以Anderson型多酸和同多酸为建筑单元的金属-吡啶衍生物配合物的合成、表征与性能

发布时间：2018-07-02 20:12

本文选题：多金属氧酸盐 + 单晶X-射线衍射　；参考：《渤海大学》2017年硕士论文

【摘要】：本论文以双吡啶双酰胺、吡啶联三氮唑及吡嗪酰胺吡啶为有机配体,在水热条件下与A系列、B系列Aderson型多酸及同多钒酸盐、八钼酸盐阴离子簇和过渡金属离子反应,设计并合成了 29个多酸基金属有机配合物。通过红外(IR)、热重分析(TG)、X射线粉末衍射(PXRD)和单晶X-射线衍射对化合物的组成、结构及热稳定性进行了分析表征,并进一步对本文中的多酸基功能配合物的电化学行为、对有机染料亚甲基蓝(MB)、罗丹明B(RhB)及刚果红(CR)降解的光催化性质进行了探究。1.以经典A系列Anderson型多酸(NH4)6[TeMo6024]·7H20为无机建筑单元,在水热条件下与过渡金属Cu、Zn、Co、Mn和具有不同间隔子长度及不同含N位点的柔性双吡啶双酰胺(3-dpye=N,N'-双(3-吡啶酰胺)-1,2 乙烷,4-dpye=N,N'-双(4-吡啶酰胺)-1,2 乙烷,3-dpyp=N,N'-双(3-吡啶酰胺)-1,3丙烷,4-dpyp=N,N'-双(4-吡啶酰胺)-1,3丙烷,3-dpyb=N,N'-双(3-吡啶酰胺)-1,2 丁烷,4-dpyb=N,N'-双(4-吡啶酰胺)-1,2 丁烷,4-dpyh=N,N'-双(4-吡啶酰胺)-1,2已烷)进行水热反应,得到了 12个新型多酸基金属有机配合物。[Mn2(3-H2dpye)(TeMo6O24)(H2O)6]·4H2O(1)[Cu4(μ3-OH)2(H20)6(4-dpye)2(TeMo6O24)]· 2H2O(2)[Cu2(4-Hdpye)2(TeMo6O24)(H2O)6]·4H2O(3)H2[Zn4(3-Hdpyp)2(TeMo6O24)2(H2O)16]·6H2O(4)[Cu2(4-Hdpyp)2(TeMo6O24)(H2O)6]·4H2O(5)[Cu3(3-dpyb)2(TeMo6O24)(H2O)8]·4H2O(6)[Zn3(3-dpyb)2(TeMo6O24)(H2O)12]·8H2O(7)[Co2(H20)6(TeMo6O24)](3-H2dpyb)·2H2O(8)[Cu2(4-Hdpyb)2(TeMo6O24)(H2O)6]·4H2O(9)[Zn2(4-Hdpyb)2(H2O)6(TeMo6O24)]· 6H2O(10)[Co2(4-Hdpyb)2(H2O)6(TeMo6O24)]· 6H2O(11)[Cu4(μ2-OH)(μ3-OH)(H2O)6(4-dpyh)(TeMo6O24)]· H2O(12)单晶X-射线衍射分析显示化合物1为一个由A系列Anderson型[TeMo6024]6-(TeMo6)阴离子和柔性双吡啶双酰胺配体及金属Mn构成的二维层状结构。化合物2是一个基于Cu4-TeMo6无机链与配体形成的二维有机层。化合物3与化合物9同构,分别为基于不同间隔子长度的0D独立单元。化合物4是由两个多酸阴离子桥接金属离子Zn形成的独立单元结构。化合物5是由金属Cu与TeMo6多酸阴离子簇形成的2D无机层,其中有机配体悬挂于2D层两侧,对化合物的结构起到加固的作用。化合物6为一个基于TeMo6多酸的3D笼状结构。化合物7是一个基于金属Zn的一维波状链。化合物8是一个由金属和TeMo6多酸阴离子构筑的1D链。化合物10与11为同构的0D独立单元。化合物12是一个由金属离子Cu、TeMo6多酸及配体构筑的3D有机金属框架。研究结果表明配体的不同长度、不同含N位点和金属离子的种类、pH的调控对最终配合物的结构都有重要影响。化合物1对Br03-及H2O2的还原具有良好的电催化活性。化合物1-12在紫外条件下对亚甲基蓝、罗丹明B的降解有明显的光催化作用。2.选择B系列Anderson型多酸、三种吡啶衍生物配体和CuⅡ/MnⅡ离子在水热条件下反应,合成了 11个多酸基金属-有机配合物:[Cu2(2-pdya)(CrMo6(OH)5O19)(H2O)2]·3H2O(13)[Mn2(4-pdtz)2[CrMo6(OH)5O19](H2O)4](14)[Cu(3-dpye)0.5(γ-Mo8O26)0.5(H2O)4]·H2O(15){Mn(3-dpye)0.5[CrMo6(OH)6O18](H2O)}·(3-H2dpye)0.5(16)[Cu(4-Hdpyp)2(β-Mo8O26)(H2O)2]· 4H2O(17)H[Cu2(3-dpyb)2(C2O4)(CrMo6(OH)6O18)]· 8H2O(18)[Cu(4-dpyb)(CrMo6(OH)6O18)2(H2O)2][Cu(4-dpyb)(H2O)4](4-H2dpyb)·6 H2O(19)[Cu4(μ3-OH)2(H2O)4(3-dpyh)(γ-Mo8O27)]· 4H2O(20)[Cu2(4-dpyh)(CrMo6(OH)5O19)(H2O)8]·10H2O(21)Cu5(μ2-OH)2(4-dpye)2[(CrMo6(OH)5O19)]2(H2O)10(22){Cu(4-Hdpye)[CrMo6(OH)6O18](H2O)2} · 2H2O(23)[2-pdya=2-吡啶-吡嗪酰胺,4-pdtz=4-吡啶联三氮唑]化合物13是一个由B系列Anderson型多酸CrMo6和金属Cu构成的一维无机链状结构,其中2-吡啶-吡嗪酰胺提供四个配位点用以加固1D双链。化合物14为首例Anderson型多酸与4-吡啶联三氮唑相结合的一维链状结构。在化合物15、17、20中,B系列Anderson型多酸CoMo6通过原位转化为γ-Mo8O264-与β-Mo8O264-阴离子。化合物15是基于[γ-Mo8O26]n4n-链的二维层结构。化合物16是首例B系列Anderson多酸与Mn离子结合的3D金属有机框架。化合物17是一个基于Cu-β-Mo8O26鱼骨链的1D结构。化合物18是一个基于金属-混合配体的圆环型一维链结构,在此圆环型的结构中多酸阴离子起到了稳固该结构骨架的作用。化合物19同样是一个1D链状结构,在这个结构中同时包含了游离的配体及没有多酸阴离子参与的1D链。化合物20是由2D无机层[Cu4(μ3-OH)2(H2O)4(γ-Mo8O27)]构成的3D金属有机框架。化合物21是由双核[Cu2(4-dpyh)]4+单元与多酸阴离子构筑的0D独立单元。化合物22与化合物23为不同pH调控下形成的一釜双晶,其中化合物22为(3,4)-连接的3D有机框架结构,化合物23是一个基于{Cu[CrMo6(OH)6O18](H2O)2}无机层与柔性双吡啶双酰胺配体构筑的2D层结构。配体的种类、配位模式及多酸的配位模式对这些配合物的最终结构有明显的影响。化合物13对过氧化氢和溴酸钾有不同程度的电催化性能,同时可作为pH传感器。化合物13-23在紫外光照射环境下对亚甲基蓝、罗丹明B、刚果红的降解有明显的光催化作用。其中化合物23不仅有光催化作用,同时对于染料表现出了明显的物理吸附性能。3.以经典的同多钼酸盐、同多钒酸盐阴离子作为无机建筑单元,过渡金属Zn离子为中心金属,不同间隔子长度的柔性双吡啶双酰胺作为配体在水热条件下合成了 6个新颖的多酸基配合物。(3-H2dpye)(γ-Mo8O26)0.5(24)(4-H2dpye)[(4-dpye)(γ-Mo8O26)]0.5·2H2O(25)[(3-H2dpyp)2(β-Mo8O26)]·2H2O(26)[(4-H2dpyp)2(β-Mo8O26)]· 2H2O(27)[V206Zn(4-dpye)]n(28){[Zn(3-Hdpye)(H2O)5]2[V10O28]} · 4H2O(29)化合物24是一个由1D γ-Mo8O26无机链和3-H2dpye配体分子构筑的3D超分子结构。化合物25是一个含有Mo-N键的1D链结构,并通过氢键拓展成3D超分子有机框架。化合物26和27分别为3D、2D超分子有机框架。化合物28是首例由[V4O12]4-簇和Zn离子结合并通过配体连接的3D金属有机框架。化合物29是一个独立的0D结构单元。引入不同间隔子长度的配体到该多酸体系中对调节化合物的结构有重要作用。本章研究了化合物24的电化学性能,其对过氧化氢有明显的电催化效果,化合物24-29在紫外光照射条件下对亚甲基蓝及罗丹明B的降解有明显的催化效果。
[Abstract]:In this paper, with bipyridyl biamide, pyridine three azoles and pyrazine pyridine as organic ligands, 29 polyacid foundation organic complexes were designed and synthesized under hydrothermal conditions with A series, B series Aderson polyacid and same vanadate, eight molybdate Anion Cluster and transition metal ions. By infrared (IR), thermogravimetric analysis (TG), X X-ray powder diffraction (PXRD) and single crystal X- ray diffraction were used to characterize the composition, structure and thermal stability of the compounds. The electrochemical behavior of the polyacid based functional complexes in this paper, the photocatalytic properties of organic dye methylene blue (MB), Luo Danming B (RhB) and Congo red (CR) degradation were explored and.1. was used as a classical A. Series Anderson polyacid (NH4) 6[TeMo6024] / 7H20 is an inorganic building unit. Under hydrothermal conditions, the transition metal Cu, Zn, Co, Mn and flexible double pyridine double amide (3-dpye=N, N'- double (3- pyridamide)) with different spacer length and different N loci. Acetamide) -1,3 propane, 4-dpyp=N, N'- double (4- pyridamide) -1,3 propane, 3-dpyb=N, N'- double (3- pyridamide) -1,2 butane, 4-dpyb=N, N'- double (4- pyridamide) cyclohexane) and hydrothermal reaction, obtained 12 new polyacid based metal organic complexes (1). [Cu4 (H20) 6 (4-dpye) 2 (4-dpye) 2 (TeMo6O24)], 2H2O (2) [Cu2 (4-Hdpye) 2 (TeMo6O24) (H2O) 6] 4H2O (3), 2 (4) 2 Hdpyb) 2 (TeMo6O24) (H2O) 6]. 4H2O (9) [Zn2 (4-Hdpyb) 2 (H2O) 6 (TeMo6O24)] 6H2O (10) [Co2 (4-Hdpyb) 2 (11), 6 (12) single crystal (12) X-ray diffraction analysis of single crystal shows that compound 1 is a series of anion and flexible double pyridine double amide A two-dimensional layered structure composed of ligands and metal Mn. Compound 2 is a two-dimensional organic layer based on the formation of Cu4-TeMo6 inorganic chains and ligands. Compound 3 is isomorphic to compound 9, respectively, based on the independent unit of 0D based on the length of different spacers. Compound 4 is an independent unit structure formed by two polyanions bridging the gold ion Zn. Substance 5 is a 2D inorganic layer formed by metal Cu and TeMo6 polyanic anionic clusters, in which organic ligands hang on both sides of the 2D layer and reinforce the structure of the compound. Compound 6 is a TeMo6 polyacid based 3D cage structure. Compound 7 is a one-dimensional wave chain based on metal Zn. Compound 8 is a polyacid negative metal and TeMo6. The 1D chain constructed by ion. Compound 10 and 11 are isomorphic 0D independent units. Compound 12 is a 3D organometallic framework constructed by metal ions Cu, TeMo6 polyacid and ligands. The results show that the ligands have different lengths, different N sites and metal ions, and the regulation of pH has important effects on the structure of the final complexes. 1 the reduction of Br03- and H2O2 has good electrocatalytic activity. Compound 1-12 under UV conditions, the degradation of Ya Jiaji blue and Rhodamine B has obvious photocatalytic activity,.2. chooses B series Anderson polyacid, three pyridine derivative ligands and Cu II /Mn II ions react under hydrothermal conditions, and 11 polyacid base metal organic complexes are synthesized. [Cu2 (2-pdya) (CrMo6 (OH) 5O19) (H2O) 2]. 3H2O (13) [Mn2 (4-pdtz) 2[CrMo6 (OH) 0.5 (17) 0.5 (17) 2 (17) 2 ) 2 (H2O) 2][Cu (4-dpyb) (H2O) 4] (4-H2dpyb), 6 H2O (19) [Cu4 (H2O) 4 (H2O) 4 (3-dpyh) (3-dpyh), 10 (20) 10 (22) 10 (22)) Compound 13 is a one-dimensional inorganic chain structure composed of B series Anderson polyacid CrMo6 and metal Cu, in which 2- pyridine pyrazine provides four loci for strengthening 1D double strands. Compound 14 is the first one-dimensional chain structure of Anderson type polyacid and 4- pyridine combined three azoles. In compound 15,17,20, Anderson type B series series Polyacid CoMo6 is converted into gamma -Mo8O264- and beta -Mo8O264- anion in situ. Compound 15 is based on [2-D layer structure of gamma -Mo8O26]n4n- chain. Compound 16 is the first 3D metal organic framework of B series Anderson polyacid and Mn ions. Compound 17 is a 1D structure based on Cu- beta -Mo8O26 fish bone chain. Compound 18 is based on metal - The ring type one-dimensional chain structure of the mixed ligand, in which polyanic anions play a role in stabilizing the structure of the structure. Compound 19 is also a 1D chain structure in which the free ligands and 1D chains without polyanic anions are included. Compound 20 is composed of 2D inorganic layer [Cu4 (H2O) 2 (H2O) 4 ( Gamma -Mo8O27)] 3D metal organic framework. Compound 21 is a 0D independent unit constructed by a dual nucleus [Cu2 (4-dpyh)]4+ unit and polyanic anions. Compound 22 and compound 23 are formed in a single autoclave under the control of different pH, of which compound 22 is a (3,4) - connected 3D organic frame structure, and compound 23 is a {Cu[CrMo6 (OH) 6O18] (OH) 6O18]. The structure of 2D layer constructed by 2} inorganic layer and flexible bipyridyl biamide ligand. The type of ligand, coordination mode and the coordination mode of polyacid have obvious influence on the final structure of these complexes. Compound 13 has different degrees of electrocatalysis for hydrogen peroxide and potassium bromate, and can be used as a pH sensor. Compound 13-23 in ultraviolet light In the radiation environment, the degradation of methylene blue, rhodamine B, and Congo red has obvious photocatalytic activity. Compound 23 not only has the photocatalytic activity, but also shows obvious physical adsorption performance for the dye.3. with the classic ISO molybdate, the same vanadium anion as the inorganic building unit and the transition metal Zn ion as the central metal. 6 novel polyacid complexes were synthesized by flexible bipyridine biamide with different spacer lengths as ligands. (3-H2dpye) (gamma -Mo8O26) 0.5 (4-H2dpye) (4-dpye) (4-dpye),]0.5. 2H2O (25) [(3-H2dpyp) 2 (beta -Mo8O26)]. 2H2O (26) [4-H2dpyp) 2 (27) O) 5]2[V10O28]}. 4H2O (29) compound 24 is a 3D supramolecular structure constructed by 1D gamma -Mo8O26 inorganic chain and 3-H2dpye ligand molecule. Compound 25 is a 1D chain structure containing Mo-N bonds, and is extended into a 3D supramolecular organic framework through hydrogen bonds. Compounds 26 and 27 are 3D, 2D supramolecular organic frameworks. Compound 28 is the first example - a 3D metal organic frame connected by a cluster of Zn ions and connected by a ligand. Compound 29 is an independent 0D structural unit. Introducing ligands with different spacers length to the polyacid system have an important role in regulating the structure of the compound. This chapter studies the electrochemical performance of compound 24, which has an obvious electrocatalytic effect on hydrogen peroxide. Fruit compound 24-29 has obvious catalytic effect on the degradation of methylene blue and Rhodamine B under UV irradiation.
【学位授予单位】：渤海大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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