Zirconium metal organic framework material based on phenazine and preparation method and application thereof

Abstract

The invention belongs to the technical field of photoelectric functional materials, and particularly relates to a zirconium metal organic framework material based on phenazine and a preparation method and application thereof. Zirconium metal organic framework materials prepared by introducing different types of dihydrophenazine derivative ligands are grown on the surface layer of FTO conductive glass based on the oxidation-reduction property of phenazine derivatives to form a layer of metal organic framework film material, and electrochromism of the material can be realized under the condition that voltage is applied to the metal organic framework film material; good application prospects are realized in the fields of medicines, photoelectricity and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of optoelectronic functional materials, and in particular relates to a phenazine-based zirconium metal organic framework material and a preparation method and application thereof. Background Art

[0002] The information disclosed in the background of the invention is only intended to enhance the understanding of the overall background of the invention and should not be necessarily regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Metal-organic framework materials (MOFs) have shown broad application prospects in catalysis, gas adsorption, sensing and other fields due to their unique pore structure and controllability. In particular, the UiO-68 series of metal-organic framework materials have become one of the research hotspots due to their good thermal and chemical stability.

[0004] As electrochromic materials, metal organic framework materials have a high specific surface area, which enables the material to provide more active sites, thereby enhancing the electrochromic performance; they also have an adjustable pore structure, which can accurately control the transmission and storage of ions and molecules, thereby optimizing the color-changing effect. However, this type of material also has some problems, such as relatively insufficient stability. Its performance may decay to a certain extent under long-term use or complex environmental conditions; the synthesis process is often more complicated and requires strict control of reaction conditions and steps, which increases the preparation cost and difficulty to a certain extent. Summary of the invention

[0005] In response to the needs of the prior art, the purpose of the present invention is to provide a phenazine-based zirconium metal-organic framework material and a preparation method and application thereof. The present invention introduces a phenazine carboxylic acid ligand with redox properties, coordinates and self-assembles with zirconium tetrachloride, constructs a new type of UiO-68 metal-organic framework material, and applies it to the field of electrochromism.

[0006] Specifically, the present invention provides the following technical solutions:

[0007] In a first aspect of the present invention, a phenazine-based zirconium metal organic framework material is provided, wherein the chemical formula of the phenazine-based zirconium metal organic framework material is Zr6O4(OH)4L6; wherein Zr6O4(OH)4 is a hexanuclear zirconium cluster structure portion, and L is selected from 4,4'-(phenazine-5,10-diyl)dibenzoic acid and 4,4'-(5,12-diaza tetracene-5,12-diyl)dibenzoic acid in dihydrophenazine derivative ligands; the structural repeating unit of the phenazine-based zirconium metal organic framework material is as shown in Formula I:

[0008]

[0009] Preferably, the zirconium ions in the phenazine-based zirconium metal organic framework material are octa-coordinated, and six zirconium ions form a hexanuclear zirconium cluster structure Zr6O4(OH)4 and coordinate with the carboxylic acid oxygen of the dihydrophenazine derivative ligand to form a two-dimensional layered structure.

[0010] The second aspect of the present invention provides a method for preparing the above-mentioned phenazine-based zirconium metal organic framework material, specifically: mixing zirconium tetrachloride, 4,4'-(phenazine-5,10-diyl)dibenzoic acid, 4,4'-(5,12-diazatetracene-5,12-diyl)dibenzoic acid and a catalyst in an organic solvent, and conducting a solvothermal reaction to obtain the material.

[0011] Preferably, the molar ratio of the zirconium tetrachloride, 4,4'-(phenazine-5,10-diyl)dibenzoic acid, 4,4'-(5,12-diaza-tetraphenyl-5,12-diyl)dibenzoic acid and the catalyst is 1:0.1-0.9:0.9-0.1:30-60; further preferably, the molar ratio of the zirconium tetrachloride, 4,4'-(phenazine-5,10-diyl)dibenzoic acid, 4,4'-(5,12-diaza-tetraphenyl-5,12-diyl)dibenzoic acid and the catalyst is 1:0.5:0.5:50.

[0012] Preferably, the organic solvent is selected from one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), 1,4-dioxane, and dimethyl sulfoxide.

[0013] Preferably, the catalyst is selected from benzoic acid and acetic acid.

[0014] Preferably, the temperature of the solvent thermal reaction is 100-120° C. and the time is 24-72 hours.

[0015] The third aspect of the present invention provides an application of the phenazine-based zirconium metal organic framework material described in the first aspect in an electrochromic material.

[0016] A fourth aspect of the present invention provides an electrochromic thin film material, comprising the phenazine-based zirconium metal organic framework material described in the first aspect.

[0017] The beneficial effects achieved by one or more of the above technical solutions of the present invention are as follows:

[0018] (1) Based on the redox properties of phenazine derivatives, the present invention grows them on the surface of FTO conductive glass to form a metal organic framework film material. When a voltage is applied to it, the material can be electrochromic, which has excellent application prospects in the fields of medicine, optoelectronics, etc.

[0019] (2) Compared with the metal-organic framework membrane materials prepared with a single ligand component, the metal-organic framework membrane materials prepared with a mixed ligand component are more stable and can realize multiple cycle experiments of electrochromism while maintaining the integrity of the metal-organic framework structure. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0021] Figure 1 is a microscope picture of a microcrystal sample prepared in Example 1 of the present invention;

[0022] Figure 2 This is a SEM picture of nanocrystals prepared by glacial acetic acid in Example 2 of the present invention;

[0023] Figure 3 is the powder diffraction PXRD pattern of UiO-68 prepared in Example 1 of the present invention;

[0024] Figure 4 is a schematic diagram of an electrochromic experiment of Example 1 of the present invention;

[0025] Figure 5 It is a color change diagram of the present invention in the electrochromic experiment of MOF;

[0026] Figure 6 It is the powder diffraction PXRD spectrum of the MOF grown on the FTO conductive glass before and after the electrochromic test of the present invention;

[0027] Figure 7 This is a test diagram of the cyclic stability of Example 1 of the present invention in an electrochromic test;

[0028] Figure 8 This is a test chart of the cyclic stability of comparative example 1 of the present invention in an electrochromic test. DETAILED DESCRIPTION

[0029] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0030] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.

[0031] Example 1 :This embodiment provides a phenazine-based zirconium metal organic framework material and a preparation method thereof

[0032] (1) 9.3 mg of zirconium tetrachloride, 8.5 mg of 4,4'-(phenazine-5,10-diyl)dibenzoic acid and 9.5 mg of 4,4'-(5,12-diazanaphthacene-5,12-diyl)dibenzoic acid were mixed in 1.6 mL of DMF solvent system and stirred at room temperature to obtain a mixture I;

[0033] (2) Add 244 mg of catalyst benzoic acid to the mixture I obtained in step (1), then perform a solvent thermal synthesis reaction at 120° C. for 24 h, cool naturally, and wash the product with a mixed solvent of DMF and methanol, and then vacuum dry to obtain light yellow microcrystals.

[0034] Example 2 :This embodiment provides a phenazine-based zirconium metal organic framework material and a preparation method thereof

[0035] (1) 9.3 mg of zirconium tetrachloride, 8.5 mg of 4,4'-(phenazine-5,10-diyl)dibenzoic acid and 9.5 mg of 4,4'-(5,12-diazanaphthacene-5,12-diyl)dibenzoic acid were mixed in 1.6 mL of DMF solvent system and stirred at room temperature to obtain a mixture I;

[0036] (2) Add 120 μL of glacial acetic acid as a catalyst to the mixture I obtained in step (1), and then perform a solvent thermal synthesis reaction at a temperature of 120° C. for 24 hours, cool naturally, and wash the product with a mixed solvent of DMF and methanol, and then vacuum dry to obtain a light yellow powder.

[0037] Example 3 : This test example uses an electron microscope and a scanning electron microscope to observe the structure and morphology characteristics of the materials prepared in Examples 1 to 2.

[0038] like Figure 1 As shown, the electron microscope image shows that the material prepared in Example 1 (using benzoic acid as a catalyst) produces microcrystals with a size of 200 to 300 microns.

[0039] like Figure 2 As shown, the material prepared in Example 2 (using glacial acetic acid as a catalyst) has a crystal size of 15 to 20 microns.

[0040] like Figure 3 As shown, the PXRD test diagram shows that the characteristic peaks of the materials prepared in Examples 1 to 2 appear at 4.6, 5.3, 8.8, 9.2°, etc., which are basically consistent with the XRD spectrum of the UiO-68 type MOF reported in the literature, proving that the materials prepared in Examples 1 to 2 of the present invention are consistent with the UiO-68 type MOF structure.

[0041] Comparative Example 1 :

[0042] (1) mixing 9.3 mg of zirconium tetrachloride and 16.9 mg of 4,4'-(phenazine-5,10-diyl)dibenzoic acid in 1.6 mL of DMF solvent system, and stirring at room temperature to obtain a mixture I;

[0043] (2) Add 244 mg of catalyst benzoic acid to the mixture I obtained in step (1), then perform a solvent thermal synthesis reaction at 120° C. for 24 h, cool naturally, and wash the product with a mixed solvent of DMF and methanol, and then vacuum dry to obtain light yellow microcrystals.

[0044] Comparative Example 2 :

[0045] (1) mixing 9.3 mg of zirconium tetrachloride and 16.9 mg of 4,4'-(phenazine-5,10-diyl)dibenzoic acid in 1.6 mL of DMF solvent system, and stirring at room temperature to obtain a mixture I;

[0046] (2) Add 120 μL of catalyst acetic acid to the mixture I obtained in step (1), then perform a solvent thermal synthesis reaction at a temperature of 120° C. for 24 h, cool naturally, and wash the product with a mixed solvent of DMF and methanol, and then vacuum dry to obtain a light yellow powder.

[0047] Application Example 1 :

[0048] During the preparation process of the phenazine-based zirconium metal organic framework material described in Example 1 and Comparative Example 1, the FTO conductive glass was placed vertically in a reactor, and after the reaction was completed, the UiO-68-loaded FTO glass was obtained, and then an electrochromic experiment was performed on it by immersing it in a phosphate electrolyte solution.

[0049] like Figure 4 , which is a diagram of the experimental process of Example 1;

[0050] like Figure 5 The photo shown in FIG. 1 shows the electrochromic experiment of Example 1 before and after the reaction. When a voltage of +1 V is applied, the color of the conductive glass changes from the original orange-yellow to green; when a voltage of -1 V is applied, the original color is restored.

[0051] like Figure 6 As shown, the peak position in PXRD did not change before and after power was applied, proving that the synthesized crystal structure remained unchanged.

[0052] like Figure 7As shown, after 5 reciprocating cycles, the crystal structure prepared in Example 1 still exists stably and has cyclic stability.

[0053] like Figure 8 As shown, after one reciprocating cycle, it can be seen from the PXRD spectrum that the characteristic peaks of the crystal of Comparative Example 1 at 4.6 and 5.3° almost disappear after one electrochromic cycle, proving that the crystal structure prepared in Comparative Example 1 has been destroyed. This shows that the crystal of Example 1 prepared by mixed ligands has stronger structural stability and can support multiple cycle tests.

[0054] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A phenazine-based zirconium metal organic framework material, characterized in that: The chemical formula of the phenazine-based zirconium metal organic framework material is Zr6O4(OH)4L6; wherein Zr6O4(OH)4 is a hexanuclear zirconium cluster structure portion, and L is selected from 4,4'-(phenazine-5,10-diyl)dibenzoic acid and 4,4'-(5,12-diaza tetracene-5,12-diyl)dibenzoic acid in dihydrophenazine derivative ligands; the structural repeating unit of the phenazine-based zirconium metal organic framework material is shown in Formula I:

2. The phenazine-based zirconium metal organic framework material according to claim 1, characterized in that: The zirconium ions in the phenazine-based zirconium metal organic framework material are eight-coordinated, and six zirconium ions form a hexanuclear zirconium cluster structure Zr6O4(OH)4 and coordinate with the carboxylic acid oxygen of the dihydrophenazine derivative ligand to form a two-dimensional layered structure.

3. A method for preparing a phenazine-based zirconium metal organic framework material according to any one of claims 1 to 2, characterized in that: Specifically, zirconium tetrachloride, 4,4'-(phenazine-5,10-diyl)dibenzoic acid, 4,4'-(5,12-diazanaphthacene-5,12-diyl)dibenzoic acid and a catalyst are mixed in an organic solvent and subjected to a solvothermal reaction to obtain the product.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the zirconium tetrachloride, 4,4'-(phenazine-5,10-diyl)dibenzoic acid, 4,4'-(5,12-diaza-naphthene-5,12-diyl)dibenzoic acid and the catalyst is 1:0.1-0.9:0.9-0.1:30-60.

5. The preparation method according to claim 4, characterized in that: The molar ratio of the zirconium tetrachloride, 4,4'-(phenazine-5,10-diyl)dibenzoic acid, 4,4'-(5,12-diaza-naphthene-5,12-diyl)dibenzoic acid and the catalyst is 1:0.5:0.5:

50.

6. The preparation method according to claim 3, characterized in that: The organic solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, 1,4-dioxane and dimethyl sulfoxide.

7. The preparation method according to claim 3, characterized in that: The catalyst is selected from benzoic acid and acetic acid.

8. The preparation method according to claim 3, characterized in that: The temperature of the solvent thermal reaction is 100-120° C. and the time is 24-72 hours.

9. Use of the phenazine-based zirconium metal organic framework material according to any one of claims 1 to 2 in electrochromic materials.

10. An electrochromic thin film material, characterized in that: The invention comprises the phenazine-based zirconium metal organic framework material as described in any one of claims 1 to 2.

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