稀土金属有机骨架化合物的合成、结构、光催化及磁性研究
发布时间：2019-03-05 16:03
【摘要】：金属有机骨架化合物(Metal-Organic Frameworks,MOFs)具有较大的比表面积且兼具结构可设计、功能可调控等特点,近些年来在气体吸附、荧光、催化、和光电磁等方面展现了其巨大的应用优势。其中基于镧系金属的Ln-MOFs,鉴于自身特殊的4f电子层结构,相比于过渡态金属离子构成的MOFs而言具有更高的配位数以及更加丰富的配位模式,受到人们广泛重视。本论文分别利用蒽基官能化的二羧酸有机配体桥连稀土离子(Ce3+,Tb3+,Dy3+),草酸配体连接稀土(Dy3+)离子簇,在溶剂热/水热条件下配位构筑出具有新颖结构特色和不同性质的系列新型稀土金属有机骨架化合物。通过单晶X-射线衍射、粉末X-射线衍射、紫外、荧光、热重、红外、表面光电压(SPV)、电化学和磁性测试等表征手段对所制备Ln-MOFs化合物的结构和物理化学性质进行表征,探索了所制备不同Ln-MOFs作为可见光催化剂催化降解水中有机染料的性质及单分子磁行为。具体内容如下:1、利用蒽基二羧酸配体(H2L)与Ln系离子(Ce3+,Tb3+,Dy3+)配位成功合成了系列新型Ln-MOFs NNU-15(Ce,Tb,Dy)并对它们物理化学性质进行测试。稳态吸收光谱显示该系列化合物均在可见光区展示出较宽的吸收带,表面光电压测试也表明该系列Ln-MOFs在可见光下可有效生成界面光生电荷,可以作为光催化剂进行可见光驱动化学反应。我们对该系列MOFs在可见光下催化降解有机染料进行了实验探究。实验数据表明,在氧化性物质H2O2的存在下,该系列化合物可作为较好的光催化剂进行有机染料降解。本工作是少数使用Ln-MOFs化合物对有机染料在可见光条件下进行光催化降解的研究,扩展了Ln-MOFs材料在可见光催化降解有机染料方面的应用。2、利用低成本草酸为配体与Ln系金属离子Dy3+配位,成功合成了一例具有新颖结构特征的三维Dy-MOF([Dy4(OH)4(ox)5]·2H3O·11H2O)。该化合物中存在极少报道的Cubane-like四核Dy簇,可能存在有趣的磁性质。磁性测试表明该化合物表现出单分子磁体行为。
[Abstract]:Organometallic framework compounds (Metal-Organic Frameworks,MOFs) have the characteristics of large specific surface area, structural design and functional regulation. In recent years, they have been used in gas adsorption, fluorescence, catalysis, and so on. And optical electromagnetism and so on have shown its huge application superiority. Among them, lanthanide-based Ln-MOFs, has higher coordination number and richer coordination mode than transition metal ions in view of its own special 4f electron layer structure, so it has been paid more attention to. In this paper, the rare earth ions (Ce3, Tb3, Dy3) were bridged by anthracene functionalized dicarboxylic acid organic ligands, and the rare earth (Dy3) ion clusters were connected by oxalic acid ligands. A series of novel rare earth metal organic framework compounds with novel structural characteristics and different properties were synthesized by coordination under solvothermal / hydrothermal conditions. Single crystal X-ray diffraction, powder X-ray diffraction, ultraviolet, fluorescence, thermogravimetric, infrared, surface photovoltage (SPV), The structure and physicochemical properties of the prepared Ln-MOFs compounds were characterized by electrochemical and magnetic measurements. The properties and monomolecular magnetic behavior of different Ln-MOFs as visible light catalysts for degradation of organic dyes in water were investigated. The main contents are as follows: 1. A series of novel Ln (Ce,Tb,Dy) were synthesized by coordination of anthracarboxylic acid ligand (H2L) with Ce3, Tb3, Dy3, and their physicochemical properties were tested. The steady-state absorption spectra show that the series of compounds exhibit wide absorption bands in the visible light region. The surface photovoltage measurements also show that the series of Ln-MOFs can effectively generate light-generated charges at the interface under visible light. It can be used as photocatalyst for visible light-driven chemical reaction. This series of MOFs catalyzes the degradation of organic dyes under visible light. The experimental data show that these compounds can be used as photocatalysts for degradation of organic dyes in the presence of H2O2. This work is a few studies on the photocatalytic degradation of organic dyes under visible light using Ln-MOFs compounds, which extends the application of Ln-MOFs materials in visible light catalytic degradation of organic dyes. A novel three-dimensional Dy-MOF ([Dy4 (OH) 4 (ox) 5] 2H3O 路11H2O) was successfully synthesized by using low cost oxalic acid as ligand to coordinate with Ln metal ion Dy3. There are few reported Cubane-like quaternary Dy clusters in this compound, which may have interesting magnetic properties. Magnetic tests show that the compound exhibits monomolecular magnet behavior.
【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】：O641.4
本文编号：2435077
[Abstract]:Organometallic framework compounds (Metal-Organic Frameworks,MOFs) have the characteristics of large specific surface area, structural design and functional regulation. In recent years, they have been used in gas adsorption, fluorescence, catalysis, and so on. And optical electromagnetism and so on have shown its huge application superiority. Among them, lanthanide-based Ln-MOFs, has higher coordination number and richer coordination mode than transition metal ions in view of its own special 4f electron layer structure, so it has been paid more attention to. In this paper, the rare earth ions (Ce3, Tb3, Dy3) were bridged by anthracene functionalized dicarboxylic acid organic ligands, and the rare earth (Dy3) ion clusters were connected by oxalic acid ligands. A series of novel rare earth metal organic framework compounds with novel structural characteristics and different properties were synthesized by coordination under solvothermal / hydrothermal conditions. Single crystal X-ray diffraction, powder X-ray diffraction, ultraviolet, fluorescence, thermogravimetric, infrared, surface photovoltage (SPV), The structure and physicochemical properties of the prepared Ln-MOFs compounds were characterized by electrochemical and magnetic measurements. The properties and monomolecular magnetic behavior of different Ln-MOFs as visible light catalysts for degradation of organic dyes in water were investigated. The main contents are as follows: 1. A series of novel Ln (Ce,Tb,Dy) were synthesized by coordination of anthracarboxylic acid ligand (H2L) with Ce3, Tb3, Dy3, and their physicochemical properties were tested. The steady-state absorption spectra show that the series of compounds exhibit wide absorption bands in the visible light region. The surface photovoltage measurements also show that the series of Ln-MOFs can effectively generate light-generated charges at the interface under visible light. It can be used as photocatalyst for visible light-driven chemical reaction. This series of MOFs catalyzes the degradation of organic dyes under visible light. The experimental data show that these compounds can be used as photocatalysts for degradation of organic dyes in the presence of H2O2. This work is a few studies on the photocatalytic degradation of organic dyes under visible light using Ln-MOFs compounds, which extends the application of Ln-MOFs materials in visible light catalytic degradation of organic dyes. A novel three-dimensional Dy-MOF ([Dy4 (OH) 4 (ox) 5] 2H3O 路11H2O) was successfully synthesized by using low cost oxalic acid as ligand to coordinate with Ln metal ion Dy3. There are few reported Cubane-like quaternary Dy clusters in this compound, which may have interesting magnetic properties. Magnetic tests show that the compound exhibits monomolecular magnet behavior.
【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】：O641.4
【参考文献】
相关期刊论文 前1条
1 Jing-Wen Ran;Shao-Wen Liu;Peng Wu;Jun Pei;;Efficient photocatalytic properties of a dinuclear iron complex with bis[2-hydroxybenzaldehyde]hydrazonate ligand[J];Chinese Chemical Letters;2013年05期
，本文编号：2435077
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