钒酸盐晶态材料的水热合成及表征
发布时间：2019-02-17 10:45
【摘要】：钒酸盐是一类新型的多功能材料,具有独特的分子结构与优异的物理、化学性质,使其在光学、磁学、电学、催化等方面展现出良好的应用前景,是新一代激光器、钒电池、磁信息记录器等器件的关键材料,使得科研工作者对它的合成、结构和性能有浓厚的研究兴趣。为了开发具有潜在应用价值的新型钒酸盐材料,本文通过水热反应,成功地合成了11种配合物,并探索新配合物结构与性能间的关系。通过红外光谱、紫外光谱、热重分析、X-射线粉末衍射、X-射线单晶衍射等对配合物进行表征,并对其中一些配合物的荧光、光催化、磁性和热稳定性等性能进行了初步研究。1、钒酸盐:在水热条件下,合成了5种新型钒酸盐[Cu_4(biimpy)4(V_4O_(12))]n·-2H_2O(biimpy=2,6-双(1-咪唑基)吡啶)(1)、[V_2O_2(H_2O)_2Cl_4(4,4′-bpy)3](2)、[VOCl(2,2′-bpy)_2]Cl·2H_2O(3)、[V_2O_2(C_2O_4)]·5H_2O(4)、{VO_2[NH(CH_2COOH)_2]}(5),并对其进行表征。化合物1包含1-D亚铜咪唑链和环[V_4O_(12)]4-簇,是首例包含2类建筑单元的2-D异-钒-亚铜咪唑聚合物。化合物2中的1-D[V_2O_2(H_2O)_2Cl_4(4,4′-bpy)3]链通过氢键相互作用,形成3-D氢键网络结构。化合物3包含阳离子[VOCl(2,2′-bpy)_2]+和阴离子Cl-。化合物4~5展示1-D链状结构,链与链以平行方式排列。化合物1展示良好的光催化性能。2、硼钒酸盐:在水热条件下,合成了2种新型的三维硼钒酸盐{[Cd(H_2O)_2]3V_(12)B_(18)O_(54)(OH)6}·4H_3O·26H_2O(6)和[K6(H_2O)10Zn_4V_(10)B_(32)O_(74)-(OH)10]·5H_2O(7)。化合物6的三维硼钒酸盐框架是由[V_(12)B_(18)O_(54)(OH)6]簇和[CdO6]八面体桥接而成,其展示新颖的三维骨架。化合物7含有[Zn_4V_(10)B_(32)O_(74)(OH)10]簇和二维[K6O_(35)]n层,它们互相连接形成另一种三维[K6(H_2O)10Zn_4V_(10)B_(32)O_(74)(OH)10]结构,其中游离水分子填充在一维孔道中。虽然,已有少量的三维硼钒酸盐报道,但是它们的建筑单元都是三元B-O-V簇。而化合物7是首例含四元[Zn_4V_(10)B_(32)O_(74)(OH)10]簇的三维硼钒酸盐。化合物6和7展示了良好的磁性和光催化性能。3、咪唑类配位聚合物:在水热条件下,合成了4种新型的咪唑类配位聚合物[CuI_2Cl(μ5-L)]n(HL=1-四唑-4-咪唑-苯(HL)(8)、[CuI(L)]n(L=异烟酸乙酯)(9)、[Co_2(OH)ClL_2]·3.5H_2O(HL=1-四唑-4-咪唑-苯)(10)、[MnO_2L_2](HL=1-四唑-4-咪唑-苯)(11)。化合物8是3-D氯化亚铜聚合物,是[CuI_2Cl]+阳离子和L-配体构建的3-D网络结构,并研究其荧光性能,热稳定性能和能带结构。化合物9是1-D异烟酸乙酯铜(I)配位聚合物[CuI(L)]n(9),并研究其荧光性能和能带结构。化合物10是由新的无机[Co_4(OH)_2Cl2]簇与L配体连接,形成3-D网状结构。化合物11展示了1-D链状结构。
[Abstract]:Vanadate is a new kind of multifunctional materials with unique molecular structure and excellent physical and chemical properties. It has shown a good application prospect in optics, magnetism, electricity, catalysis and so on. It is a new generation of lasers, vanadium batteries, etc. Because of the key materials of magnetic information recorder and other devices, researchers are interested in its synthesis, structure and properties. In order to develop new vanadate materials with potential application value, 11 complexes have been successfully synthesized by hydrothermal reaction, and the relationship between the structure and properties of the new complexes has been explored. The complexes were characterized by IR, UV, TGA, X ray powder diffraction and X ray single crystal diffraction, and some of the complexes were characterized by fluorescence and photocatalysis. The magnetic properties and thermal stability of vanadate were studied. 1. Vanadate: under hydrothermal conditions, Five new vanadate [Cu_4 (biimpy) _ 4 (VS _ 4O _ (12)] n 2H_2O (biimpy=2,6- bis (1-imidazolyl) pyridine) (1) were synthesized. [V_2O_2 (H _ 2O) _ 2Cl_4 (4H _ 2O _ 2Cl_4) _ 3] (2), [VOCl (2H _ 2O) _ 2] Cl 2H_2O (3), [V_2O_2 (C_2O_4)] 5H_2O (4), {VO_2 [NH (CH_2COOH) 2]} (5) and characterized. Compound 1 contains 1-D cuprous imidazole chain and ring [V _ 4O _ (12)] _ 4-cluster, which is the first 2-D iso-vanadium-cuprous imidazole polymer containing two building units. The chain of 1-D [V_2O_2 (H2O) _ 2Cl_4 (4H _ 2O _ BPY) _ 3] in compound 2 interacts with hydrogen bond to form 3-D hydrogen bond network structure. Compound 3 contains cationic [VOCl (2O2PY) 2] and anionic Cl-. Compound 4: 5 exhibits a 1-D chain structure in which chains are arranged in parallel with chains. Compound 1 shows good photocatalytic properties. 2, boron vanadate: in hydrothermal conditions, Two new three dimensional borovanadate {[Cd (Hs _ 2O) _ 2] 3V _ (12) B _ (18) O _ (54) (OH) 6)} 4H_3O 26H_2O (6) and [K _ 6 (H _ 2O) _ 10 Zn _ 4V _ (10)] have been synthesized. B _ (32) O _ (74)-(OH) 10] 5H_2O (7). The three-dimensional borovanadate frame of compound 6 is bridged by [V12B18O54) (OH) 6] cluster and [CdO6] octahedron. Compound 7 contains [Zn_4V_ (10) B _ (32) O _ (74) (OH) 10)] clusters and two-dimensional [K _ 6O _ (35)] n layers, They are connected to each other to form another three-dimensional [K6 (H2O) 10Zn4Zn4V32 O74) (OH) 10] structure in which free water molecules are filled in one-dimensional channels. Although a small number of three dimensional boron vanadates have been reported, their building units are ternary B-O-V clusters. Compound 7 is the first three-dimensional boron vanadate containing Zn_4V_ (10) B _ (32) O _ (74) (OH) _ (10) clusters. Compounds 6 and 7 exhibit good magnetic and photocatalytic properties. 3, imidazole coordination polymers: in hydrothermal conditions, Four new imidazole coordination polymers [CuI_2Cl (渭 5-L)] n (HL=1- tetrazole-4-imidazole-benzene (HL) (8), [CuI (L)] n (L = ethyl isonicotinate) (9) were synthesized. [Co_2 (OH) ClL_2] 3.5H_2O (HL=1- tetrazole-4-imidazole-benzene) (10), [MnO_2L_2] (HL=1- tetrazole-4-imidazole-benzene) (11). Compound 8 is a 3-D copperous chloride polymer, which is a 3-D network constructed by [CuI_2Cl] cations and L- ligands. The fluorescence properties, thermal stability and band structure of compound 8 are studied. Compound 9 is a (I) coordination polymer [CuI (L)] n (9) with 1-D ethyl isonicotinic acid, and its fluorescence properties and band structure are studied. Compound 10 is composed of new inorganic [Co_4 (OH) _ 2Cl2] clusters and L ligands to form 3-D reticular structures. Compound 11 shows a 1-D chain structure.
【学位授予单位】：重庆师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2425084
[Abstract]:Vanadate is a new kind of multifunctional materials with unique molecular structure and excellent physical and chemical properties. It has shown a good application prospect in optics, magnetism, electricity, catalysis and so on. It is a new generation of lasers, vanadium batteries, etc. Because of the key materials of magnetic information recorder and other devices, researchers are interested in its synthesis, structure and properties. In order to develop new vanadate materials with potential application value, 11 complexes have been successfully synthesized by hydrothermal reaction, and the relationship between the structure and properties of the new complexes has been explored. The complexes were characterized by IR, UV, TGA, X ray powder diffraction and X ray single crystal diffraction, and some of the complexes were characterized by fluorescence and photocatalysis. The magnetic properties and thermal stability of vanadate were studied. 1. Vanadate: under hydrothermal conditions, Five new vanadate [Cu_4 (biimpy) _ 4 (VS _ 4O _ (12)] n 2H_2O (biimpy=2,6- bis (1-imidazolyl) pyridine) (1) were synthesized. [V_2O_2 (H _ 2O) _ 2Cl_4 (4H _ 2O _ 2Cl_4) _ 3] (2), [VOCl (2H _ 2O) _ 2] Cl 2H_2O (3), [V_2O_2 (C_2O_4)] 5H_2O (4), {VO_2 [NH (CH_2COOH) 2]} (5) and characterized. Compound 1 contains 1-D cuprous imidazole chain and ring [V _ 4O _ (12)] _ 4-cluster, which is the first 2-D iso-vanadium-cuprous imidazole polymer containing two building units. The chain of 1-D [V_2O_2 (H2O) _ 2Cl_4 (4H _ 2O _ BPY) _ 3] in compound 2 interacts with hydrogen bond to form 3-D hydrogen bond network structure. Compound 3 contains cationic [VOCl (2O2PY) 2] and anionic Cl-. Compound 4: 5 exhibits a 1-D chain structure in which chains are arranged in parallel with chains. Compound 1 shows good photocatalytic properties. 2, boron vanadate: in hydrothermal conditions, Two new three dimensional borovanadate {[Cd (Hs _ 2O) _ 2] 3V _ (12) B _ (18) O _ (54) (OH) 6)} 4H_3O 26H_2O (6) and [K _ 6 (H _ 2O) _ 10 Zn _ 4V _ (10)] have been synthesized. B _ (32) O _ (74)-(OH) 10] 5H_2O (7). The three-dimensional borovanadate frame of compound 6 is bridged by [V12B18O54) (OH) 6] cluster and [CdO6] octahedron. Compound 7 contains [Zn_4V_ (10) B _ (32) O _ (74) (OH) 10)] clusters and two-dimensional [K _ 6O _ (35)] n layers, They are connected to each other to form another three-dimensional [K6 (H2O) 10Zn4Zn4V32 O74) (OH) 10] structure in which free water molecules are filled in one-dimensional channels. Although a small number of three dimensional boron vanadates have been reported, their building units are ternary B-O-V clusters. Compound 7 is the first three-dimensional boron vanadate containing Zn_4V_ (10) B _ (32) O _ (74) (OH) _ (10) clusters. Compounds 6 and 7 exhibit good magnetic and photocatalytic properties. 3, imidazole coordination polymers: in hydrothermal conditions, Four new imidazole coordination polymers [CuI_2Cl (渭 5-L)] n (HL=1- tetrazole-4-imidazole-benzene (HL) (8), [CuI (L)] n (L = ethyl isonicotinate) (9) were synthesized. [Co_2 (OH) ClL_2] 3.5H_2O (HL=1- tetrazole-4-imidazole-benzene) (10), [MnO_2L_2] (HL=1- tetrazole-4-imidazole-benzene) (11). Compound 8 is a 3-D copperous chloride polymer, which is a 3-D network constructed by [CuI_2Cl] cations and L- ligands. The fluorescence properties, thermal stability and band structure of compound 8 are studied. Compound 9 is a (I) coordination polymer [CuI (L)] n (9) with 1-D ethyl isonicotinic acid, and its fluorescence properties and band structure are studied. Compound 10 is composed of new inorganic [Co_4 (OH) _ 2Cl2] clusters and L ligands to form 3-D reticular structures. Compound 11 shows a 1-D chain structure.
【学位授予单位】：重庆师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
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2 杜晓迪;李承辉;;一个基于多钒酸盐与柔性吡啶基配体的三维非中心对称杂化物(英文)[J];无机化学学报;2010年09期
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