corresponding PW17CoP17NiP17NiW15V3 homogeneous photocatalytic water decomposition system, and the hydrogen production of P2W15V3 composite is about 1.5 times higher than that of the corresponding PW17CoV PW17NiN P2W15V3 homogeneous photocatalytic water decomposition system. The comparison of the hydrogen-producing effect of V-1Ni-1Co-1P2W15V3PW17NiPW17Co.(2)Mo2S12@MIL-101 composites with that of Mo2S12 in the photocatalytic water decomposition of hydrogen production was made by encapsulating Mo2S12 into MIL-101 composites. Under visible light irradiation for 8 h, the rate of hydrogen production was up to 25578 渭 mol h-1 g-1, and the amount of hydrogen produced by photocatalytic water decomposition was about twice as high as that of homogeneous catalysis.
【学位授予单位】：东北师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;TQ116.2

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