多酸基高維雜化材料的設(shè)計與制備
發(fā)布時間：2018-10-16 16:59
【摘要】：多酸基金屬有機無機高維雜化材料協(xié)同多酸(POMs)與金屬有機配合物(MOFs)的優(yōu)點,具有新穎的結(jié)構(gòu)和優(yōu)異的催化、電化學(xué)、磁性等性能,因此設(shè)計合成多酸基金屬高維雜化材料已成為近年來多酸方向的研究熱點之一。本論文在水熱條件下,通過改變配體的種類,增加配體的位阻,多酸陰離子的種類,反應(yīng)體系的溫度制備了4個以d金屬、柔性乙二胺配體/剛性氮唑配體/柔性雙氮唑配體修飾的多酸基高維雜化材料。通過單晶X-射線衍射,紅外測試(IR),粉末X-射線衍射(PXRD),元素分析(EA)等多種手段對所得晶體材料進行了結(jié)構(gòu)表征,初步研究了其電化學(xué)性質(zhì)。制備材料過程中,考察了反應(yīng)體系的溫度、多酸陰離子種類與金屬的連接方式、有機配體的構(gòu)型及位阻等多種影響因素對多酸雜化材料產(chǎn)物結(jié)構(gòu)的影響,探究了配體的配位點個數(shù)及增加柔性間隔子對產(chǎn)物結(jié)構(gòu)的影響。主要研究結(jié)果如下:1.采用水熱合成技術(shù),向[Cu2(en)2(ox)]2+雙核銅反應(yīng)體系中,引入BW12Keggin多酸陰離子,設(shè)計制備了Cu-en/ox片段修飾的BW12一維雜化材料,該化合物代表首例由柔性有機胺-草酸雙核銅構(gòu)筑的多酸基擴展結(jié)構(gòu)。2.Ag-trz修飾[SiW12O40]4-(SiW12)構(gòu)筑的新穎三維POMOFs雜化材料。水熱反應(yīng)條件下,固定多酸為SiW12,選用1H-1,2,4-triazole-3-carboxylic acid配體(1H-1,2,4-三氮唑-3-羧酸配體,簡稱為tda),通過tda原位脫羧生成triazole配體(1H-1,2,4-三氮唑,簡稱為trz),設(shè)計制備了Ag-trz修飾[SiW12O40]4-(SiW12)構(gòu)筑的新穎三維POMOFs雜化材料化合物2和3。此外,初步的電化學(xué)行為研究結(jié)果表明化合物2的循環(huán)伏安曲線中的峰電流與其掃速呈線性關(guān)系,從而說明該化合物電化學(xué)行為是表面控制過程,電子傳輸速率較快。3.Cu-bpte修飾的[β-Mo8O26]4-(Mo8)三維雜化材料。通過選用位阻較小的Mo8簇、配位模式豐富的Cu離子及多種構(gòu)象的雙三氮唑柔性配體bpte,水熱條件下制備出Cu-bpte修飾的β-Mo8O26多酸基擴展結(jié)構(gòu)4�；衔�4為首例由bpte-Cu-Mo8構(gòu)筑的三維POMOF結(jié)構(gòu)。
[Abstract]:Polyacid-base metal-organic-inorganic high-dimensional hybrid materials have the advantages of coordination of polyacid (POMs) with organometallic complex (MOFs), with novel structure and excellent catalytic, electrochemical and magnetic properties. Therefore, the design and synthesis of polyacid-based metals with high dimensional hybrid materials has become one of the research focuses in the direction of polyacid in recent years. In this paper, four d metals were prepared by changing the type of ligands, increasing the steric resistance of ligands, the kinds of polyacid anions, and the temperature of the reaction system under hydrothermal conditions. Flexible ethylenediamine ligands / rigid azazole ligands / flexible diazazole ligands modified polyacid high dimensional hybrid materials. The structure of the crystal was characterized by single crystal X-ray diffraction and X-ray diffraction of (IR), powder by (PXRD), elemental analysis of (EA). The electrochemical properties of the crystal were preliminarily studied. In the process of preparation, the effects of reaction temperature, the type of polyacid anions and metal, the configuration and steric resistance of organic ligands on the structure of polyacid hybrid materials were investigated. The effects of the number of ligand coordination points and the increase of flexible spacers on the structure of the product were investigated. The main results are as follows: 1. The one-dimensional BW12 hybrid material modified by Cu-en/ox fragment was designed and prepared by introducing BW12Keggin polyacid anions into [Cu2 (en) _ 2 (ox)] _ 2 binuclear copper reaction system by hydrothermal synthesis technique. The compound represents the first polyacid-group expanded structure constructed from flexible organoamine-oxalate binuclear copper. 2.Ag-trz modified [SiW12O40] 4- (SiW12) as a novel three-dimensional POMOFs hybrid material. Under hydrothermal reaction conditions, the fixed polyacids were used as SiW12, ligands (1H-1O2-triazole-3-carboxylic acid ligands) (1H-1O2A4-triazole-3-carboxylic acid ligands), which were called tda), in situ decarboxylation via tda to produce triazole ligands (1H-1O2C2-triazole-3-carboxylic ligands). Ag-trz modified [SiW12O40] 4- (SiW12) novel three dimensional POMOFs hybrid compounds 2 and 3 were designed and prepared by trz), for short. In addition, the preliminary study of electrochemical behavior shows that the peak current in cyclic voltammetry curve of compound 2 is linearly related to its sweep speed, which indicates that the electrochemical behavior of compound is a surface controlled process. 3.Cu-bpte modified [尾-Mo8O26] 4-(Mo8) three-dimensional hybrid materials. The 尾-Mo8O26 polyacid extension structure modified by Cu-bpte was prepared under hydrothermal conditions by using Mo8 clusters with low steric resistance, rich coordination mode Cu ions and a variety of conformational ditriazole flexible ligands, bpte,. Compound 4 is the first three-dimensional POMOF structure constructed by bpte-Cu-Mo8.
【學(xué)位授予單位】：哈爾濱理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4
本文編號：2275041
[Abstract]:Polyacid-base metal-organic-inorganic high-dimensional hybrid materials have the advantages of coordination of polyacid (POMs) with organometallic complex (MOFs), with novel structure and excellent catalytic, electrochemical and magnetic properties. Therefore, the design and synthesis of polyacid-based metals with high dimensional hybrid materials has become one of the research focuses in the direction of polyacid in recent years. In this paper, four d metals were prepared by changing the type of ligands, increasing the steric resistance of ligands, the kinds of polyacid anions, and the temperature of the reaction system under hydrothermal conditions. Flexible ethylenediamine ligands / rigid azazole ligands / flexible diazazole ligands modified polyacid high dimensional hybrid materials. The structure of the crystal was characterized by single crystal X-ray diffraction and X-ray diffraction of (IR), powder by (PXRD), elemental analysis of (EA). The electrochemical properties of the crystal were preliminarily studied. In the process of preparation, the effects of reaction temperature, the type of polyacid anions and metal, the configuration and steric resistance of organic ligands on the structure of polyacid hybrid materials were investigated. The effects of the number of ligand coordination points and the increase of flexible spacers on the structure of the product were investigated. The main results are as follows: 1. The one-dimensional BW12 hybrid material modified by Cu-en/ox fragment was designed and prepared by introducing BW12Keggin polyacid anions into [Cu2 (en) _ 2 (ox)] _ 2 binuclear copper reaction system by hydrothermal synthesis technique. The compound represents the first polyacid-group expanded structure constructed from flexible organoamine-oxalate binuclear copper. 2.Ag-trz modified [SiW12O40] 4- (SiW12) as a novel three-dimensional POMOFs hybrid material. Under hydrothermal reaction conditions, the fixed polyacids were used as SiW12, ligands (1H-1O2-triazole-3-carboxylic acid ligands) (1H-1O2A4-triazole-3-carboxylic acid ligands), which were called tda), in situ decarboxylation via tda to produce triazole ligands (1H-1O2C2-triazole-3-carboxylic ligands). Ag-trz modified [SiW12O40] 4- (SiW12) novel three dimensional POMOFs hybrid compounds 2 and 3 were designed and prepared by trz), for short. In addition, the preliminary study of electrochemical behavior shows that the peak current in cyclic voltammetry curve of compound 2 is linearly related to its sweep speed, which indicates that the electrochemical behavior of compound is a surface controlled process. 3.Cu-bpte modified [尾-Mo8O26] 4-(Mo8) three-dimensional hybrid materials. The 尾-Mo8O26 polyacid extension structure modified by Cu-bpte was prepared under hydrothermal conditions by using Mo8 clusters with low steric resistance, rich coordination mode Cu ions and a variety of conformational ditriazole flexible ligands, bpte,. Compound 4 is the first three-dimensional POMOF structure constructed by bpte-Cu-Mo8.
【學(xué)位授予單位】：哈爾濱理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O641.4
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