CN115124730A - Dissimilar metal zirconium-based metal organic framework complex with semiconductor behavior and preparation method and application thereof - Google Patents
Dissimilar metal zirconium-based metal organic framework complex with semiconductor behavior and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of dissimilar metal organic framework materials, and provides a dissimilar metal zirconium-based metal organic framework complex with a semiconductor behavior, a preparation method and an application thereof, wherein the molecular formula of the complex is as follows: [ Zr ] 6 (μ 3 ‑OH) 8 (OH) 8 ][(Cu 2 I 2 )(INA) 4 ] 2 Xguest, where INA represents isonicotinate. The preparation of the complex of the invention is that ZrCl is weighed in turn 4 Dissolving CuI and isonicotinic acid in an organic solvent, placing the obtained mixed solution in a reaction kettle, reacting under heating condition, and cooling to obtain the final product. The complex is a rare Kagome type zirconium-based metal organic framework constructed by taking different metal clusters as nodes, has a typical semiconductor behavior, and can be used for preparing semiconductor materials.
Description
Technical Field
The invention relates to the technical field of dissimilar metal organic framework materials, in particular to a dissimilar metal zirconium-based metal organic framework complex with a semiconductor behavior, and a preparation method and application thereof.
Background
The dissimilar metal organic framework material has the advantages of two or even multiple metal nodes and organic ligands, has potential application prospects in multiple fields and is concerned by researchers at home and abroad. Due to the coordination competition relationship among metal ions, the synthesis of the dissimilar metal organic framework material faces huge challenges. The zirconium-based dissimilar metal organic framework material has the characteristics of low crystallinity and difficulty in obtaining a single crystal structure, so that the design and synthesis of the material become particularly difficult.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides a dissimilar metal zirconium-based metal organic framework complex with semiconductor behavior, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a dissimilar metal zirconium-based metal organic framework complex with semiconductor behavior, which has a chemical formula as follows: [ Zr ] 6 (μ 3 -OH) 8 (OH) 8 ][(Cu 2 I 2 )(INA) 4 ] 2 Xguest, where INA is the isonicotinic acid anion and guest represents the guest molecule in the pore channel.
In the invention, furthermore, the asymmetric unit of the complex contains 0.75 Zr 4+ Ion, 0.5 Cu + Ion, 0.5I – 1 isonicotinate, 1 OH – And 1 μ 3 -OH; the complex is quadrilateral [ Cu ] 2 I 2 ]Cluster and dodecahedron [ Zr ] 6 O 8 ]The clusters are nodes, and are connected through isonicotinate to form a kagome type metal-organic framework with a novel structure.
In the present invention, further, the complex belongs to the hexagonal system, P6/mmm space group; the unit cell parameters are as follows:
c＝13.8480(17)，α＝90.0°，β＝90°，γ＝120°，
the invention also provides a preparation method of the dissimilar metal zirconium-based metal organic framework complex, which comprises the following steps: weighing ZrCl in sequence 4 Dissolving CuI and isonicotinic acid in an organic solvent, placing the obtained mixed solution in a reaction kettle, reacting under heating condition, and cooling to obtain the final product.
Wherein, the ZrCl 4 The molar ratio of CuI to isonicotinic acid is 1.5: 4: 14.6.
wherein the organic solvent is N, N-dimethylformamide and acetic acid with a volume ratio of 20: 1.
Preferably, the reaction is carried out at a heating rate of 30 ℃/h to 1115-125 ℃ under heating.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention provides a preparation method of a dissimilar metal zirconium-based organic framework with a novel structure, and the complex shows a semiconductor behavior and can be used for preparing a semiconductor material.
Drawings
FIG. 1 is a diagram showing the coordination environment of Zr1 in the complex of the present invention;
FIG. 2 is a diagram showing the coordination environment of Zr2 in the complex of the present invention;
FIG. 3 shows [ Zr ] in the complex of the present invention 6 (μ 3 -OH) 8 (OH) 8 ] 8+ A cluster map;
FIG. 4 is a diagram showing the coordination environment of Cu1 in the complex of the present invention;
FIG. 5 shows [ Cu ] in the complex of the present invention 2 I 2 ]A unit diagram;
FIG. 6 is a diagram of the coordination environment of the ligands in the complex of the present invention;
FIG. 7 is a three-dimensional block diagram of a complex of the present invention;
FIG. 8 is a topological diagram of a complex of the present invention;
FIG. 9 is the powder diffraction experimental spectrum and the simulated spectrogram of the complex of the invention;
FIG. 10 is a graph of the conductivity of a complex of the present invention at room temperature;
FIG. 11 is a graph of the temperature swing conductivity of a complex of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a dissimilar metal zirconium-based metal organic framework complex with semiconductor behavior, which has a chemical formula as follows: [ Zr ] 6 (μ 3 -OH) 8 (OH) 8 ][(Cu 2 I 2 )(INA) 4 ] 2 Xguest, where INA is the isonicotinic acid anion, guest represents the guest solvent molecule in the pore channel, and both x and guest require a series of characterizations to be determined.
Example 1
Accurately weighing isonicotinic acid (180mg, 1.46mmol) and ZrCl respectively 4 (35mg, 0.15 mmol), CuI (76mg, 0.4mmol) in a 25mL reactor in a polytetrafluoroethylene liner, 8mL of N, N-Dimethylformamide (DMF) and 0.4mL of acetic acid were added. After being mixed evenly, the inner cover is covered tightly and is arranged in a stainless steel jacket to be screwed tightly. The reaction kettle is put into an oven, the temperature is raised to 120 ℃ at the heating rate of 30 ℃/h, the reaction is carried out for 48h, and then the temperature is lowered to room temperature at the cooling rate of 2.5 ℃/h, so that orange strip-shaped body crystals are obtained, and the yield is about 60 percent (based on zirconium salt).
The product obtained in example 1 was characterized and characterized:
1) structural characterization:
selecting under microscope with proper size, regular shape and clean and intact surfaceUsing Supernova type single crystal X-ray diffractometer, using Mo Ka rays monochromatized by a graphite monochromator
As a source of incident light, to
And collecting diffraction points in a scanning mode. The crystal structure of the complex is solved by a direct method through Shelxtl and Olex2 software, and non-hydrogen atom coordinates and anisotropic thermal parameters utilize full-matrix least squares F 2 And (4) correcting the method. Because the solvent molecules in the pore channels are highly disordered, the number of electrons in the pore channels is calculated by adopting a SQUEEZE command in PLATON software, so that the guest molecules in the crystal structure can be roughly presumed. The relevant crystallographic parameters are listed in table 1.
TABLE 1
The asymmetric unit of the complex contains 0.75 Zr (IV) ion, 0.5 Cu (I) ion and 0.5I – 1 isonicotinate radical, 1 OH – And 1 μ 3 -OH. The complex contains two types of Zr (IV) ions: zr1 coordinated to 8 oxygen atoms from 4 μ 3 -OH (O1, O1C, O2, O2B) and the oxygen atoms on the 4 isonicotinic acid carboxylic acid groups (O6, O6B, O6C, O6D), forming a double-capped triangular prism configuration (fig. 1); zr2 is also coordinated to 8 oxygen atoms, each from 4. mu. 3 -OH (O1, O1E, O2, O2D), 2 OH – And oxygen atoms (O3, O4) on 2 isonicotinic acid carboxylic acid groups (O5, O15E) form an inverse quadrangular prism configuration (fig. 2). Two Zr1 atoms lying in the axial plane and four Zr2 atoms lying in the equatorial plane, passing through 8 μ 3 -OH bridges to form one tenOf dihedral configuration [ Zr 6 (μ 3 -OH) 8 (OH) 8 ] 8+ Cluster (fig. 3). The tetracoordinated Cu1 atom coordinates with the N atoms (N1, N1F) and 2I atoms (I1, I2) on 2 isonicotinates, forming a distorted tetrahedral configuration (fig. 4). Two Cu atoms and two I – The ions forming a planar quadrilateral [ Cu ] 2 I 2 ]The cell (fig. 5). A Zr-O bond length of
A Cu-N bond length of
A Cu-I bond length of
To
They are all within the range of bond lengths reported in the literature. As shown in FIG. 6, isonicotinic acid is expressed in μ 3 -η 1 :η 1 :η 1 The coordination mode of (a), each isonicotinic acid molecule may coordinate with two zr (iv) and one cu (i).
Each of [ Zr ] 6 (μ 3 -OH) 8 (OH) 8 ] 8+ The cluster passes through 8 isonicotinate radicals and 8 [ Cu ] 2 I 2 ]Are clustered each [ Cu ] 2 I 2 ]Clustering through 4 isonicotinic acids and 4 [ Zr ] 6 (μ 3 -OH) 8 (OH) 8 ] 8+ And the clusters are connected to form a kagome type three-dimensional frame with hexagonal and triangular pore channels, wherein the inner diameters of the two pore channels are 2.6nm and 1.3nm respectively (figure 7). Is reaction of [ Zr ] 6 (μ 3 -OH) 8 (OH) 8 ] 8+ Cluster and [ Cu 2 I 2 ]Respectively simplified into nodes and isonicotinic acid into lines, and then csq topological structures of 8 and 4 connections are formed, wherein the topological symbol is {4 } 16 .6 12 }{4 4 .6 2 } 2 (FIG. 8).
The complex belongs to the hexagonal system, P6/mmm space group. The unit cell parameters are:
c＝13.8480(17)，α＝90.0°，β＝90°，γ＝120°，
2) and (3) semiconductor performance measurement:
to characterize the complex semiconductor properties, electrical testing was performed on a Keithley 4200A-SCS and probe station lakeshore instrument. The sample was ground to a uniform powder in a mortar and then added to a standard circular tablet die with a diameter of 3mm, and pressed for 20 minutes under a pressure of 0.5T to obtain a compact tablet sample. And measuring the thickness of the wafer by using a vernier caliper, uniformly coating conductive silver paste on the upper surface and the lower surface, and connecting gold wires. And applying a voltage of-5V to the test sample by a two-electrode method, testing the change of the current and obtaining an I-V volt-ampere curve of the test sample. The conductivity of the sample is estimated in conjunction with the formula σ L/(R · S), where σ: electrical conductivity; l, measuring the thickness of the round sample by using a vernier caliper; r: resistance obtained through the slope of the volt-ampere characteristic curve; s: cross-sectional area of the wafer sample. From FIG. 10, it can be understood that the conductivities of the samples are 1.95X 10, respectively -8 S/cm。
In addition, the samples were tested for conductivity change at varying temperatures. As shown in fig. 11, as the temperature increases, the current gradually increases, the resistance gradually decreases, and the conductivity gradually increases, indicating that the complex has a typical semiconductor behavior.
The above description is for the purpose of illustrating the preferred embodiments of the present invention, but the present invention is not limited thereto, and all changes and modifications that can be made within the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. A dissimilar metal zirconium based metal organic framework complex having semiconducting behavior characterized by: the chemical formula is as follows: [ Zr ] 6 (μ 3 -OH) 8 (OH) 8 ][(Cu 2 I 2 )(INA) 4 ] 2 Xguest, where INA is isonicotinic acid anion and guest represents guest molecules in the channel.
2. The dissimilar metal zirconium-based metal-organic framework complex according to claim 1, wherein: the asymmetric unit of the complex contains 0.75 Zr 4+ Ion, 0.5 Cu + Ion, 0.5I – 1 isonicotinate radical, 1 OH – And 1 μ 3 -OH; the complex is in quadrilateral [ Cu ] 2 I 2 ]Cluster and dodecahedron [ Zr ] 6 O 8 ]The clusters are nodes which are connected through isonicotinate to form a kagome type metal organic framework.
3. The dissimilar metal zirconium-based metal-organic framework complex according to claim 1, wherein: the complex belongs to a hexagonal crystal system, P6/mmm space group; the unit cell parameters are as follows:
c＝13.8480(17)，α＝90.0°，β＝90°，γ＝120°，
4. a process for the preparation of a dissimilar metal zirconium based metal organic framework complex according to any one of claims 1 to 3, comprising the steps of: weighing ZrCl in sequence 4 Dissolving CuI and isonicotinic acid in an organic solvent, placing the obtained mixed solution in a reaction kettle, reacting under heating condition, and cooling to obtain the final product.
5. The method for preparing a dissimilar metal zirconium-based metal-organic framework complex according to claim 4, wherein: said ZrCl 4 The molar ratio of CuI to isonicotinic acid is 1.5: 4: 14.6.
6. the method for preparing a dissimilar metal zirconium-based metal-organic framework complex according to claim 4, wherein: the volume ratio of the organic solvent is 20:1, and acetic acid.
7. The method of preparing a dissimilar metal zirconium-based metal-organic framework complex according to claim 4, wherein: the temperature of the reaction is raised to 115-125 ℃ at the heating rate of 30 ℃/h, and then the reaction is carried out at the temperature.
8. Use of the isometalzirconium-based metal-organic framework complex according to any one of claims 1 to 3 for the manufacture of a semiconducting material.
9. Use of the isometal zirconium-based metal-organic framework complex prepared by the preparation method of any one of claims 4 to 7 in the preparation of semiconductor materials.
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| US20150291870A1 (en) * | 2012-08-15 | 2015-10-15 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| CN105622654A (en) * | 2015-12-25 | 2016-06-01 | 厦门大学 | Rare earth metal organic frame material with isonicotinic acid and glycolic acid as mixed ligand and preparing method thereof |
| CN112521618A (en) * | 2020-10-30 | 2021-03-19 | 山东大学 | Bismuth-based metal organic framework material and preparation method and application thereof |
| CN114409915A (en) * | 2022-01-20 | 2022-04-29 | 中国计量大学 | Fluorescent material based on zirconium-based metal organic framework structure and preparation method and application thereof |
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Patent Citations (5)
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| US20150291870A1 (en) * | 2012-08-15 | 2015-10-15 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| CN104892518A (en) * | 2014-03-05 | 2015-09-09 | 中国科学院大连化学物理研究所 | Preparation method and application of porous nano metal organic framework material |
| CN105622654A (en) * | 2015-12-25 | 2016-06-01 | 厦门大学 | Rare earth metal organic frame material with isonicotinic acid and glycolic acid as mixed ligand and preparing method thereof |
| CN112521618A (en) * | 2020-10-30 | 2021-03-19 | 山东大学 | Bismuth-based metal organic framework material and preparation method and application thereof |
| CN114409915A (en) * | 2022-01-20 | 2022-04-29 | 中国计量大学 | Fluorescent material based on zirconium-based metal organic framework structure and preparation method and application thereof |
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