基于芳香四羧酸MOFs的合成、結構及其電容性能研究
發(fā)布時間：2018-11-10 18:59
【摘要】：可設計的金屬有機骨架(MOFs)因具有比表面積大和孔道結構豐富的等優(yōu)點,使得這類材料在超級電容器領域具有很好的應用潛力。本文基于剛性L1=3,3′,5,5′-聯(lián)二苯四羧酸(H_4BPTC)配體,及柔性芳香四羧酸L2=5-(2-((3,5-二羥基)氧)氧乙基)間二苯甲酸(H_4PDTA)、L3=5-(5'-(1,4-苯雙環(huán)(亞甲基)二氧)間二苯甲酸(H_4PDPA)和L4=1,3-二(3',5'-二苯甲酸)苯(H_4DPB)配體,以Cd、Co、In和Li為金屬中心合成了8個結構新穎的配合物:{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)并對這8個配合物進行了單晶結構的解析、X-射線粉末衍射、紅外光譜分析、熱重分析、熒光光譜分析、半導體性能研究以及電容性質等全面的理化性能表征。(1)基于剛性配體L1與金屬Cd、Co、In和Li構筑了配合物1-5:同構配合物1和2中均有雙核金屬簇M_2(COO)_3(M=Cd~(2+),Co~(2+)),雙核簇與配體L1在ac平面擴展成二維層,二維層與二維層間通過配體在b軸方向形成具有兩種不同類型孔道的三維結構。同分異構的配合物3和4均是In和L1在不同溶劑為模板劑的導向作用下自組裝而成,這兩個配合物中配體的兩個苯環(huán)所在平面間二面角分別為61.9°和16.0°,使得二者呈現(xiàn)出不同的三維結構。配合物5中存在由LiO_4四面體共邊連接形成四核簇(LiO_4)_4,四核簇之間連接成近似波浪狀的一維鏈{(LiO_4)_4}_n,一維鏈與獨立的四面體通過配體連接形成兩種類似三明治的二維層,兩種不同的二維層又通過配體交替連接形成三維結構。對以上5個配合物進行電容測試,當電流密度為1 A g~(-1)時,配合物1-5的質量比電容值依次為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)基于柔性配體L2、L3和L4,以Li~+為中心金屬離子,構筑了多核鋰簇配合物6-8。配合物6中的三核鋰簇Li_3(COO_)3與L2配體形成一條柱狀一維鏈,兩條柱狀鏈之間通過共用彎曲配體形成三維孔道,進而形成(6,6)-連接的拓撲網絡結構。配合物7中的一維鏈由四核鋰簇Li_4(μ_2-O)_2(COO)_4之間通過共用兩個羧基形成;一維鋰鏈之間通過完整的配體L3形成(6,6)-連接的三維孔道。配合物8中有單核鋰簇(Li(1)O_4),雙核簇(Li_2(COO)_4)和蝴蝶型六核簇(Li_6(COO)_6)三種鋰簇;沿b方向,兩個蝴蝶型六核簇之間通過連接兩個不同配體L4形成兩種不同的四方網格狀的二維層;剪刀狀的二維平面之間通過共用六核簇相交成三維菱形孔道結構。并對以上三個配合物進行電容測試,當電流密度為1 A g~(-1)時,配合物6-8的質量比電容值依次為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 擄and 16.0 擄, 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.
【學位授予單位】：山西師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O641.4
本文編號：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 擄and 16.0 擄, 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.
【學位授予單位】：山西師范大學
【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 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
，本文編號：2323326
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