Universal preparation method for in-situ growth of carboxylic acid Zr-MOFs on macroscopic interface

Abstract

The invention discloses a universal preparation method for in-situ growth of carboxylic acid Zr-MOFs on a macroscopic interface. Soaking the glass bottle in a NaOH solution and a hydrochloric acid solution in sequence, then adding a piranha solution to activate surface hydroxyl, and modifying amino on the surface through APTES to obtain an aminated glass bottle; the preparation method comprises the following steps: directly adding a carboxylic acid ligand of Zr-MOFs to be synthesized as a carboxyl group introducing agent into an MES buffer solution, adding EDC and NHS to activate carboxyl groups, adding a PBS buffer solution, subpackaging into an aminated glass bottle, and modifying the surface of the glass bottle with the carboxylic acid ligand through an amide coupling reaction; and finally, growing different Zr-MOFs in situ. The universal preparation method provided by the invention not only solves the problem that powder Zr-MOFs are difficult to recycle and reuse, but also solves the problem that in-situ growth is limited by the coordination ability of anchoring groups, and provides a design thought for the development of novel composite materials.

Description

Technical Field

[0001] The invention relates to a universal preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs, belonging to the technical field of functional nanomaterial preparation. Background Art

[0002] Metal-organic frameworks (MOFs) are a class of crystalline materials self-assembled from metal ions and organic ligands through coordination bonds. Due to their high specific surface area, rich chemical functionality, and unique pore structure, MOFs show broad application prospects in gas adsorption and separation, drug controlled release, wastewater purification, catalysis, and sensing. However, after synthesis, MOFs typically exist in the form of fine powders. Despite their excellent structural properties, MOFs suffer from poor processability, difficulty in shaping, insufficient mechanical stability, and difficulties in recycling and reuse during use, which severely restrict their promotion and application in practical scenarios. To overcome these limitations, researchers in recent years have been committed to developing composite strategies for loading MOFs onto matrices such as carbon aerogels, polymer foams, and cellulose aerogels, to construct functional composite materials that combine the high microporous / mesoporous structure of MOFs with the good formability and mechanical stability of the matrix.

[0003] Two strategies are commonly used for loading MOFs: post-synthesis hybridization and in situ growth. The post-synthesis hybridization strategy involves compounding pre-synthesized MOFs with processable materials such as polymers, resins, or gels. By embedding MOF powder into a polymer matrix, a hybrid bulk material or matrix membrane is constructed. In such materials, MOFs exist solely as fillers, and the intrinsic pore structure of the polymer matrix plays a significant role in their physicochemical properties. However, MOF particles have poor dispersion within the matrix, are prone to agglomeration, and exhibit limited interactions with the matrix, making high loading and uniform distribution challenging. The in situ growth strategy, on the other hand, involves inducing MOF crystal growth directly on the support surface, exposing the MOFs as an active coating to the environment. This creates a material with MOFs as the functional host. Chemical modification introduces functional groups that facilitate the stable and uniform in situ growth of MOFs at the interface. This method has been widely used to grow MOFs in situ at the interfaces of ceramics, polymers, and metal oxides, and is suitable for applications in gas separation, electrochemical devices, and analytical detection (such as SPME fibers for solid-phase microextraction).

[0004] Introducing functional modification groups to construct anchoring sites is a generally effective strategy to achieve stable and uniform in situ growth of MOFs. In the construction of in situ growth systems of carboxylic acid Zr-MOFs, functional groups with coordination ability such as carboxyl groups are usually introduced into the substrate or interface, and then the Zr 4+ Pre-coordination occurs, thereby achieving Zr 4+The anchoring at the interface can effectively promote the orderly nucleation and growth of subsequent Zr-MOFs crystals. However, due to the differences in acidity (pKa) and electron donor ability between the anchoring modification group and the target carboxylic acid Zr-MOFs organic ligand, the Zr 4+ When the ligand is introduced into the system, its strong coordination ability may compete with the anchored functional group, thereby replacing the original coordination site, making the pre-coordinated Zr 4+ Dissociation occurs, and this competitive coordination process will interfere with Zr 4+ The spatial anchoring of MOFs hinders the directional nucleation and in situ assembly of MOFs at the interface. Summary of the Invention

[0005] In order to solve the problems that powdered carboxylic acid Zr-MOFs are difficult to recycle and reuse and their in-situ growth is limited by the coordination capacity of anchoring groups, the present invention provides a universal preparation method for in-situ growth of carboxylic acid Zr-MOFs at a macroscopic interface.

[0006] The present invention provides a general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs using the following technical solutions: The general preparation method comprises the following steps: Step 1): Soak the glass bottle in NaOH solution and hydrochloric acid solution in sequence, wash with deionized water until neutral, and heat and dry in an oven to obtain a glass bottle with a smooth surface; Step 2): adding piranha solution to the glass bottle with a smooth surface obtained in step 1) and soaking it, washing it with deionized water until it is neutral, and heating and drying it in an oven to obtain a hydroxyl-activated glass bottle; Step 3): Add APTES to the hydroxyl-activated glass bottle obtained in step 2), heat in an oven for reaction, wash with ethanol and deionized water three times respectively, and then heat and dry to obtain an amino-activated glass bottle; Step 4): Add the carboxyl ligand of the carboxylic acid Zr-MOFs to MES buffer, then add EDC and NHS to the buffer for reaction, then add PBS buffer, and then divide the mixed solution into the amino-treated glass bottles obtained in step 3), incubate on a shaker overnight, wash with ethanol and deionized water three times respectively, and heat dry in an oven to obtain glass bottles modified with the carboxyl ligand of the carboxylic acid Zr-MOFs; Step 5): PCN-777, MOF-525, NU-1000 or Zr-MOF-H4L carboxylic acid Zr-MOFs are in situ grown on the interface of the glass bottle modified with the carboxyl ligand obtained in step 4).

[0007] Preferably, in step 1), the concentration of the NaOH solution is 1 mol / L; the concentration of the hydrochloric acid solution is 0.1 mol / L; the soaking time is 6 h; and the heating and drying temperature is 60°C.

[0008] Preferably, the volume of the piranha solution in step 2) is 10 mL; the soaking time is 4 h; and the heating and drying temperature is 60°C.

[0009] Preferably, in step 3), the APTES solution is prepared by mixing 10 mL of ethanol with a volume concentration of 5% APTES; the heating reaction temperature is 60° C.; the heating reaction time is 24 h; the heating drying temperature is 120° C.; and the heating drying time is 1 h.

[0010] Preferably, in step 4), the carboxylic acid ligand is 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine, 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene, meso-tetrakis(4-carboxyphenyl)porphine or 4,4,4",4"-(pyrazino[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid; the amount of the carboxylic acid ligand added is 20 mg; the MES buffer is 15 mL of 0.1 mol / L MES buffer at a pH of 6; the amount of EDC added is 80 mg; the amount of NHS added is 120 mg; the reaction temperature is 37° C.; the reaction time is 15 min; the PBS buffer is 15 mL of 0.15 mol / L PBS buffer at a pH of 7.4, and the mixed solution is dispensed in 10 mL / bottle; the shaker temperature is 37° C.; and the shaker speed is 200 rpm.

[0011] Preferably, in the step 5), the in situ growth of PCN-777 is as follows: 360 mg of ZrOCl2·8H2O and 90 mg of the carboxyl ligand 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine are added to 12 mL of DEF, and then 0.6 mL of trifluoroacetic acid is added. After mixing, the mixture is added to the glass bottle modified with the 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine carboxyl ligand obtained in step 4), and the mixture is reacted in an oil bath at 120° C. for 24 hours, washed three times with DEF and ethanol respectively, and dried in an oven at 60° C.

[0012] Preferably, in the in situ growth of MOF-525 in step 5), 210 mg of ZrOCl2·8H2O and 2.7 g of benzoic acid are added to 16 mL of DMF, heated in an oven at 100°C for 1 hour, cooled to room temperature, added with 90 mg of the carboxyl ligand meso-tetra(4-carboxyphenyl)porphine, mixed, and added to the glass bottle modified with the meso-tetra(4-carboxyphenyl)porphine carboxyl ligand obtained in step 4), reacted in an oil bath at 120°C for 24 hours, washed three times with DMF and ethanol, respectively, and dried in an oven at 60°C.

[0013] Preferably, the in situ growth of NU-1000 in step 5) is as follows: 198 mg of ZrOCl2·8H2O and 5.4 g of benzoic acid are dissolved in 16 mL of DMF, heated at 100°C for 1 h, 160 mg of the carboxyl ligand 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene and 160 µL of trifluoroacetic acid are added, and the mixture is added to the glass bottle modified with the 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene carboxyl ligand obtained in step 4), and the mixture is reacted in an oil bath at 120°C for 24 h. The mixture is washed three times with DMF and ethanol, respectively, and dried in an oven at 60°C.

[0014] Preferably, in the in situ growth of Zr-MOF-H4L in step 5), 198 mg of ZrOCl2·8H2O and 5.4 g of benzoic acid were dissolved in 16 mL of DMF, heated at 100° C. for 1 h, and then 160 mg of the carboxyl ligand 4,4,4",4"-(pyrazino[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid and 160 µL of trifluoroacetic acid were added. The mixture was added to the glass bottle modified with the carboxyl ligand of 4,4,4",4"-(pyrazino[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid obtained in step 4), and the mixture was reacted in an oil bath at 120° C. for 24 h. The mixture was washed three times with DMF and ethanol, respectively, and dried in an oven at 60° C.

[0015] Compared with the prior art, the present invention has the following beneficial effects: This invention discloses a universal method for preparing carboxylic acid Zr-MOFs for in situ macroscopic interfacial growth. This method directly uses the ligands of the synthesized Zr-MOFs as carboxyl-introducing agents, eliminating the need for additional molecules to introduce carboxyl anchoring groups. This design not only addresses the difficulty in recycling and reusing powdered carboxylic acid Zr-MOFs, but also overcomes the limitation of the anchoring group's coordination capacity during in situ growth of carboxylic acid Zr-MOFs, enabling the efficient preparation of Zr-MOF composite materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 In the embodiments of the present invention, NU-1000, PCN-777, MOF-525 and Zr-H4L-MOF carboxylic acid Zr-MOFs are in situ grown on the glass bottle interface; Figure 2 SEM images of carboxylic acid Zr-MOFs in the examples of the present invention: (A) NU-1000, (B) PCN-777, (C) MOF-525, and (D) Zr-MOF-H4L. DETAILED DESCRIPTION

[0017] To make the present invention more clearly understood, preferred embodiments are described in detail below with reference to the accompanying drawings.

[0018] The present invention provides a universal preparation method for in-situ growth of carboxylic acid Zr-MOFs on a macroscopic interface. A glass bottle is sequentially soaked in a NaOH solution and a hydrochloric acid solution, and then a piranha solution is added to activate the surface hydroxyl groups, and the amino groups are modified on the surface by APTES to obtain an amino-treated glass bottle; the carboxylic acid ligand of the Zr-MOFs to be synthesized is directly added to the MES buffer as a carboxyl group introduction agent, and then EDC and NHS are added to activate the carboxyl groups. After adding PBS buffer, the mixture is divided into amino-treated glass bottles, and the carboxylic acid ligand is modified to the surface of the glass bottle by an amide coupling reaction; finally, different Zr-MOFs are grown in situ. The universal preparation method provided by the present invention not only solves the problem that powdered Zr-MOFs are difficult to recycle and reuse, but also solves the problem that in-situ growth is limited by the coordination capacity of the anchoring group.

[0019] Example 1: In situ growth of PCN-777 The present invention provides a general preparation method for macroscopic interface in situ growth of carboxylic acid Zr-MOFs, comprising the following steps: Step 1): Place a 20 mL glass bottle in 1 mol / L NaOH and 0.1 mol / L hydrochloric acid solutions in sequence and soak for 6 hours. Wash with deionized water until neutral and then dry in an oven at 60°C to obtain a glass bottle with a smooth surface. Step 2): Add 10 mL of piranha solution (prepared with concentrated sulfuric acid and hydrogen peroxide) to the smooth-surfaced glass bottle obtained in step 1) and soak for 4 hours. Wash with deionized water until neutral, and heat dry in an oven at 60°C to obtain a hydroxyl-activated glass bottle. Step 3): Add 10 mL of 5% APTES (prepared in ethanol) to the hydroxyl-activated glass bottle obtained in step 2), heat in a 60°C oven for 24 h, wash three times with ethanol and deionized water, respectively, and then heat and dry in a 120°C oven for 1 h to obtain an amino-activated glass bottle; Step 4): 20 mg of the carboxyl ligand 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine of the carboxyl group Zr-MOFs was added to 15 mL of MES buffer (0.1 mol / L, pH = 6), and then 80 mg of EDC and 120 mg of NHS were added to the buffer for reaction. The mixture was incubated at 37 ° C for 15 min, and then 15 mL of PBS buffer (0.15 mol / L, pH = 7.4) was added. The mixed solution was then divided into the amino-treated glass bottles (10 mL / bottle) obtained in step 3), placed at 37 ° C and incubated on a shaker at 200 rpm overnight, washed three times with ethanol and deionized water, respectively, and dried in an oven at 60 ° C to obtain a glass bottle modified with 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine carboxyl ligand; Step 5): 360 mg ZrOCl2·8H2O and 90 mg carboxyl ligand 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine were added to 12 mL DEF, and then 0.6 mL trifluoroacetic acid was added. After mixing, the mixture was added to the glass bottle modified with 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine carboxyl ligand obtained in step 4), and the mixture was reacted in an oil bath at 120°C for 24 h. The mixture was washed with DEF and ethanol three times, and dried in an oven at 60°C to obtain the following: Figure 1 The PCN-777 shown is in situ grown on the interface of the glass bottle modified with 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine carboxyl ligand, as shown in the scanning electron microscope SEM image. Figure 2 As shown in B.

[0020] Example 2: In situ growth of MOF-525 The present invention provides a general preparation method for macroscopic interface in situ growth of carboxylic acid Zr-MOFs, comprising the following steps: Step 1), step 2), step 3) and step 4) are the same as in Example 1, except that: in step 4), the carboxyl ligand of the carboxylic acid Zr-MOFs is meso-tetrakis(4-carboxyphenyl)porphine; Step 5): 210 mg ZrOCl2·8H2O and 2.7 g benzoic acid were added to 16 mL DMF, heated in an oven at 100 ° C for 1 h, and after cooling to room temperature, 90 mg of the carboxyl ligand -tetrakis (4-carboxyphenyl) porphine was added, mixed, and added to the glass bottle modified with the carboxyl ligand of -tetrakis (4-carboxyphenyl) porphine obtained in step 4), and reacted in an oil bath at 120 ° C for 24 h. The mixture was washed with DMF and ethanol three times, and dried in an oven at 60 ° C to obtain the following: Figure 1 The MOF-525 shown is in situ grown on the interface of the glass bottle modified with the carboxyl ligand of tetra(4-carboxyphenyl)porphine. The scanning electron microscope SEM image is shown in FIG. Figure 2 As shown in C.

[0021] Example 3: In situ growth of NU-1000 The present invention provides a general preparation method for macroscopic interface in situ growth of carboxylic acid Zr-MOFs, comprising the following steps: Step 1), step 2), step 3) and step 4) are the same as in Example 1, except that: in step 4), the carboxyl ligand of the carboxylic acid Zr-MOFs is 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene; Step 5): 198 mg ZrOCl2·8H2O and 5.4 g benzoic acid were dissolved in 16 mL DMF, heated at 100 ° C for 1 h, and then 160 mg carboxyl ligand 1,3,6,8-tetrakis (4-carboxyphenyl) pyrene and 160 μL trifluoroacetic acid were added. After mixing, the mixture was added to the glass bottle modified with 1,3,6,8-tetrakis (4-carboxyphenyl) pyrene carboxyl ligand obtained in step 4), and the mixture was reacted in an oil bath at 120 ° C for 24 h. The mixture was washed with DMF and ethanol three times, and dried in an oven at 60 ° C to obtain the following: Figure 1 The NU-1000 shown is in situ grown on the interface of the glass bottle modified with 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene carboxyl ligand, as shown in the scanning electron microscope SEM image. Figure 2 As shown in A.

[0022] Example 4: In situ growth of Zr-MOF-H4L The present invention provides a general preparation method for macroscopic interface in situ growth of carboxylic acid Zr-MOFs, comprising the following steps: Step 1), step 2), step 3) and step 4) are the same as in Example 1, except that: in step 4), the carboxyl ligand of the carboxylic acid Zr-MOFs is 4,4,4",4"-(pyrazino[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid; Step 5): 198 mg ZrOCl2·8H2O and 5.4 g benzoic acid were dissolved in 16 mL DMF, heated at 100 ° C for 1 h, and then 160 mg carboxyl ligand 4,4,4",4"-(pyrazine [2,3-G] quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid and 160 μL trifluoroacetic acid were added. After mixing, the mixture was added to the glass bottle modified with the 4,4,4",4"-(pyrazine [2,3-G] quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid carboxyl ligand obtained in step 4) and reacted in an oil bath at 120 ° C for 24 h. The mixture was washed with DMF and ethanol three times, and dried in an oven at 60 ° C to obtain the following: Figure 1 The Zr-MOF-H4L shown is in situ grown on the interface of a glass bottle modified with 4,4,4",4"-(pyrazino[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid carboxyl ligand, as shown in the scanning electron microscopy SEM image. Figure 2 As shown in D.

[0023] In summary, the present invention provides a universal preparation method for the in situ growth of carboxylic acid Zr-MOFs at a macroscopic interface. The ligands of the synthesized Zr-MOFs are directly used as carboxyl introducing agents, without the need to use additional molecules to introduce carboxyl anchoring groups, thereby achieving efficient preparation of Zr-MOFs composite materials.

[0024] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form or substance. It should be pointed out that ordinary technicians in this technical field can make several improvements and supplements without departing from the present invention, and these improvements and supplements should also be regarded as the scope of protection of the present invention. Any equivalent changes, modifications and evolutions made by technicians familiar with this profession without departing from the spirit and scope of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention; at the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A general preparation method for macro-interface in situ growth of carboxylic acid Zr-MOFs, characterized in that: The following steps are involved: Step 1): Soak the glass bottle in NaOH solution and hydrochloric acid solution in sequence, wash with deionized water until neutral, and heat and dry in an oven to obtain a glass bottle with a smooth surface; Step 2): adding piranha solution to the glass bottle with a smooth surface obtained in step 1) and soaking it, washing it with deionized water until it is neutral, and heating and drying it in an oven to obtain a hydroxyl-activated glass bottle; Step 3): Add APTES to the hydroxyl-activated glass bottle obtained in step 2), heat in an oven for reaction, wash with ethanol and deionized water three times respectively, and then heat and dry to obtain an amino-activated glass bottle; Step 4): Add the carboxyl ligand of the carboxylic acid Zr-MOFs to MES buffer, then add EDC and NHS to the buffer for reaction, then add PBS buffer, and then divide the mixed solution into the amino-treated glass bottles obtained in step 3), incubate on a shaker overnight, wash with ethanol and deionized water three times respectively, and heat dry in an oven to obtain glass bottles modified with the carboxyl ligand of the carboxylic acid Zr-MOFs; Step 5): PCN-777, MOF-525, NU-1000 or Zr-MOF-H4L carboxylic acid Zr-MOFs are in situ grown on the interface of the glass bottle modified with the carboxyl ligand obtained in step 4).

2. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In step 1), the concentration of the NaOH solution is 1 mol / L; the concentration of the hydrochloric acid solution is 0.1 mol / L; the soaking time is 6 hours; and the heating and drying temperature is 60°C.

3. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In step 2), the volume of the piranha solution is 10 mL; the soaking time is 4 h; and the heating and drying temperature is 60° C.

4. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In step 3), APTES is prepared by preparing a 5% APTES solution with 10 mL of ethanol; the heating reaction temperature is 60° C.; the heating reaction time is 24 h; the heating drying temperature is 120° C.; and the heating drying time is 1 h.

5. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In step 4), the carboxylic acid ligand is 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine, 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene, meso-tetrakis(4-carboxyphenyl)porphine, or 4,4,4",4"-(pyrazine[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid; the amount of the carboxylic acid ligand added is 20 mg; the MES buffer is 15 mL of a 0.1 mol / L MES buffer with a pH of 6; the amount of EDC added is 80 mg; the amount of NHS added is 120 mg; the reaction temperature is 37° C.; the reaction time is 15 min; the PBS buffer is 15 mL of a 0.15 mol / L PBS buffer with a pH of 7.4; the mixed solution is dispensed into 10 mL bottles; the shaker temperature is 37° C.; and the shaker speed is 200 rpm.

6. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In situ growth of PCN-777 in step 5): 360 mg of ZrOCl2·8H2O and 90 mg of the carboxyl ligand 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine were added to 12 mL of DEF, and then 0.6 mL of trifluoroacetic acid was added. After mixing, the mixture was added to a glass bottle modified with the 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine carboxyl ligand obtained in step 4), and the mixture was reacted in an oil bath at 120°C for 24 h. The mixture was washed three times with DEF and ethanol, respectively, and dried in an oven at 60°C.

7. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In situ growth of MOF-525 in step 5): 210 mg of ZrOCl2·8H2O and 2.7 g of benzoic acid were added to 16 mL of DMF and heated in an oven at 100°C for 1 h. After cooling to room temperature, 90 mg of the carboxyl ligand meso-tetrakis(4-carboxyphenyl)porphine was added, mixed, and added to a glass bottle modified with the meso-tetrakis(4-carboxyphenyl)porphine carboxyl ligand obtained in step 4). The mixture was reacted in an oil bath at 120°C for 24 h, washed three times with DMF and ethanol, respectively, and dried in an oven at 60°C.

8. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In situ growth of NU-1000 in step 5): 198 mg of ZrOCl2·8H2O and 5.4 g of benzoic acid were dissolved in 16 mL of DMF and heated at 100°C for 1 h. Then, 160 mg of the carboxyl ligand 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene and 160 µL of trifluoroacetic acid were added. The mixture was added to the glass bottle modified with the 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene carboxyl ligand obtained in step 4). The mixture was reacted in an oil bath at 120°C for 24 h. The mixture was washed three times with DMF and ethanol, respectively, and dried in an oven at 60°C.

9. The general preparation method for macro-interface in-situ growth of carboxylic acid Zr-MOFs according to claim 1, characterized in that: In situ growth of Zr-MOF-H4L in step 5): 198 mg of ZrOCl2·8H2O and 5.4 g of benzoic acid were dissolved in 16 mL of DMF and heated at 100°C for 1 h. Then, 160 mg of the carboxyl ligand 4,4,4",4"-(pyrazino[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid and 160 µL of trifluoroacetic acid were added. The mixture was added to a glass bottle modified with the carboxyl ligand 4,4,4",4"-(pyrazino[2,3-G]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid obtained in step 4). The mixture was reacted in an oil bath at 120°C for 24 h. The mixture was washed three times with DMF and ethanol, respectively, and dried in an oven at 60°C.

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