CN108774323B - 一种基于四齿羧酸配体的Zr的金属有机骨架材料和制备方法及其应用 - Google Patents
一种基于四齿羧酸配体的Zr的金属有机骨架材料和制备方法及其应用 Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 title claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000013110 organic ligand Substances 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 13
- 238000010791 quenching Methods 0.000 abstract description 4
- 230000000171 quenching effect Effects 0.000 abstract description 4
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002178 crystalline material Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 abstract description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- HZBFIFVFNJLHAY-UHFFFAOYSA-L oxygen(2-) zirconium(4+) dichloride hexahydrate Chemical compound O.O.O.O.O.O.[O--].[Cl-].[Cl-].[Zr+4] HZBFIFVFNJLHAY-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
一种基于四齿羧酸配体的Zr的金属有机骨架材料和制备方法及其应用,属于晶态材料的技术领域。化学分子式为[Zr6O4(OH)8(H2O)4(L)2],L为有机配体反式苯乙烯‑3,3’,5,5’‑四羧酸。该金属‑有机骨架的合成为封闭条件下,有机配体反式苯乙烯‑3,3’,5,5’‑四羧酸与氯化锆或者氯氧锆在N,N‑二甲基甲酰胺中,经由溶剂热反应得到金属有机骨架材料的晶体;此金属有机骨架材料显示出被重铬酸根选择性淬灭。
Description
技术领域
本发明属于晶态材料的技术领域,技术涉及金属-有机配位聚合物材料,特征是一种Zr的金属-有机骨架材料、制备方法及其应用研究。
背景技术
金属-有机骨架材料(Metal-Organic Frameworks,MOFs),由金属离子或金属簇与有机配体通过配位键链接而成,作为一类新型的多孔材料,具有比表面积大、孔隙率高、孔道可调等特征,在气体吸附与分离、催化、荧光、电化学等领域具有潜在的应用。MOFs结构的多样性主要源于有机配体多样性以及金属离子或金属簇多样的配位几何构型,因此,可通过四齿羧酸配体获得具有新颖结构的MOFs。
Zr-MOF具有良好的化学稳定性、水热稳定性和机械稳定性。基于此,荧光Zr-MOFs已经大量用于传感检测,不同孔径的MOFs对不同尺寸的客体分子有不同的响应,被选择的粒子与MOFs内表面有特殊的作用,如氢键、电子供体与受体的相互作用、形成配位共价键,这些相互作用对MOFs应用于传感检测有非常大的意义。
发明内容
本发明的目的在于提供一种基于四齿羧酸配体的Zr的金属有机骨架材料和制备方法及其应用。
本发明的一种基于四齿羧酸配体的Zr的金属-有机骨架材料,其特征在于,化学分子式为[Zr6O4(OH)8(H2O)4(L)2],L为有机配体反式苯乙烯-3,3’,5,5’-四羧酸。
该金属-有机骨架中,6个Zr原子结合8个μ3-OH/O形成D4h高对称的正八面体金属中心,在Zr6正八面体团簇中的8个边缘被配体中的羧基占据,而剩下的8个边缘连接-OH/H2O形成次级构筑单元(SBU),然后次级构筑单元链接四齿羧酸配体从而构成了具有四方形孔道的三维骨架结构。
从拓扑学角度看,若将该金属-有机骨架中的Zr6O8簇简化成八链接节点,将四齿羧酸配体简化成四连接的节点,那么整个骨架可以简化成一个(4,8)-c连接的网状结构,其施莱夫利符号(symbol)为{416.612}{44.62}2,是scu拓扑。
其中四齿羧酸配体L(反式苯乙烯-3,3’,5,5’-四羧酸)的结构式如下所示。
本发明金属-有机骨架材料的合成方法,包括以下步骤:
密封条件下,有机配体L(反式苯乙烯-3,3’,5,5’-四羧酸)与氯化锆(ZrCl4)或者六水合氯氧锆(ZrOCl2·6H2O)在DMF(N,N-二甲基甲酰胺)和甲酸的混合溶液中,经由溶剂热反应得到该金属-有机骨架的晶体;进一步优选有机配体L(反式苯乙烯-3,3’,5,5’-四羧酸)与ZrCl4或ZrOCl2·6H2O的摩尔比为1:(1~4),每0.03mmol的ZrCl4或ZrOCl2·6H2O对应1mL~2mL的DMF,0.5-3mL的甲酸,热反应的温度为100℃-135℃,反应时间为60-120小时。
本发明的金属-有机骨架具有稳定性好、荧光性强等优点,使得该MOFs在检测方面具有潜在应用。
附图说明
图1为该金属-有机骨架的次级构筑单元图。
图2为该金属-有机骨架的三维结构示意图。
图3为该金属-有机骨架材料的不同离子的选择性淬灭百分比柱状图。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实施例1
将有机配体L(0.03mmol)与ZrCl4(0.03mmol)在1.0mL的N,N-二甲基甲酰胺中混合均匀,加入甲酸,封入小瓶中。在120℃下经由热反应120小时得到该金属-有机骨架的晶体。
实施例2
将有机配体L(0.03mmol)与ZrOCl2·6H2O(0.09mmol)在1.0mL的N,N-二甲基甲酰胺中混合均匀,加入1.8mL甲酸,封入小瓶中。在135℃下经由热反应96小时得到该金属-有机骨架的晶体。
上述实施例所得的产品的测试结果相同,具体见下述:
(1)晶体结构的确定:
选取大小合适的粉末,在173K下,利用PANalytical X’Pert PRO高分辨粉末衍射仪收集数据。数据收集使用经石墨单色器单色化的Cu-Kα 靶射线。数据的吸收校正使用SCALE3ABSPACK软件完成。晶体结构使用SHELXTL-97程序通过直接法解析得到。先用差值函数法和最小二乘法确定全部非氢原子坐标,并用理论加氢法得到氢原子位置,然后用SHELXTL-97对晶体结构进行精修。结构图见图1至图2。晶体学数据见表1。
表1金属有机骨架材料的晶体学数据
图1的结构图表明:6个Zr原子结合8个μ3-OH/O形成D4h高对称的正八面体金属中心,剩余的Zr配位中心被-OH/H2O占据,正八面体的12个边上的O其中8个通过配位键和羧基相链接形成次级构筑单元(SBU)。
图2的结构图表明:在该金属-有机骨架属于(4,8)-c的三位金属有机骨架结构,其中包括四方形的孔道结构。
(2)离子选择性检测
图3为本发明材料在水溶液中不同阴离子的荧光淬灭百分比,可以看出该材料能对重铬酸根选择性淬灭。图3中本发明材料在水溶液中的浓度0.5mg/mL,加入不同阴离子(浓度分别为5×10-4mol/L)后的荧光淬灭效果。
Claims (1)
1.一种基于四齿羧酸配体的金属-有机骨架材料的应用,作为荧光物质的应用,基于四齿羧酸配体的金属-有机骨架材料化学分子式为[Zr6O4(OH)8(H2O)4(L)2],L为有机配体反式苯乙烯-3,3’,5,5’-四羧酸;从骨架连接构筑的角度看,该金属-有机骨架的晶体结构属于单斜晶系,空间群为I2/m,晶胞参数为: α=γ=90°,β=110.062(13)°;该金属-有机骨架中,6个Zr原子结合8个μ3-OH/O形成D4h高对称的正八面体金属中心,在Zr6正八面体团簇中的8个边缘被配体中的羧基占据,而剩下的8个边缘连接-OH/H2O形成次级构筑单元(SBU),然后次级构筑单元链接四齿羧酸配体从而构成了具有四方形孔道的三维骨架结构;在该金属-有机骨架中存在四方形孔道结构;从拓扑学角度看,若将该金属-有机骨架中的Zr6O8簇简化成八链接节点,将四齿羧酸配体简化成四连接的节点,那么整个骨架可以简化成一个(4,8)-c连接的网状结构,其施莱夫利符号(symbol)为{416.612}{44.62}2,是scu拓扑。
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---|
"Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers";Hao Wang et al.;《NATURE COMMUNICATIONS》;20180501;第9卷;第1-11页 * |
Modulated Synthesis of Zr-Based Metal–Organic Frameworks: From Nano to;Andreas Schaate et al.;《CHEMISTRY A EUROPEAN JOURNAL》;20111231;第17卷;第6643-6651页 * |
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