Zirconium-based metal organic framework and preparation method thereof

Abstract

The invention relates to a zirconium-based metal organic framework which is synthesized by introducing a reaction system containing a diketone building block, an aldehyde building block, ammonium acetate and a Zr metal source into an in-situ building block one-pot method system through a Debus-Radziszewski reaction. Wherein in the reaction process, diketone building blocks, aldehyde building blocks and ammonium acetate synthesize an organic ligand, meanwhile, the organic ligand and a Zr metal source are coordinated to synthesize the zirconium-based metal organic framework, and the zirconium-based metal organic framework is polycarboxylic acid Zr-MOFs. The zirconium-based metal organic framework Zr-MOF synthesized by the invention has good luminescence characteristic, so that the Zr-based metal organic framework Zr-MOF can be applied to the field of substance detection or biological imaging.

Description

Technical Field

[0001] The invention relates to the technical field of metal organic frameworks, in particular to a zirconium-based metal organic framework and a preparation method thereof. Background Art

[0002] Metal-organic frameworks (MOFs) are constructed from organic ligands and metal ions or clusters, and have the characteristics of adjustable composition and structure, easy functionalization and inherent porosity. Among them, MOFs with zirconium clusters (Zr clusters) as inorganic building blocks, referred to as Zr-MOFs, have a variety of carboxylic acid organic ligands and Zr clusters. The connection number and strong Zr-O bond show predictable and diverse topological structures, better thermodynamic and chemical stability, and are widely used in many research fields such as chemical adsorption, separation, storage, photoelectrocatalysis, chemical sensing, and bioimaging.

[0003] For Zr-MOFs, the traditional construction method is to first obtain carboxylic acid ester compounds through multi-step organic synthesis, separation and purification, then acidify to obtain the target organic ligand, and then perform solvothermal reaction to construct Zr-MOFs. For the organic ligands of polycarboxylic acids, the organic synthesis process is usually more complicated, and the low solubility of the compounds often makes the separation and purification method more difficult, resulting in fewer reports on polycarboxylic acid Zr-MOFs. Therefore, developing a new method for synthesizing organic ligands and the corresponding method for constructing Zr-MOFs is the only way to promote the development of polycarboxylic acid-Zr-MOFs, and is the key method to further enrich the structure and functional system of MOFs.

[0004] As an alternative to traditional MOFs construction, the in situ “one-pot” strategy, in which the synthesis of organic ligands and the construction of MOFs occur simultaneously, has been used in the design and development of MOFs. It was first reported by Champness and Schröder et al. in 1997. However, to date, most of the work has focused on nitrogen-containing organic ligands for use with low-valent metal ions such as Ag. + , Cu 2+ , Zn 2+ etc., to form MOFs. It was not until 2018 that this method was used for the construction of Zr-MOFs. The reactions used for the in-situ one-pot method include the diazo coupling reaction of nitro compounds, boric acid condensation reaction, Schiff base reaction, reaction of anhydride and amino group, and the reaction of o-phenylenediamine and aldehyde to form benzimidazole.

[0005] The in-situ one-pot method has more advantages than the traditional method, but the number of reactions that can be used for the in-situ one-pot method is small and its development is slow. Therefore, the development of a new reaction system suitable for the in-situ one-pot method can provide a new idea for the development of polycarboxylic acid Zr-MOFs and provide a reference for further enriching the structure and functional system of Zr-MOFs. Summary of the invention

[0006] The technical problem to be solved by the present invention is: to synthesize polycarboxylic acid Zr-MOFs by an in-situ one-pot method.

[0007] In order to solve the above technical problems, the present invention adopts the following technical solutions: The zirconium-based metal organic framework is synthesized by a one-pot system of introducing in-situ building blocks through the Debus-Radziszewski reaction from a reaction system comprising diketone building blocks, aldehyde building blocks, ammonium acetate and a Zr metal source; wherein during the reaction, the diketone building blocks, aldehyde building blocks and ammonium acetate synthesize organic ligands, and at the same time, the organic ligands coordinate with the Zr metal source to synthesize the zirconium-based metal organic framework, which is a polycarboxylic acid Zr-MOFs.

[0008] Furthermore, the molecular formula of the zirconium-based metal organic framework is Zr6O4(OH)8(H2O)4(ligand)2.

[0009] Specifically, in the reaction process: diketone building blocks, aldehyde building blocks, and ammonium acetate are used as reaction building blocks to synthesize organic ligands, and the organic ligands are coordinated and synthesized with Zr metal sources in the same reaction system; and a solvent and a regulator are added to the reaction system.

[0010] As a non-limiting example, the relative amount of diketone building blocks in the reaction system is 0.01 ~ 0.1 mmol, the relative amount of aldehyde building blocks is 0.01 ~ 0.06 mmol, the relative amount of ammonium acetate is 0.1 ~ 1.0 mmol, and the relative amount of the Zr metal source is 0.1 ~ 0.5 mmol; amide is added to the reaction system as a solvent, and an organic acid is added to the reaction system as a regulator.

[0011] In some embodiments, the diketone building block is 4,4'-oxalyldibenzoic acid; the aldehyde building block is benzo[c][1,2,5]thiadiazole-4,7-dicarboxaldehyde or 5'-formyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid, and the Zr metal source is ZrCl4.

[0012] In some embodiments, the organic ligand is organic ligand A, and the organic ligand A is 4,4',4'',4''-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(1H-imidazole-2,4,5-triyl))tetrabenzoic acid; the zirconium-based metal organic framework is HIAM-4029-op; and the synthesis reaction of the zirconium-based metal organic framework includes reaction formulas (1) and (3) occurring before and after: + +NH4OAc → (1) (3) The synthesis reactions of formula (1) and formula (3) occur successively in the same reaction system.

[0013] In some embodiments, the organic ligand is an organic ligand B, and the organic ligand B is 5'-(4,5-bis(4-carboxyphenyl)-1H-imidazole-2-yl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid; the zirconium-based metal organic framework is HIAM-4028-op; and the synthesis reaction of the zirconium-based metal organic framework includes reaction equations (2) and (4) occurring successively: + +NH4OAc → (2) (4) The synthesis reactions of formula (2) and formula (4) occur successively in the same reaction system.

[0014] In some embodiments, the zirconium-based metal organic framework is a crystal with an scu-type topological structure, and its crystal structure has a quadrilateral channel with a channel radius of 5-6Å and a hexagonal channel of 9-10Å; in the molecular structure of the zirconium-based metal organic framework, each Zr6 cluster is connected to 8 tetracarboxylic acid ligands and 8 terminal H2O / OH - group, each tetracarboxylic acid ligand corresponds to four Zr6 clusters.

[0015] In some embodiments, the zirconium-based metal-organic framework emits fluorescence when excited by 365nm light, and its maximum emission peak is 700nm, which belongs to the luminescence range of the near-infrared region, and the maximum ultraviolet absorption value is 800nm, which has a wide absorption range. The zirconium-based metal-organic framework is used in the field of biological imaging.

[0016] In some embodiments, the zirconium-based metal-organic framework emits fluorescence when excited by 365nm light, with a maximum emission peak of 450nm, which belongs to blue light emission in the visible light range, and a maximum ultraviolet absorption value of 600nm. The zirconium-based metal-organic framework is applied in the field of material detection.

[0017] The present invention provides a method for preparing a zirconium-based metal organic framework, comprising the following steps: Step 1, preparing the reaction system, in which zirconium tetrachloride is used as a Zr metal source, diketone building blocks, aldehyde building blocks, and ammonium acetate are used as reaction building blocks to synthesize organic ligands for coordination with the Zr metal source, formamide is used as an organic solvent, and formic acid and / or acetic acid and / or trifluoroacetic acid are used as regulators to regulate the growth of the zirconium-based metal organic framework; Step 2, after the reaction system is uniformly mixed, the organic ligand is constructed and synthesized at 90-150° C., and the organic ligand and the metal source are coordinated and synthesized; Step 3: After reacting for a predetermined time, cool the mixture to obtain the zirconium-based metal organic framework described in any of the above embodiments.

[0018] The beneficial effects of the present invention are: The present invention synthesizes polycarboxylic acid Zr-MOFs through an in-situ one-pot method, thereby further enriching the structure and functional system of Zr-MOFs.

[0019] Furthermore, the zirconium-based metal organic framework Zr-MOF synthesized by the present invention has good luminescence properties, so that it can be used in the field of material detection or biological imaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 It is a crystal photograph of HIAM-4029-op according to an embodiment of the present invention.

[0021] Figure 2 It is a crystal photograph of HIAM-4028-op according to an embodiment of the present invention.

[0022] Figure 3 It is a fluorescence spectrum diagram of HIAM-4029-op according to an embodiment of the present invention.

[0023] Figure 4 It is the ultraviolet absorption spectrum of HIAM-4029-op of the embodiment of the present invention.

[0024] Figure 5 It is a fluorescence spectrum diagram of HIAM-4028-op according to an embodiment of the present invention.

[0025] Figure 6 It is the ultraviolet absorption spectrum of HIAM-4028-op of the embodiment of the present invention.

[0026] Figure 7 1 is a crystal structure diagram of HIAM-4029-op according to an embodiment of the present invention.

[0027] Figure 8 1 is a crystal structure diagram of HIAM-4028-op according to an embodiment of the present invention. DETAILED DESCRIPTION

[0028] The exemplary embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although the exemplary embodiments of the present application are shown in the accompanying drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present application and to fully convey the scope of the present application to those skilled in the art.

[0029] It should be understood that the terms used herein are only for the purpose of describing specific example embodiments and are not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "one", "an" and "said" as used herein may also be meant to include plural forms. The terms "include", "comprise", "contain", and "have" are inclusive, and therefore specify the existence of stated features, steps, operations, elements and / or parts, but do not exclude the existence or addition of one or more other features, steps, operations, elements, parts, and / or combinations thereof. The method steps, processes, and operations described herein are not interpreted as necessarily requiring them to be performed in the specific order described or illustrated, unless the execution order is clearly indicated. It should also be understood that additional or alternative steps may be used.

[0030] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0031] The endpoints and any values ​​of the endpoint values ​​disclosed in the present invention are not limited to the precise range or value, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0032] The present invention introduces the Debus-Radziszewski reaction into the one-pot system of in-situ building blocks, and uses diketone building blocks, ammonium acetate and aldehyde building blocks to construct MOFs, thereby increasing the reaction system of the one-pot method of in-situ building blocks and enriching the structure and functional system of Zr-MOFs. The Zr-MOFs of the present invention use diketone building blocks, ammonium acetate and aldehyde building blocks to construct MOFs from the perspective of molecular design and regulation. Specifically, it is a reaction system comprising diketone building blocks, aldehyde building blocks, ammonium acetate and Zr metal sources. During the reaction, diketone building blocks, aldehyde building blocks and ammonium acetate are used for organic ligand synthesis. At the same time, the organic ligands are coordinated with the Zr metal source to synthesize the zirconium-based metal organic framework, and the zirconium-based metal organic framework is a polycarboxylic acid Zr-MOFs.

[0033] In the embodiments of the present invention, examples of diketone blocks and aldehyde building blocks are as follows: Diketone building block (4,4'-oxalyldibenzoic acid): ; Aldehyde building blocks: Aldehyde building block No. 1 (Benzo[c][1,2,5]thiadiazole-4,7-dicarboxaldehyde) ;or Aldehyde building block No. 2 (5'-formyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid) .

[0034] The exemplary reaction system comprises a diketone building block (4,4'-oxalyldibenzoic acid), an aldehyde building block No. 1 (benzo[c][1,2,5]thiadiazole-4,7-dicarboxaldehyde), ammonium acetate and a metal source ZrCl4; during the synthesis reaction, the diketone building block (4,4'-oxalyldibenzoic acid), the aldehyde building block No. 1 (benzo[c][1,2,5]thiadiazole-4,7-dicarboxaldehyde) and ammonium acetate in the reaction system are used as reaction building blocks to synthesize an organic ligand A (4,4', 4'',4''-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(1H-imidazole-2,4,5-triyl))tetrabenzoic acid), at the same time, the organic ligand A generated in the reaction system coordinates with the metal source ZrCl4 in the reaction system to synthesize the zirconium-based metal organic framework HIAM-4029-op, with the molecular formula of Zr6O4(OH)8(H2O)4(ligand A)2; the whole synthesis reaction is as shown in the above reaction formulas (1) and (3).

[0035] Another exemplary reaction system includes a diketone building block (4,4'-oxalyldibenzoic acid), an aldehyde building block No. 2 (5'-formyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid), ammonium acetate and a metal source ZrCl4; during the synthesis reaction, the diketone building block (4,4'-oxalyldibenzoic acid), the aldehyde building block No. 2 (5'-formyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid), and ammonium acetate in the reaction system are used as reaction building blocks. An organic ligand B (5'-(4,5-bis(4-carboxyphenyl)-1H-imidazole-2-yl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid) is synthesized. At the same time, the organic ligand B generated in the reaction system coordinates with the metal source ZrCl4 in the reaction system to synthesize a zirconium-based metal organic framework HIAM-4028-op, with a molecular formula of Zr6O4(OH)8(H2O)4(ligand B)2. The overall synthesis reaction is as shown in the above reaction formulas (2) and (4).

[0036] Among them, HIAM: Hoffmann Institute of Advanced Materials refers to the Hoffmann Institute of Advanced Materials, HIAM-4028-op and HIAM-4029-op are custom names; the synthesis reaction formulas of HIAM-4028-op and HIAM-4029-op by coordination of organic ligands A and B with ZrCl4 are as follows (3) and (4): (3) Organic ligand AZrCl4HIAM-4029-op (4) Organic ligand BZrCl4HIAM-4028-op. Example

[0037] The Zr-MOF of this embodiment has a molecular formula of Zr6O4(OH)8(H2O)4(ligand A)2 and is named HIAM-4029-op. Zirconium tetrachloride, diketone building blocks, ammonium acetate, and a regulator are added to an organic solvent to synthesize an organic ligand first, and then synthesize Zr-MOF. The exemplary synthesis method includes the following steps: Step 1, preparing a reaction system, which includes: zirconium tetrachloride (relative amount of 0.1 ~ 0.2 mmol or 23.3 ~ 46 mg) as a metal source, diketone building block (4,4'-oxalyldibenzoic acid) (relative amount of 0.042 ~ 0.084 mmol or 12.5 ~ 25 mg), No. 1 aldehyde building block (benzo[c][1,2,5]thiadiazole-4,7-dicarboxaldehyde) (relative amount of 0.02 ~ 0.04 mmol or 4 ~ 8 mg), ammonium acetate (relative amount of 0.4 ~ 0.8 mmol or 30.8 ~ 61.6 mg) as a reaction building block to synthesize an organic ligand A (4,4',4'',4''-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(1H-imidazole-2,4,5-triyl))tetrabenzoic acid), a regulator includes a relative amount of 0.5 ~ 1 mL formic acid and 50 ~ 100 μL trifluoroacetic acid, and each component is added to a relative amount of 3 ~ 5 mL dimethylformamide as an organic solvent to form a reaction system; the reaction system can be placed in a 3 mL small bottle; Step 2: After the reaction system is evenly mixed by ultrasonication for 3 to 5 minutes, it is placed in an oven at 120° C. to react and carry out the coordination synthesis reaction of the organic ligand and the metal source for 24 to 72 hours; Step 3: After the reaction system is cooled to room temperature, a red cubic crystal product of HIAM-4029-op is obtained.

[0038] Wherein, in step 2, the diketone building block, the aldehyde building block No. 1, and ammonium acetate in the reaction system react to synthesize the organic ligand A (4,4',4'',4''-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(1H-imidazole-2,4,5-triyl))tetrabenzoic acid) (relative amount is 0.042 ~ 0.084 mmol or 26 ~ 52 mg), and at the same time, the organic ligand A is coordinated with the Zr metal source to synthesize the zirconium-based metal organic framework HIAM-4029-op. Wherein, dimethylformamide is used as an organic solvent to provide a reaction environment for the reactants, and formic acid and trifluoroacetic acid are used as regulators to regulate the growth of the zirconium-based metal organic framework. The relative amount of the reactants is appropriately adjusted for complete reaction, and the amount of the organic solvent and the regulator can be appropriately adjusted.

[0039] Take pictures with an optical microscope, such as Figure 1 The figure shows the crystal morphology of HIAM-4029-op. The composition and structure of the red crystal of HIAM-4029-op were determined by single crystal diffraction. The single crystal diffraction results show that HIAM-4029-op crystallizes in an orthorhombic system with a Cmmm space group. Each Zr6 cluster is connected to 8 completely deprotonated organic ligands and 8 terminal H2O / OH -Each organic ligand connects four Zr6 clusters. The molecular formula is Zr6O4(OH)8(H2O)4(ligand A)2, refer to Figure 7 The figure shows the crystal structure of HIAM-4029-op, where (a), (b), and (c) are views of the crystal structure from different directions. It is found that the crystal structure has three different sizes of quadrilateral and hexagonal channels, one Zr6 cluster connected to eight organic ligands, and one organic ligand connected to four Zr6 clusters, forming an scu-type topological structure with eight connections of tetracarboxylic acids.

[0040] HIAM-4029-op has good optical properties and emits fluorescence under light excitation conditions. Its maximum emission peak can reach 700nm, which belongs to the near-infrared region I. It has a wide absorption range and can be used in fields such as biological imaging. Specifically, the fluorescence spectrum of HIAM-4029-op can be found at Figure 3 Its UV absorption spectrum is shown in Figure 4 ,Depend on Figure 3 As shown, the maximum emission peak of HIAM-4029-op is 700 nm when excited at 365 nm, which belongs to the luminescence range of the near-infrared region. Figure 4 As shown, the maximum UV absorption value is 800 nm, which has a wide absorption range. The luminescence characteristics of HIAM-4029-op make it suitable for use in the field of biological imaging. Example

[0041] The Zr-MOF of this embodiment has a molecular formula of Zr6O4(OH)8(H2O)4(ligand B)2 and is named HIAM-4028-op. Zirconium tetrachloride, diketone building blocks, ammonium acetate, and a regulator are added to an organic solvent to synthesize an organic ligand first, and then synthesize Zr-MOF. The exemplary synthesis method includes the following steps: Step 1, preparing a reaction system, which includes: zirconium tetrachloride (relative amount of 0.1 ~ 0.2 mmol or 23.3 ~ 46.6 mg) as a metal source, diketone building block (4,4'-oxalyldibenzoic acid) (relative amount of 0.022 ~ 0.044 mmol or 5.9 ~ 11.8 mg), aldehyde building block No. 2 (5'-formyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid) (relative amount of 0.024 ~ 0.048 mmol or 8.3 ~ 16.6 mg), ammonium acetate (relative amount of 0.2 ~ 0.4 mmol or 15.4 ~ 30.8 mg); mg) as a reaction building block to synthesize an organic ligand B (5'-(4,5-bis(4-carboxyphenyl)-1H-imidazol-2-yl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid), a regulator including 0.7 ~ 1 mL acetic acid and 50 ~ 100 μL trifluoroacetic acid, which are added to an organic solvent of 3 ~ 5 mL diethylformamide to form a reaction system, and the reaction system can be contained in a 3 mL small bottle; Step 2: After the reaction system is evenly mixed by ultrasonication for 3 to 5 minutes, it is placed in an oven at 120° C. to react and carry out a coordination synthesis reaction between the organic ligand and the metal source for 24 to 72 hours; Step 3: After the reaction system is cooled to room temperature, transparent cubic crystals of HIAM-4028-op are obtained.

[0042] In step 2, the diketone building block (4,4'-oxalyldibenzoic acid), aldehyde building block No. 2, and ammonium acetate in the reaction system are used as reaction building blocks to synthesize organic ligand B (5'-(4,5-bis(4-carboxyphenyl)-1H-imidazole-2-yl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid). Diethylformamide is used as an organic solvent to provide a reaction environment for the reactants, and acetic acid and trifluoroacetic acid are used as regulators to regulate the growth of the zirconium-based metal organic framework.

[0043] Take pictures with an optical microscope, refer to Figure 2 The crystal morphology of HIAM-4028-op is shown in Figure 1. Single crystal diffraction of HIAM-4028-op was performed to determine the composition and structure of the single crystal. The single crystal diffraction results show that HIAM-4028-op crystallizes in the tetragonal system of the P42 / mnm space group. In the structure of HIAM-4028-op, each Zr6 cluster is connected to 8 completely deprotonated tetracarboxylic acid ligands and 8 terminal H2O / OH - Each deprotonated tetracarboxylic acid ligand corresponds to four Zr6 clusters. Figure 8The crystal structure diagram of HIAM-4028-op is shown, where (a), (b), and (c) are observations of the crystal structure from different directions. It is found that the crystal structure has four different sizes of quadrilateral and hexagonal channels, one Zr6 cluster connects 8 organic ligands, and one organic ligand connects 4 Zr6 clusters.

[0044] The optical properties of HIAM-4028-op are within the visible light emission range and can be used in detection and other fields. Figure 5 As shown, its ultraviolet absorption spectrum is shown in Figure 6 As shown by Figure 5 It can be seen that the maximum emission peak of HIAM-4028-op is 450 nm when excited at 365 nm, which belongs to the blue light emission in the visible light range. Figure 6 It can be seen that the maximum ultraviolet absorption value is 600 nm. HIAM-4028-op has good luminescence properties, which makes it applicable in the detection field.

[0045] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. The zirconium-based metal organic framework is synthesized by a one-pot system of in-situ building blocks introduced by a reaction system comprising diketone building blocks, aldehyde building blocks, ammonium acetate and a Zr metal source through a Debus-Radziszewski reaction; wherein, During the reaction, diketone building blocks, aldehyde building blocks and ammonium acetate synthesize organic ligands. Meanwhile, the organic ligands coordinate with Zr metal sources to synthesize the zirconium-based metal organic framework, which is polycarboxylic acid Zr-MOFs.

2. The zirconium-based metal-organic framework according to claim 1, characterized in that: The molecular formula of the zirconium-based metal organic framework is Zr6O4(OH)8(H2O)4(ligand)2.

3. The zirconium-based metal-organic framework according to claim 1, characterized in that: In the reaction process, diketone building blocks, aldehyde building blocks and ammonium acetate are used as reaction building blocks to synthesize organic ligands, and the organic ligands and Zr metal sources are coordinated and synthesized in the same reaction system; and an organic solvent and a regulator are added to the reaction system.

4. The zirconium-based metal-organic framework according to claim 1, characterized in that: In the reaction system, the relative amount of diketone building blocks is 0.01 to 0.1 mmol, the relative amount of aldehyde building blocks is 0.01 to 0.06 mmol, the relative amount of ammonium acetate is 0.1 to 1.0 mmol, and the relative amount of Zr metal source is 0.1 to 0.5 mmol; an organic acid is added to the reaction system as a regulator, and an amide is added to the reaction system as a solvent.

5. The zirconium-based metal-organic framework according to claim 1, characterized in that: The diketone building block is 4,4'-oxalyldibenzoic acid; the aldehyde building block is benzo[c][1,2,5]thiadiazole-4,7-dicarboxaldehyde or 5'-formyl-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid, and the Zr metal source is ZrCl4.

6. The zirconium-based metal-organic framework according to claim 5, characterized in that: The organic ligand is an organic ligand A, and the organic ligand A is 4,4',4'',4''-(benzo[c][1,2,5]thiadiazole-4,7-diylbis(1H-imidazole-2,4,5-triyl))tetrabenzoic acid; the zirconium-based metal organic framework is HIAM-4029-op; the synthesis reaction of the zirconium-based metal organic framework includes reaction formulas (1) and (3) occurring before and after: + +NH4OAc → （1） (3) The synthesis reactions of formula (1) and formula (3) occur successively in the same reaction system.

7. The zirconium-based metal-organic framework according to claim 4, characterized in that: The organic ligand is an organic ligand B, and the organic ligand B is 5'-(4,5-bis(4-carboxyphenyl)-1H-imidazole-2-yl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid; the zirconium-based metal organic framework is HIAM-4028-op; The synthesis reaction of the zirconium-based metal organic framework includes reaction formulas (2) and (4) occurring one after the other: + +NH4OAc → （2） (4) The synthesis reactions of formula (2) and formula (4) occur successively in the same reaction system.

8. The zirconium-based metal-organic framework according to any one of claims 1 to 7, characterized in that: The zirconium-based metal organic framework is a crystal with an scu-type topological structure, and its crystal structure has a quadrilateral channel with a channel radius of 5-6Å and a hexagonal channel with a channel radius of 9-10Å; In the molecular structure of the zirconium-based metal organic framework, each Zr6 cluster is connected to 8 tetracarboxylic acid ligands and 8 terminal H2O / OH - group, each tetracarboxylic acid ligand corresponds to four Zr6 clusters.

9. The zirconium-based metal-organic framework according to claim 8, characterized in that: The zirconium-based metal organic framework emits fluorescence when excited by 365nm light, and its maximum emission peak is 700nm, which belongs to the luminescence range of the near-infrared region, and the maximum ultraviolet absorption value is 800nm, which has a wide absorption range. The zirconium-based metal organic framework is used in the field of biological imaging; or, The zirconium-based metal-organic framework emits fluorescence when excited by 365nm light, with a maximum emission peak of 450nm, belonging to blue light emission in the visible light range, and a maximum ultraviolet absorption value of 600nm. The zirconium-based metal-organic framework is applied in the field of material detection.

10. A method for preparing a zirconium-based metal organic framework, comprising the following steps: Step 1, preparing the reaction system, in which zirconium tetrachloride is used as a Zr metal source, diketone building blocks, aldehyde building blocks, and ammonium acetate are used as reaction building blocks to synthesize organic ligands for coordination with the Zr metal source, formamide is used as an organic solvent, and formic acid and / or acetic acid and / or trifluoroacetic acid are used as regulators to regulate the growth of the zirconium-based metal organic framework; Step 2, after the reaction system is uniformly mixed, the organic ligand is constructed and synthesized at 90-150° C., and the organic ligand and the metal source are coordinated and synthesized; Step 3: After reacting for a predetermined time, cool the mixture to obtain the zirconium-based metal organic framework according to any one of claims 1 to 9.

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