本文選題：多金屬氧酸鹽 + 金屬有機(jī)骨架材料�。� 參考：《東北師范大學(xué)》2017年碩士論文

【摘要】：化石燃料被廣泛應(yīng)用于工業(yè)生產(chǎn)及日常生活中。但因其不可再生、燃燒會(huì)產(chǎn)生許多毒害物質(zhì)對環(huán)境造成污染等諸多弊端,使得人們越來越多的關(guān)注太陽能這一新型能源。多金屬氧酸鹽(POMs)具有優(yōu)良的結(jié)構(gòu),可以在化學(xué)反應(yīng)中進(jìn)行快速的,可逆的,逐步的多電子轉(zhuǎn)移而不改變其結(jié)構(gòu)。因此,越來越多的多金屬氧酸鹽被應(yīng)用于光催化水分解領(lǐng)域中。金屬有機(jī)骨架材料(MOF)是一類有機(jī)配體-無機(jī)金屬/金屬簇配位的三維多孔分子材料,因其結(jié)構(gòu)的多孔性和穩(wěn)定性常作為載體應(yīng)用于各種光催化反應(yīng)中。POMs本身具有較高的負(fù)電荷,通過將POMs裝入穩(wěn)定的MOF材料中可以對陽離子型MOF材料進(jìn)行電荷調(diào)控,從而得到局部過陰離子化的POMs@MOF復(fù)合材料。利用該復(fù)合材料吸附陽離子型光敏劑如{Ru(bpy)32+},從而獲得具有光催化水分解活性的復(fù)合材料。因此,本文結(jié)合多金屬氧酸鹽和金屬有機(jī)骨架材料二者的優(yōu)良特性,構(gòu)筑了一系列陰離子型的Wells-Dawson多酸基金屬有機(jī)骨架復(fù)合材料(WDPOM@MIL-101),并研究了它們的光催化水分解產(chǎn)氫性能。此外,為了證明該方法的有效性和普適性,我們采用金屬有機(jī)骨架復(fù)合材料連續(xù)吸附陰離子簇與陽離子的光敏劑{Ru(bpy)32+}進(jìn)而構(gòu)筑了具有光催化產(chǎn)氫性能的復(fù)合材料(光敏劑@Mo2S12@MIL-101)。該類材料在水溶液中均具有很好的穩(wěn)定性,可以回收并循環(huán)使用,具有廣闊的應(yīng)用前景。主要成果如下:1.設(shè)計(jì)與合成了一系列WDPOM@MOF復(fù)合材料及分子簇基金屬有機(jī)骨架復(fù)合材料,進(jìn)一步通過ICP,TG,XRD,FTIR,EDX和N2吸附-脫附測試證明不同復(fù)合材料的成功合成。(1)P2W17(CoH2O)O61@MIL-101(PW17Co@MIL-101),通過調(diào)節(jié)不同的多酸擔(dān)載量,分別獲得了多例POM@MOF復(fù)合材料:Co-1,Co-2,......Co-7。(2)P2W17(NiH2O)O61@MIL-101(PW17Ni@MIL-101),通過調(diào)節(jié)不同的多酸擔(dān)載量,分別獲得了多例POM@MOF復(fù)合材料:Ni-1,Ni-2,......Ni-7。(3)P2W15V3O62@MIL-101(P2W15V3@MIL-101),通過調(diào)節(jié)不同的多酸擔(dān)載量,分別獲得了多例POM@MOF復(fù)合材料:V-1,V-2,......V-7。(4)Mo2(S2)6@MIL-101(Mo2S12@MIL-101)2.WDPOM@MIL-101復(fù)合材料選擇性吸附陽離子染料及光敏劑性能的研究對不同染料分子的吸附性能研究表明,WDPOM@MIL-101復(fù)合材料可以選擇性的吸附陽離子燃料分子,如:亞甲藍(lán)(MB);同時(shí)也可以吸附陽離子的光敏劑如:{Ru(bpy)32+}。3.WDPOM@MIL-101與Mo2S12@MIL-101復(fù)合材料光催化水分解產(chǎn)氫性能的研究。(1)WDPOM@MIL-101復(fù)合材料與WDPOMs光催化水分解產(chǎn)氫性能的比較。在可見光照射8h的條件下,PW17Co@MIL-101(Co-1),PW17Ni@MIL-101(Ni-1),P2W15V3@MIL-101(V-1)復(fù)合材料的產(chǎn)氫量是其相應(yīng)PW17Co,PW17Ni,P2W15V3均相光催化水分解體系提高1.5倍左右,且產(chǎn)氫效果V-1Ni-1Co-1P2W15V3PW17NiPW17Co。(2)Mo2S12@MIL-101復(fù)合材料與Mo2S12光催化水分解產(chǎn)氫性能的比較將Mo2S12封裝進(jìn)MIL-101中得到的Mo2S12@MIL-101復(fù)合材料,在可見光照射下8 h的產(chǎn)氫的速率高達(dá)25578μmol·h-1·g-1,光催化水分解產(chǎn)氫量比均相催化提高約一倍。
[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.
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;TQ116.2

【參考文獻(xiàn)】

相關(guān)碩士學(xué)位論文 前1條

1 王真理;多金屬氧酸鹽可見光催化產(chǎn)氫活性的研究[D];東北師范大學(xué);2012年

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本文編號：1942740