稀土金屬有機骨架化合物的合成、結(jié)構(gòu)、光催化及磁性研究
發(fā)布時間：2019-03-05 16:03
【摘要】：金屬有機骨架化合物(Metal-Organic Frameworks,MOFs)具有較大的比表面積且兼具結(jié)構(gòu)可設計、功能可調(diào)控等特點,近些年來在氣體吸附、熒光、催化、和光電磁等方面展現(xiàn)了其巨大的應用優(yōu)勢。其中基于鑭系金屬的Ln-MOFs,鑒于自身特殊的4f電子層結(jié)構(gòu),相比于過渡態(tài)金屬離子構(gòu)成的MOFs而言具有更高的配位數(shù)以及更加豐富的配位模式,受到人們廣泛重視。本論文分別利用蒽基官能化的二羧酸有機配體橋連稀土離子(Ce3+,Tb3+,Dy3+),草酸配體連接稀土(Dy3+)離子簇,在溶劑熱/水熱條件下配位構(gòu)筑出具有新穎結(jié)構(gòu)特色和不同性質(zhì)的系列新型稀土金屬有機骨架化合物。通過單晶X-射線衍射、粉末X-射線衍射、紫外、熒光、熱重、紅外、表面光電壓(SPV)、電化學和磁性測試等表征手段對所制備Ln-MOFs化合物的結(jié)構(gòu)和物理化學性質(zhì)進行表征,探索了所制備不同Ln-MOFs作為可見光催化劑催化降解水中有機染料的性質(zhì)及單分子磁行為。具體內(nèi)容如下:1、利用蒽基二羧酸配體(H2L)與Ln系離子(Ce3+,Tb3+,Dy3+)配位成功合成了系列新型Ln-MOFs NNU-15(Ce,Tb,Dy)并對它們物理化學性質(zhì)進行測試。穩(wěn)態(tài)吸收光譜顯示該系列化合物均在可見光區(qū)展示出較寬的吸收帶,表面光電壓測試也表明該系列Ln-MOFs在可見光下可有效生成界面光生電荷,可以作為光催化劑進行可見光驅(qū)動化學反應。我們對該系列MOFs在可見光下催化降解有機染料進行了實驗探究。實驗數(shù)據(jù)表明,在氧化性物質(zhì)H2O2的存在下,該系列化合物可作為較好的光催化劑進行有機染料降解。本工作是少數(shù)使用Ln-MOFs化合物對有機染料在可見光條件下進行光催化降解的研究,擴展了Ln-MOFs材料在可見光催化降解有機染料方面的應用。2、利用低成本草酸為配體與Ln系金屬離子Dy3+配位,成功合成了一例具有新穎結(jié)構(gòu)特征的三維Dy-MOF([Dy4(OH)4(ox)5]·2H3O·11H2O)。該化合物中存在極少報道的Cubane-like四核Dy簇,可能存在有趣的磁性質(zhì)。磁性測試表明該化合物表現(xiàn)出單分子磁體行為。
[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.
【學位授予單位】：東北師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4
本文編號：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.
【學位授予單位】：東北師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4
【參考文獻】
相關期刊論文 前1條
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
，本文編號：2435077
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