基于芳香四羧酸MOFs的合成、结构及其电容性能研究
发布时间：2018-11-10 18:59
【摘要】：可设计的金属有机骨架(MOFs)因具有比表面积大和孔道结构丰富的等优点,使得这类材料在超级电容器领域具有很好的应用潜力。本文基于刚性L1=3,3′,5,5′-联二苯四羧酸(H_4BPTC)配体,及柔性芳香四羧酸L2=5-(2-((3,5-二羟基)氧)氧乙基)间二苯甲酸(H_4PDTA)、L3=5-(5'-(1,4-苯双环(亚甲基)二氧)间二苯甲酸(H_4PDPA)和L4=1,3-二(3',5'-二苯甲酸)苯(H_4DPB)配体,以Cd、Co、In和Li为金属中心合成了8个结构新颖的配合物:{Cd_2(L1)(CH_3CH_2O)(DMA)(H_2O)}_n(1){Co_2(L1)(DMA)(H_2O)_2?(DMA)_2}_n(2){In(L1)?(DMP)}_n(3){In(L1)?(DMF)}_n(4){[Li_(5.5)(L1)_4(DMF)(H_2O)?(H_2O)]}_n(5){[Li_3(L2)(DMF)(H_2O)?(H_2O)]}_n(6){[Li_4(L3)(DMF)_2]}_n(7){[Li_5(L4)_2(H_2O)?(H_2O)]}_n(8)并对这8个配合物进行了单晶结构的解析、X-射线粉末衍射、红外光谱分析、热重分析、荧光光谱分析、半导体性能研究以及电容性质等全面的理化性能表征。(1)基于刚性配体L1与金属Cd、Co、In和Li构筑了配合物1-5:同构配合物1和2中均有双核金属簇M_2(COO)_3(M=Cd~(2+),Co~(2+)),双核簇与配体L1在ac平面扩展成二维层,二维层与二维层间通过配体在b轴方向形成具有两种不同类型孔道的三维结构。同分异构的配合物3和4均是In和L1在不同溶剂为模板剂的导向作用下自组装而成,这两个配合物中配体的两个苯环所在平面间二面角分别为61.9°和16.0°,使得二者呈现出不同的三维结构。配合物5中存在由LiO_4四面体共边连接形成四核簇(LiO_4)_4,四核簇之间连接成近似波浪状的一维链{(LiO_4)_4}_n,一维链与独立的四面体通过配体连接形成两种类似三明治的二维层,两种不同的二维层又通过配体交替连接形成三维结构。对以上5个配合物进行电容测试,当电流密度为1 A g~(-1)时,配合物1-5的质量比电容值依次为35.9 F g~(-1)、111.9 F g~(-1)、25.0 F g~(-1)、34.7 F g~(-1)和49.6F g~(-1)。(2)基于柔性配体L2、L3和L4,以Li~+为中心金属离子,构筑了多核锂簇配合物6-8。配合物6中的三核锂簇Li_3(COO_)3与L2配体形成一条柱状一维链,两条柱状链之间通过共用弯曲配体形成三维孔道,进而形成(6,6)-连接的拓扑网络结构。配合物7中的一维链由四核锂簇Li_4(μ_2-O)_2(COO)_4之间通过共用两个羧基形成;一维锂链之间通过完整的配体L3形成(6,6)-连接的三维孔道。配合物8中有单核锂簇(Li(1)O_4),双核簇(Li_2(COO)_4)和蝴蝶型六核簇(Li_6(COO)_6)三种锂簇;沿b方向,两个蝴蝶型六核簇之间通过连接两个不同配体L4形成两种不同的四方网格状的二维层;剪刀状的二维平面之间通过共用六核簇相交成三维菱形孔道结构。并对以上三个配合物进行电容测试,当电流密度为1 A g~(-1)时,配合物6-8的质量比电容值依次为34.1 F g~(-1)、35.0 F g~(-1)和17.9 F g~(-1)。
[Abstract]:Due to the advantages of large specific surface area and abundant pore structure, the metal-organic skeleton (MOFs) has good application potential in the field of supercapacitors. Based on the ligands of rigid L _ (1) C _ (3) O _ (5) -biphenyl tetracarboxylic acid (H_4BPTC) and flexible aromatic tetracarboxylic acid L _ (2) O _ (5-) (3) (3) (3) (3) (5) dihydroxyethyl) dibenzoic acid ( Ligands L3O5- (1O4-Bicyclic (methylene) dioxy) m-dibenzoic acid (H_4PDPA) and L4C1O3- bis (3OBX) -dibenzoic acid (H_4DPB), ligands with Cd,Co, In and Li have synthesized eight novel complexes: {Cd_2 (L1) (CH_3CH_2O) (DMA) (H2O)} _ n (1) {Co_2 (L1) (DMA) (H2O) _ 2 (DMA) ) _ 2} _ n (2) {In (L1)? (DMP)} _ n (3) {In (L1)? (DMF)} _ n (4) {[Li_ (5.5) (L1) _ 4 (DMF) (H2O)? (H2O)]} N (5) {[Li_3 (L2) (DMF) (H2O)? (H2O)]} _ n (6) {[Li_4 (L3) (DMF) _ 2]} _ n (7) {[Li_5 (L4) 2 (H2O)]? ( H2O]} _ n (8) and the single crystal structures of these complexes were elucidated. X-ray powder diffraction, infrared spectroscopy, thermogravimetric analysis, fluorescence spectrum analysis, semiconductor properties and capacitive properties. (1) based on the rigid ligand L1 and metal Cd,Co,. In and Li have constructed complexes 1-5: isomorphic complexes 1 and 2 have binuclear metal clusters Ms2 (COO) _ 3 (MtCd2), Co~ (2), binuclear clusters and ligand L1) expand into two-dimensional layers in the ac plane. Two dimensional layers and two dimensional layers pass through the ligands to form three dimensional structures with two different types of pores in the b axis direction. The isomeric complexes 3 and 4 were self-assembled by In and L1 under the guidance of different solvents as templates. The dihedral angles between the two benzene rings were 61.9 掳and 16.0 掳, respectively. It makes them present different three-dimensional structure. In complex 5, a tetrahedral LiO_4 tetrahedron is formed to form a tetranuclear cluster (LiO_4) _ 4, and a wave like one-dimensional chain {(LiO_4) _ 4} _ n is formed between the tetrahedral clusters. One-dimensional chains and independent tetrahedrons form two sandwich like two-dimensional layers by ligand bonding, and two different two-dimensional layers form three-dimensional structures through alternating ligand connections. When the current density is 1 A g ~ (-1), the specific capacitance values of the complexes 1-5 are 35.9 F g ~ (-1), 111.9 F g ~ (-1), 25.0 F g ~ (-1), respectively, when the current density is 1 A g ~ (-1), and the specific capacitance values of the complexes are 35.9 F g ~ (-1), 111.9 F g ~ (-1), 25.0 F g ~ (-1), respectively. 34.7 F g ~ (-1) and 49.6 F g ~ (-1). (_ 2 based on the flexible ligands L _ 2N _ 3 and L _ 4, the polynuclear lithium cluster complexes 6-8 were constructed with Li~ as the center metal ions. The trinuclear lithium cluster Li_3 (COO_) 3 forms a columnar one-dimensional chain with L _ 2 ligand in complex 6, and a three-dimensional pore structure is formed between the two columnar chains by common curved ligands, thus forming a topological network structure of (6 ~ (6) -junction. The one-dimensional chain in complex 7 is formed by sharing two carboxyl groups between tetranuclear lithium clusters Li_4 (渭 _ 2-O) _ 2 (COO) _ 4, and between one-dimensional lithium chains through a complete ligand L3 to form a three-dimensional channel of (6 ~ (6) -junction. There are three kinds of lithium clusters in complex 8: mononuclear lithium cluster (Li (_ 1) O _ 4) binuclear cluster (Li_2 (COO) _ 4) and butterfly hexanuclear cluster (Li_6 (COO) _ 6). Along the b direction, two different tetragonal meshes are formed between two butterfly clusters by connecting two different ligands L4, and the shear-shaped two-dimensional planes intersect to form a three-dimensional rhombic pore structure by sharing the six-core clusters. When the current density is 1 A g ~ (-1), the specific capacitance values of the complexes 6-8 are 34.1 F g ~ (-1), 35.0 F g ~ (-1) and 17.9 F g ~ (-1), respectively.
【学位授予单位】：山西师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2323326
[Abstract]:Due to the advantages of large specific surface area and abundant pore structure, the metal-organic skeleton (MOFs) has good application potential in the field of supercapacitors. Based on the ligands of rigid L _ (1) C _ (3) O _ (5) -biphenyl tetracarboxylic acid (H_4BPTC) and flexible aromatic tetracarboxylic acid L _ (2) O _ (5-) (3) (3) (3) (3) (5) dihydroxyethyl) dibenzoic acid ( Ligands L3O5- (1O4-Bicyclic (methylene) dioxy) m-dibenzoic acid (H_4PDPA) and L4C1O3- bis (3OBX) -dibenzoic acid (H_4DPB), ligands with Cd,Co, In and Li have synthesized eight novel complexes: {Cd_2 (L1) (CH_3CH_2O) (DMA) (H2O)} _ n (1) {Co_2 (L1) (DMA) (H2O) _ 2 (DMA) ) _ 2} _ n (2) {In (L1)? (DMP)} _ n (3) {In (L1)? (DMF)} _ n (4) {[Li_ (5.5) (L1) _ 4 (DMF) (H2O)? (H2O)]} N (5) {[Li_3 (L2) (DMF) (H2O)? (H2O)]} _ n (6) {[Li_4 (L3) (DMF) _ 2]} _ n (7) {[Li_5 (L4) 2 (H2O)]? ( H2O]} _ n (8) and the single crystal structures of these complexes were elucidated. X-ray powder diffraction, infrared spectroscopy, thermogravimetric analysis, fluorescence spectrum analysis, semiconductor properties and capacitive properties. (1) based on the rigid ligand L1 and metal Cd,Co,. In and Li have constructed complexes 1-5: isomorphic complexes 1 and 2 have binuclear metal clusters Ms2 (COO) _ 3 (MtCd2), Co~ (2), binuclear clusters and ligand L1) expand into two-dimensional layers in the ac plane. Two dimensional layers and two dimensional layers pass through the ligands to form three dimensional structures with two different types of pores in the b axis direction. The isomeric complexes 3 and 4 were self-assembled by In and L1 under the guidance of different solvents as templates. The dihedral angles between the two benzene rings were 61.9 掳and 16.0 掳, respectively. It makes them present different three-dimensional structure. In complex 5, a tetrahedral LiO_4 tetrahedron is formed to form a tetranuclear cluster (LiO_4) _ 4, and a wave like one-dimensional chain {(LiO_4) _ 4} _ n is formed between the tetrahedral clusters. One-dimensional chains and independent tetrahedrons form two sandwich like two-dimensional layers by ligand bonding, and two different two-dimensional layers form three-dimensional structures through alternating ligand connections. When the current density is 1 A g ~ (-1), the specific capacitance values of the complexes 1-5 are 35.9 F g ~ (-1), 111.9 F g ~ (-1), 25.0 F g ~ (-1), respectively, when the current density is 1 A g ~ (-1), and the specific capacitance values of the complexes are 35.9 F g ~ (-1), 111.9 F g ~ (-1), 25.0 F g ~ (-1), respectively. 34.7 F g ~ (-1) and 49.6 F g ~ (-1). (_ 2 based on the flexible ligands L _ 2N _ 3 and L _ 4, the polynuclear lithium cluster complexes 6-8 were constructed with Li~ as the center metal ions. The trinuclear lithium cluster Li_3 (COO_) 3 forms a columnar one-dimensional chain with L _ 2 ligand in complex 6, and a three-dimensional pore structure is formed between the two columnar chains by common curved ligands, thus forming a topological network structure of (6 ~ (6) -junction. The one-dimensional chain in complex 7 is formed by sharing two carboxyl groups between tetranuclear lithium clusters Li_4 (渭 _ 2-O) _ 2 (COO) _ 4, and between one-dimensional lithium chains through a complete ligand L3 to form a three-dimensional channel of (6 ~ (6) -junction. There are three kinds of lithium clusters in complex 8: mononuclear lithium cluster (Li (_ 1) O _ 4) binuclear cluster (Li_2 (COO) _ 4) and butterfly hexanuclear cluster (Li_6 (COO) _ 6). Along the b direction, two different tetragonal meshes are formed between two butterfly clusters by connecting two different ligands L4, and the shear-shaped two-dimensional planes intersect to form a three-dimensional rhombic pore structure by sharing the six-core clusters. When the current density is 1 A g ~ (-1), the specific capacitance values of the complexes 6-8 are 34.1 F g ~ (-1), 35.0 F g ~ (-1) and 17.9 F g ~ (-1), respectively.
【学位授予单位】：山西师范大学
【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 Long Kang;Shi-Xiong Sun;Ling-Bin Kong;Jun-Wei Lang;Yong-Chun Luo;;Investigating metal-organic framework as a new pseudo-capacitive material for supercapacitors[J];Chinese Chemical Letters;2014年06期
，本文编号：2323326
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2323326.html
教材专著
