A method for one-pot synthesis of metal-organic framework materials in aqueous phase

Abstract

This invention belongs to the field of environmental protection and discloses a method for synthesizing metal-organic frameworks (MOFs) using a one-pot aqueous phase method. The method includes the following steps: mixing an amino- or aldehyde-containing pyrazolyl derivative, an aldehyde- or amino-containing linker, a copper salt, and pyruvate; adding an acidic solution of water; and then sonicating or stirring at room temperature to obtain a highly crystalline MOF. The amount of pyruvate used may be zero or not zero. When an amino-containing pyrazolyl derivative is selected as the raw material, an aldehyde-containing linker is selected; when an aldehyde-containing pyrazolyl derivative is selected as the raw material, an amino-containing linker is selected. The one-pot aqueous phase synthesis method provided by this invention eliminates the use of organic solvents, greatly reducing environmental impact. It also allows for large-scale synthesis with good reproducibility, a simple synthesis process, and strong operability, showing broad application prospects.

Description

Technical Field

[0001] This invention belongs to the field of environmental protection, and specifically relates to a method for synthesizing metal-organic framework materials in an aqueous one-pot process. Background Technology

[0002] Metal-organic frameworks (MOFs) are a class of crystalline porous materials self-assembled from metal ions / clusters and organic linkers. Due to their tunable pore size, large specific surface area, and ease of functionalization, MOF materials have been extensively studied in various fields such as energy storage, sensing, and drug delivery. However, MOF synthesis typically requires the use of large amounts of high-boiling-point organic solvents, such as N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), which can have severe environmental impacts when scaling up production. Furthermore, current practices for functionalizing MOFs often employ pre-assembly or post-modification strategies, which can significantly increase the complexity of the synthesis process. In addition, although mixed metal or mixed ligand strategies offer an alternative approach to constructing multi-component MOFs, the lack of structural precision hinders a full understanding of the structure-activity relationship. Therefore, there is an urgent need to create multi-component MOFs with structural precision in a sustainable manner. Summary of the Invention

[0003] To overcome the shortcomings and deficiencies of the prior art, the primary objective of this invention is to provide a method for synthesizing metal-organic framework materials using a one-pot aqueous phase method. This preparation method is simple and requires no complex post-modification or pre-synthesis. It achieves structural diversity of copper-based metal-organic frameworks by introducing tricyclic copper as metal nodes and constructing them with two-, three-, and four-linked building blocks, resulting in rhombic and hexagonal channels.

[0004] Another object of the present invention is to provide metal-organic framework materials prepared by the above method.

[0005] Another objective of this invention is to provide applications of the aforementioned metal-organic framework materials in fields such as energy storage, sensing, and drug delivery.

[0006] The objective of this invention is achieved through the following solution:

[0007] A method for synthesizing metal-organic framework materials in an aqueous one-pot process includes the following steps:

[0008] A highly crystalline metal-organic framework material is obtained by mixing a pyrazolyl derivative containing an amino or aldehyde group, a linker containing an aldehyde or amino group, a copper salt, and pyruvic acid, adding an acidic solution of water, and reacting the mixture with ultrasound or stirring at room temperature. The amount of pyruvic acid used is 0 or not 0.

[0009] When an amino-containing pyrazolyl derivative is selected as the raw material, an aldehyde-containing linker is selected as the corresponding linker; when an aldehyde-containing pyrazolyl derivative is selected as the raw material, an amino-containing linker is selected as the corresponding linker.

[0010] The structures of the pyrazolyl derivatives containing amino or aldehyde groups are shown below:

[0011]

[0012] In the pyrazolyl derivative containing an amino or aldehyde group, R1 is one of H or -CH3; R2 is one of H or -CH3; and R3 is one of -CHO, -NH2, or -CON2H3.

[0013] Preferably, the pyrazolyl derivative containing an amino or aldehyde group has one of the following structures:

[0014]

[0015] The aldehyde- or amino-containing linker includes at least one of a two-toothed linker, a three-toothed linker, and a four-toothed linker, wherein the two-toothed linker includes one of the following structures:

[0016]

[0017] The three-tooth connector includes one of the following structures:

[0018]

[0019]

[0020] The four-tooth connector includes one of the following structures:

[0021]

[0022] The copper salt is at least one of cuprous oxide, copper nitrate, cuprous bromide, cuprous iodide, and copper sulfate, preferably at least one of cuprous oxide and copper nitrate.

[0023] The molar ratio of the copper salt, the pyrazolyl derivative containing an amino or aldehyde group, the linker containing an aldehyde or amino group, and pyruvic acid is (6-12):12:(3-12):(0-12); the addition of pyruvic acid as a fourth component can construct an imine-locked and functionalized metal-organic framework.

[0024] The acidic solution of water, also known as an aqueous solution of acid, is at least one of acetic acid and trifluoroacetic acid, with a concentration of 1.0 M to 17.5 M. The amount of acidic solution used is such that 1.0 to 18 mL of acidic solution is added for every 0.20 mmol of copper salt.

[0025] The power of the ultrasound is 200W-650W, no additional temperature control is required, and the duration of the ultrasound is 1min-120min.

[0026] The stirring mentioned refers to stirring at 200-1500 rpm for 1-7 days;

[0027] The ultrasonic treatment is followed by a purification step, specifically as follows: after ultrasonication, centrifugation is performed, followed by washing with anhydrous ethanol, followed by extraction and drying to obtain the purified copper-based metal-organic framework material. Here, extraction refers to extraction with ethanol.

[0028] A copper-based metal-organic framework material prepared by the above method has one of the following structural formulas:

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] The mechanism of this invention is as follows:

[0038] We propose a linker removal strategy to address the solubility issue in the synthesis of aqueous MOFs. Specifically, decomposing the organic linker into amines and aldehydes increases their solubility in water, enabling the simultaneous co-assembly of MOFs with imine organic linkers via dynamic covalent and coordinate bonds. This synthetic strategy also improves the efficiency of MOF formation by simplifying reaction steps by eliminating the need for complex organic linkers.

[0039] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0040] 1. The metal-organic framework material successfully synthesized in this invention exhibits high crystallinity and porosity, as shown by powder X-ray diffraction and nitrogen adsorption-desorption.

[0041] 2. The aqueous one-pot synthesis method provided by this invention eliminates the use of organic solvents when preparing metal-organic framework materials, thus greatly reducing the impact on the environment.

[0042] 3. The one-pot method of this invention introduces multi-component raw materials, which eliminates the need for pre-synthesized complex organic ligands and simplifies the reaction steps.

[0043] 4. The raw materials used in this invention can change the type and position of substituents, thereby increasing the structural diversity of copper-based metal-organic frameworks.

[0044] 5. This invention utilizes ultrasound to significantly reduce the time required for traditional solvothermal synthesis methods, enabling the acquisition of highly crystalline copper-based metal-organic frameworks in a shorter time. It allows for large-scale, reproducible synthesis with a simple and highly operable process, demonstrating broad application prospects. Attached Figure Description

[0045] Figure 1 Powder XRD diffraction comparison pattern of compound 1 prepared in Example 1 and its raw material (a), PXRD pattern of compound 1 prepared in Example 1 and comparison pattern of PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 1 prepared in Example 1 (c).

[0046] Figure 2 Powder XRD diffraction comparison pattern of compound 2 prepared in Example 2 and its raw material (a), PXRD pattern of compound 2 prepared in Example 2 and comparison pattern of PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 2 prepared in Example 2 (c).

[0047] Figure 3 Powder XRD diffraction comparison pattern of compound 3 prepared in Example 3 and its raw material (a), PXRD pattern of compound 3 prepared in Example 3 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 3 prepared in Example 3 (c).

[0048] Figure 4 Powder XRD diffraction pattern of compound 4 prepared in Example 4 compared with its raw material (a), PXRD pattern of compound 4 prepared in Example 4 compared with PXRD patterns of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 4 prepared in Example 4 (c).

[0049] Figure 5Powder XRD diffraction comparison pattern of compound 5 prepared in Example 5 and its raw material (a), PXRD pattern of compound 5 prepared in Example 5 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 5 prepared in Example 5 (c).

[0050] Figure 6 Powder XRD diffraction comparison pattern of compound 6 prepared in Example 6 and its raw material (a), PXRD pattern of compound 6 prepared in Example 6 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 6 prepared in Example 6 (c).

[0051] Figure 7 Powder XRD diffraction comparison pattern of compound 7 prepared in Example 7 and its raw materials (a), PXRD pattern of compound 7 prepared in Example 7 and comparison pattern of PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 7 prepared in Example 7 (c).

[0052] Figure 8 Powder XRD diffraction comparison pattern of compound 8 prepared in Example 8 and its raw material (a), PXRD pattern of compound 8 prepared in Example 8 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 8 prepared in Example 8 (c).

[0053] Figure 9 Powder XRD diffraction comparison pattern of compound 9 prepared in Example 9 and its raw material (a), PXRD pattern of compound 9 prepared in Example 9 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 9 prepared in Example 9 (c).

[0054] Figure 10 Powder XRD diffraction comparison pattern of compound 10 prepared in Example 10 and its raw materials (a), PXRD pattern of compound 10 prepared in Example 10 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 10 prepared in Example 10 (c).

[0055] Figure 11 Powder XRD diffraction comparison pattern of compound 11 prepared in Example 11 and its raw material (a), PXRD pattern of compound 11 prepared in Example 11 and comparison pattern of PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 11 prepared in Example 11 (c).

[0056] Figure 12Powder XRD diffraction comparison pattern of compound 12 prepared in Example 12 and its raw material (a), PXRD pattern of compound 12 prepared in Example 12 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 12 prepared in Example 12 (c).

[0057] Figure 13 Powder XRD diffraction comparison pattern of compound 13 prepared in Example 13 and its raw material (a), PXRD pattern of compound 13 prepared in Example 13 and PXRD pattern of different simulated stacked structures (c), nitrogen adsorption isotherm of compound 13 prepared in Example 13.

[0058] Figure 14 Powder XRD diffraction comparison pattern of compound 14 prepared in Example 14 and its raw material (a), PXRD pattern of compound 14 prepared in Example 14 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 14 prepared in Example 14 (c).

[0059] Figure 15 Powder XRD diffraction comparison pattern of compound 15 prepared in Example 15 and its raw material (a), PXRD pattern of compound 15 prepared in Example 15 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 15 prepared in Example 15 (c).

[0060] Figure 16 Powder XRD diffraction comparison pattern of compound 16 prepared in Example 16 and its raw material (a), PXRD pattern of compound 16 prepared in Example 16 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 16 prepared in Example 16 (c).

[0061] Figure 17 Powder XRD diffraction comparison pattern of compound 17 prepared in Example 17 and its raw material (a), PXRD pattern of compound 17 prepared in Example 17 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 17 prepared in Example 17 (c).

[0062] Figure 18 Powder XRD diffraction comparison pattern of compound 18 prepared in Example 18 and its raw material (a), PXRD pattern of compound 18 prepared in Example 18 and comparison pattern of PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 18 prepared in Example 18 (c).

[0063] Figure 19Powder XRD diffraction comparison pattern of compound 19 prepared in Example 19 and its raw material (a), PXRD pattern of compound 19 prepared in Example 19 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 19 prepared in Example 19 (c).

[0064] Figure 20 Powder XRD diffraction comparison pattern of compound 20 prepared in Example 20 and its raw materials (a), PXRD pattern of compound 20 prepared in Example 20 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 20 prepared in Example 20 (c).

[0065] Figure 21 Powder XRD diffraction comparison pattern of compound 21 prepared in Example 21 and its raw material (a), PXRD pattern of compound 21 prepared in Example 21 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 21 prepared in Example 21 (c).

[0066] Figure 22 Powder XRD diffraction comparison pattern of compound 22 prepared in Example 22 and its raw material (a), PXRD pattern of compound 22 prepared in Example 22 and comparison pattern of PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 22 prepared in Example 22 (c).

[0067] Figure 23 Powder XRD diffraction comparison pattern of compound 23 prepared in Example 23 and its raw material (a), PXRD pattern of compound 23 prepared in Example 23 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 23 prepared in Example 23 (c).

[0068] Figure 24 Powder XRD diffraction comparison pattern of compound 24 prepared in Example 24 and its raw material (a), PXRD pattern of compound 24 prepared in Example 24 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 24 prepared in Example 24 (c).

[0069] Figure 25 Powder XRD diffraction comparison pattern of compound 25 prepared in Example 25 and its raw material (a), PXRD pattern of compound 25 prepared in Example 25 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 25 prepared in Example 25 (c).

[0070] Figure 26Powder XRD diffraction comparison pattern of compound 26 prepared in Example 26 and its raw material (a), PXRD pattern of compound 26 prepared in Example 26 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 26 prepared in Example 26 (c).

[0071] Figure 27 Powder XRD diffraction comparison pattern of compound 27 prepared in Example 27 and its raw material (a), PXRD pattern of compound 27 prepared in Example 27 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 27 prepared in Example 27 (c).

[0072] Figure 28 Powder XRD diffraction comparison pattern of compound 28 prepared in Example 28 and its raw material (a), PXRD pattern of compound 28 prepared in Example 28 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 28 prepared in Example 28 (c).

[0073] Figure 29 Powder XRD diffraction comparison pattern of compound 29 prepared in Example 29 and its raw material (a), PXRD pattern of compound 29 prepared in Example 29 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 29 prepared in Example 29 (c).

[0074] Figure 30 Powder XRD diffraction comparison pattern of compound 30 prepared in Example 30 and its raw materials (a), PXRD pattern of compound 30 prepared in Example 30 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 30 prepared in Example 30 (c).

[0075] Figure 31 Powder XRD diffraction comparison pattern of compound 31 prepared in Example 31 and its raw material (a), PXRD pattern of compound 31 prepared in Example 31 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 31 prepared in Example 31 (c).

[0076] Figure 32 Powder XRD diffraction comparison pattern of compound 32 prepared in Example 32 and its raw material (a), PXRD pattern of compound 32 prepared in Example 32 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 32 prepared in Example 32 (c).

[0077] Figure 33Powder XRD diffraction comparison pattern of compound 33 prepared in Example 33 and its raw material (a), PXRD pattern of compound 33 prepared in Example 33 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 33 prepared in Example 33 (c).

[0078] Figure 34 Powder XRD diffraction comparison pattern of compound 34 prepared in Example 34 and its raw material (a), PXRD pattern of compound 34 prepared in Example 34 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 34 prepared in Example 34 (c).

[0079] Figure 35 Powder XRD diffraction comparison pattern of compound 35 prepared in Example 35 and its raw material (a), PXRD pattern of compound 35 prepared in Example 35 and PXRD pattern of different simulated stacked structures (b), nitrogen adsorption isotherm of compound 35 prepared in Example 35 (c). Detailed Implementation

[0080] The present invention will be further described in detail below with reference to embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0081] Unless otherwise specified, all reagents used in the examples are commercially available.

[0082] In this invention, compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 21, 3, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, and 35 represent copper-based metal-organic frameworks with different structures. For ease of explanation, copper-based metal-organic frameworks prepared in different reaction processes are labeled with different names. The ultrasonic instrument used in the examples is a 250W BransonSonifier SFX250 cell disruptor. In the examples, "ultrasonic" refers to an ultrasonic instrument with a power of 200W and a 3mm amplitude bar.

[0083] Example 1: Preparation of Compound 1

[0084] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and p-phenylenediamine (PD, 24.3 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0085] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 1.

[0086] The crystallinity of 35 copper-based metal-organic frameworks was characterized using X-ray powder diffraction (PXRD). The structures were simulated and refined using Materials Studio software. Figure 1 The graph shows a comparison of the PXRD patterns of component 1 and its raw material, as well as a comparison of the experimentally measured PXRD pattern of component 1 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of component 1 was tested at 77 K using a gas adsorption analyzer. Figure 1 As can be seen from the data, 1 exhibits significant porosity, with a specific surface area (BET) of 525 m². 2 g -1 .

[0087] Example 2: Preparation of Compound 2

[0088] (1) Mix Cu2O (41.5 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and p-4,4'-biphenyldiamine (DAPB, 41.5 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0089] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 2.

[0090] Figure 2 This chart shows a comparison of the PXRD patterns of compound 2 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of compound 2 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of compound 2 was tested at 77 K using a gas adsorption analyzer. Figure 2 As can be seen from the data, 2 exhibits significant porosity, with a specific surface area (BET) of 817 m². 2 g -1 .

[0091] Example 3: Preparation of Compound 3

[0092] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4'-diamino-[1,1'-biphenyl]-3,3'-diol (DABP-OH, 48.7 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0093] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 3.

[0094] Figure 3 The figures show a comparison of the PXRD patterns of 3 and its raw materials, as well as a comparison of the experimentally measured PXRD pattern of 3 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests on 3 were performed at 77 K using a gas adsorption analyzer. Figure 3 As can be seen from the data, compound 3 exhibits significant porosity, with a specific surface area (BET) of 336 m². 2 g -1 .

[0095] Example 4: Preparation of Compound 4

[0096] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 3,3'-dimethoxy-[1,1'-biphenyl]-4,4'-diamine (DABP-OMe, 55 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0097] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 4.

[0098] Figure 4 This chart shows a comparison of the PXRD patterns of compound 4 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of compound 4 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of compound 4 was tested at 77 K using a gas adsorption analyzer. Figure 4 As can be seen from the data, compound 4 exhibits significant porosity, with a specific surface area (BET) of 605 m². 2 g -1 .

[0099] Example 5: Preparation of Compound 5

[0100] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and anthracene-2,6-diamine (ADA, 46.9 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0101] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 5.

[0102] Figure 5 This chart compares the PXRD patterns of component 5 with those of its raw materials, as well as the experimentally measured PXRD pattern of component 5 and the PXRD patterns of different simulated stacked structures. Nitrogen adsorption of component 5 was tested at 77 K using a gas adsorption analyzer. Figure 5 As can be seen from the data, compound 5 exhibits significant porosity, with a specific surface area (BET) of 584 m². 2 g -1 .

[0103] Example 6: Preparation of Compound 6

[0104] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 2,5-diethoxyterephthalohydrazide (TPHA-OEt, 63.5 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0105] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 6.

[0106] Figure 6 This chart compares the PXRD patterns of 6 with those of its raw materials, as well as the experimentally measured PXRD pattern of 6 and the PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 6 was tested at 77 K using a gas adsorption analyzer. Figure 6 As can be seen from the data, compound 6 exhibits significant porosity, with a specific surface area (BET) of 817 m². 2 g -1 .

[0107] Example 7: Preparation of Compound 7

[0108] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 2,5-dipropoxyterephthalamide (TPHA-OPr, 69.8 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0109] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 7.

[0110] Figure 7 The figures show a comparison of the PXRD patterns of 7 and its raw materials, as well as a comparison of the experimentally measured PXRD pattern of 7 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests on 7 were performed at 77 K using a gas adsorption analyzer. Figure 7 As can be seen from the data, compound 7 exhibits significant porosity, with a specific surface area (BET) of 864 m². 2 g -1 .

[0111] Example 8: Preparation of Compound 8

[0112] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 2,5-di(allyloxy)terephthalohydrazide (TPHA-OAl, 68.9 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0113] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 8.

[0114] Figure 8 The figures show a comparison of the PXRD patterns of 8 and its raw materials, as well as a comparison of the experimentally measured PXRD pattern of 8 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 1 was tested at 77 K using a gas adsorption analyzer. Figure 8 As can be seen from the data, compound 8 exhibits significant porosity, with a specific surface area (BET) of 832 m². 2 g -1 .

[0115] Example 9: Preparation of Compound 9

[0116] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and (E)-4,4'-(diazepine-1,2-diyl)diphenylamine (DADDA, 47.8 mg, 0.225 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0117] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 9.

[0118] Figure 9 This chart shows a comparison of the PXRD patterns of compound 9 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of compound 9 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of compound 9 was tested at 77 K using a gas adsorption analyzer. Figure 9 As can be seen from the data, compound 9 exhibits significant porosity, with a specific surface area (BET) of 835 m². 2 g -1 .

[0119] Example 10: Preparation of Compound 10

[0120] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and p-4,4'-diamino-p-terphenyl (DATP, 58.6 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0121] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 10.

[0122] Figure 10 This chart shows a comparison of the PXRD patterns of compound 10 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 10 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 10 was tested at 77 K using a gas adsorption analyzer. Figure 10 As can be seen from the data, compound 10 exhibits significant porosity, with a specific surface area (BET) of 120 m². 2 g -1 .

[0123] Example 11: Preparation of Compound 11

[0124] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diphenylamine (BTDA, 71.6 mg, 0.225 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0125] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 11.

[0126] Figure 11 This chart shows a comparison of the PXRD patterns of compound 11 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 11 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 11 at 77 K using a gas adsorption analyzer. Figure 11 As can be seen from the data, compound 11 exhibits significant porosity, with a specific surface area (BET) of 829 m². 2 g -1 .

[0127] Example 12: Preparation of Compound 12

[0128] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4'-diamino-p-tetraphenyl (DAQP, 75.7 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0129] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 12.

[0130] Figure 12 This chart shows a comparison of the PXRD patterns of compound 12 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 12 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 12 was tested at 77 K using a gas adsorption analyzer. Figure 12 As can be seen from the data, compound 12 exhibits significant porosity, with a specific surface area (BET) of 83 m². 2 g -1 .

[0131] Example 13: Preparation of Compound 13

[0132] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 1,3,5-tris(4-aminophenyl)amine (TAPA, 43.6 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0133] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 13.

[0134] Figure 13 This chart shows a comparison of the PXRD patterns of compound 13 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 13 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 13 at 77 K using a gas adsorption analyzer. Figure 13 As can be seen from the data, compound 13 exhibits significant porosity, with a specific surface area (BET) of 936 m². 2 g -1 .

[0135] Example 14: Preparation of Compound 14

[0136] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 1,3,5-tris(4-aminophenyl)benzene (TAPB, 52.4 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0137] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 14.

[0138] Figure 14 This chart shows a comparison of the PXRD patterns of compound 14 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 14 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 14 at 77 K using a gas adsorption analyzer. Figure 14 As can be seen from the data, compound 14 exhibits significant porosity, with a specific surface area (BET) of 1339 m². 2 g -1 .

[0139] Example 15: Preparation of Compound 15

[0140] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4',4”-(pyridine-2,4,6-triyl)triphenylamine (PDTA, 52.9 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0141] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 15.

[0142] Figure 15 This is a comparison of the PXRD patterns of compound 15 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 15 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of compound 15 was tested at 77 K using a gas adsorption analyzer. Figure 15 As can be seen from the data, compound 15 exhibits significant porosity, with a specific surface area (BET) of 1367 m². 2 g -1 .

[0143] Example 16: Preparation of Compound 16

[0144] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 1,3,5-tris-(4-aminophenyl)triazine (TAPT, 53.2 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0145] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 16.

[0146] Figure 16 This is a comparison of the PXRD patterns of compound 16 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 16 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of compound 16 was tested at 77 K using a gas adsorption analyzer. Figure 16 As can be seen from the data, compound 16 exhibits significant porosity, with a specific surface area (BET) of 1137 m². 2 g -1 .

[0147] Example 17: Preparation of Compound 17

[0148] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4',4”-((1,3,5-triazine-2,4,6-triyl)tri(oxy))triphenylamine (TTTOT, 60.4 mg, 0.15 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0149] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 17.

[0150] Figure 17 This chart shows a comparison of the PXRD patterns of compound 17 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 17 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 17 at 77 K using a gas adsorption analyzer. Figure 17 As can be seen from the data, compound 17 exhibits significant porosity, with a specific surface area (BET) of 149 m². 2 g -1 .

[0151] Example 18: Preparation of Compound 18

[0152] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4',4”-(benzene-1,3,5-triyltri(acetylene-2,1-diyl))triphenylamine (TTEDTA, 63.6 mg, 0.15 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0153] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 18.

[0154] Figure 18 This chart shows a comparison of the PXRD patterns of compound 18 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 18 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 18 at 77 K using a gas adsorption analyzer. Figure 18 As can be seen from the data, compound 18 exhibits significant porosity, with a specific surface area (BET) of 816 m². 2 g -1 .

[0155] Example 19: Preparation of Compound 19

[0156] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and N4,N4-bis(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine (ABBD, 77.8 mg, 0.15 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0157] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 19.

[0158] Figure 19 This chart shows a comparison of the PXRD patterns of compound 19 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 19 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 19 at 77 K using a gas adsorption analyzer. Figure 19 As can be seen from the data, compound 19 exhibits significant porosity, with a specific surface area (BET) of 1567 m². 2 g -1 .

[0159] Example 20: Preparation of Compound 20

[0160] (1) Cu2O (10.7 mg, 0.075 mmol), 4-aldehyde pyrazole (Pz-CHO, 14.4 mg, 0.15 mmol) and 5”-(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1':4',1”:3”,1”':4”',1””-pentaphenyl]-4,4””-diamine (ABQA, 29 mg, 0.05 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0161] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 20.

[0162] Figure 20 This chart shows a comparison of the PXRD patterns of compound 20 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 20 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 20 was tested at 77 K using a gas adsorption analyzer. Figure 20 As can be seen from the data, compound 20 exhibits significant porosity, with a specific surface area (BET) of 712 m². 2 g -1 .

[0163] Example 21: Preparation of compound 21

[0164] (1) Cu2O (10.7 mg, 0.075 mmol), 4-aldehydepyrazole (Pz-CHO, 14.4 mg, 0.15 mmol) and 4',4”',4””-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-amine))(TTTBA, 29.1 mg, 0.05 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0165] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 21.

[0166] Figure 21 This chart shows a comparison of the PXRD patterns of compound 21 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 21 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 21 at 77 K using a gas adsorption analyzer. Figure 21 As can be seen from the data, compound 21 exhibits significant porosity, with a specific surface area (BET) of 1300 m². 2 g -1 .

[0167] Example 22: Preparation of compound 22

[0168] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4',4”,4”'-(pyrene-1,3,6,8-tetraphenyl)tetraphenylamine (PTTA, 70.8 mg, 0.1125 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0169] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 22.

[0170] Figure 22 This chart shows a comparison of the PXRD patterns of compound 22 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 22 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 22 was tested at 77 K using a gas adsorption analyzer. Figure 22 As can be seen from the data, compound 22 exhibits significant porosity, with a specific surface area (BET) of 997 m². 2 g -1 .

[0171] Example 23: Preparation of compound 23

[0172] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4,4',4”,4”'-(porphyrin-5,10,15,20-tetraphenyl)tetraphenylamine (PTTA-Por, 84.4 mg, 0.125 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0173] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 23.

[0174] Figure 23 This chart shows a comparison of the PXRD patterns of compound 23 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 23 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 23 at 77 K using a gas adsorption analyzer. Figure 23 As can be seen from the data, compound 23 exhibits significant porosity, with a specific surface area (BET) of 430 m². 2 g -1 .

[0175] Example 24: Preparation of compound 24

[0176] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4-amino-2-methoxybenzoyl hydrazide (AMBH, 40.8 mg, 0.225 mmol) in 6 mL of 4 M acetic acid aqueous solution.

[0177] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 24.

[0178] Figure 24 This chart shows a comparison of the PXRD patterns of compound 24 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 24 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 24 at 77 K using a gas adsorption analyzer. Figure 24 As can be seen from the data, compound 24 exhibits significant porosity, with a specific surface area (BET) of 301 m². 2 g -1 .

[0179] Example 25: Preparation of Compound 25

[0180] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 3-methylpyrazole-4-carboxaldehyde (Pz-1Me-CHO, 49.6 mg, 0.45 mmol) and 1,3,5-tris-(4-aminophenyl)triazine (TAPT, 53.2 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0181] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 25.

[0182] Figure 25 This chart shows a comparison of the PXRD patterns of compound 25 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 25 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 25 was tested at 77 K using a gas adsorption analyzer. Figure 25 As can be seen from the data, compound 25 exhibits significant porosity, with a specific surface area (BET) of 616 m². 2 g -1 .

[0183] Example 26: Preparation of Compound 26

[0184] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 3,5-dimethyl-pyrazole-4-carboxaldehyde (Pz-2Me-CHO, 55.9 mg, 0.45 mmol) and 1,3,5-tris-(4-aminophenyl)triazine (TAPT, 53.2 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0185] (2) Then, the cells were sonicated for one hour using a cell disruptor; centrifuged, washed with anhydrous ethanol and extracted with it, and then dried to obtain the metal-organic framework material, denoted as compound 26.

[0186] Figure 26 This chart shows a comparison of the PXRD patterns of compound 26 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 26 and PXRD patterns of different simulated stacked structures. The nitrogen adsorption isotherm of 26 at 77 K was measured using a gas adsorption analyzer. Figure 26 As can be seen from the data, compound 26 exhibits significant porosity, with a specific surface area (BET) of 927 m². 2 g -1 .

[0187] Example 27: Preparation of Compound 27

[0188] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4-amino pyrazole (Pz-NH2, 37.4 mg, 0.45 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0189] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 27.

[0190] Figure 27 This chart shows a comparison of the PXRD patterns of compound 27 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 27 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 27 at 77 K using a gas adsorption analyzer. Figure 27 As can be seen from the data, compound 27 exhibits significant porosity, with a specific surface area (BET) of 574 m². 2 g -1 .

[0191] Example 28: Preparation of compound 28

[0192] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aminopyrazole (Pz-NH2, 37.4 mg, 0.45 mmol) and 1,3,5-tris(4-carboxyphenyl)amine (TFPA, 49.4 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0193] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 28.

[0194] Figure 28 This chart shows a comparison of the PXRD patterns of compound 28 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 28 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 28 at 77 K using a gas adsorption analyzer. Figure 28 As can be seen from the data, compound 28 exhibits significant porosity, with a specific surface area (BET) of 391 m². 2 g -1 .

[0195] Example 29: Preparation of compound 29

[0196] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aminopyrazole (Pz-NH2, 37.4 mg, 0.45 mmol) and 1,3,5-tris(4-formylphenyl)benzene (TFPB, 58.6 mg, 0.15 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0197] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, which was designated as compound 29.

[0198] Figure 29 This chart shows a comparison of the PXRD patterns of compound 29 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 29 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 29 was tested at 77 K using a gas adsorption analyzer. Figure 29 As can be seen from the data, compound 29 exhibits significant porosity, with a specific surface area (BET) of 1192 m². 2 g -1 .

[0199] Example 30: Preparation of compound 30

[0200] (1) Cu2O (32.2 mg, 0.225 mmol), 4-aminopyrazole (Pz-NH2, 37.4 mg, 0.45 mmol) and 4,4',4”-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (TFPT, 59 mg, 0.15 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0201] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 30.

[0202] Figure 30 This chart shows a comparison of the PXRD patterns of compound 30 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 30 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 30 was tested at 77 K using a gas adsorption analyzer. Figure 30 As can be seen from the data, compound 30 exhibits significant porosity, with a specific surface area (BET) of 1030 m². 2 g -1 .

[0203] Example 31: Preparation of compound 31

[0204] (1) Cu2O (32.2 mg, 0.225 mmol), 3,5-dimethyl-4-amino-pyrazole (Pz-2Me-NH) 2,50 mg (0.45 mmol) and 1,3,5-tris(4-formylphenyl)benzene (TFPB, 58.6 mg, 0.15 mmol) were mixed in 6 mL of 4 M aqueous acetic acid solution;

[0205] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 31.

[0206] Figure 31 This chart shows a comparison of the PXRD patterns of compound 31 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 31 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 31 at 77 K using a gas adsorption analyzer. Figure 31 As can be seen from the data, compound 31 exhibits significant porosity, with a specific surface area (BET) of 1056 m². 2 g -1 .

[0207] Example 32: Preparation of compound 32

[0208] (1) Cu2O (32.2 mg, 0.225 mmol), 3,5-dimethyl-4-amino-pyrazole (Pz-2Me-NH2, 43.2 mg, 0.45 mmol) and 4,4',4”-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (TFPT, 59 mg, 0.15 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0209] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 32.

[0210] Figure 32 This chart shows a comparison of the PXRD patterns of compound 32 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 32 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 32 at 77 K using a gas adsorption analyzer. Figure 32 As can be seen from the data, compound 32 exhibits significant porosity, with a specific surface area (BET) of 1033 m². 2 g -1 .

[0211] Example 33: Preparation of compound 33

[0212] (1) Cu2O (32.2 mg, 0.225 mmol), 1H-pyrazole-4-carboxyhydrazide (Pz-CON2H3, 56.8 mg, 0.45 mmol) and 1,3,5-tris(4-carboxyphenyl)benzene (TFPB, 58.6 mg, 0.15 mmol) were mixed in 6 mL of 4M acetic acid aqueous solution;

[0213] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 33.

[0214] Figure 33 This chart shows a comparison of the PXRD patterns of compound 33 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 33 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 33 at 77 K using a gas adsorption analyzer. Figure 33 As can be seen from the data, compound 33 exhibits significant porosity, with a specific surface area (BET) of 1093 m². 2 g -1 .

[0215] Example 34: Preparation of compound 34

[0216] (1) Mix Cu2O (21.5 mg, 0.15 mmol), 4-aldehyde pyrazole (Pz-CHO, 28 mg, 0.30 mmol) and trialumina (Au-CTC, 95.7 mg, 0.10 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0217] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain the metal-organic framework material, denoted as compound 34.

[0218] Figure 34 This chart shows a comparison of the PXRD patterns of compound 34 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 34 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption tests were performed on 34 at 77 K using a gas adsorption analyzer. Figure 34 As can be seen from the data, compound 34 exhibits significant porosity, with a specific surface area (BET) of 534 m². 2 g -1 .

[0219] Example 35: Preparation of compound 35

[0220] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol), 1,3,5-tris-(4-aminophenyl)triazine (TAPT, 53.2 mg, 0.15 mmol) and pyruvic acid (30 μL, 0.45 mmol) in 6 mL of 4 M acetic acid aqueous solution;

[0221] (2) Then, use a cell wall disruptor to sonicate for one hour; centrifuge, wash with anhydrous ethanol and extract with it and then dry to obtain the metal-organic framework material, denoted as compound 35.

[0222] Figure 35 This chart shows a comparison of the PXRD patterns of compound 35 and its reactants, as well as a comparison of the experimentally measured PXRD pattern of 35 and PXRD patterns of different simulated stacked structures. Nitrogen adsorption of 35 was tested at 77 K using a gas adsorption analyzer. Figure 35 As can be seen from the data, compound 35 exhibits significant porosity, with a specific surface area (BET) of 348 m². 2 g -1 .

[0223] Example 36: Preparation of Compound 16

[0224] (1) Mix Cu(NO3)2·3H2O (108.72 mg, 0.45 mmol), 4-aldehydepyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 1,3,5-tris-(4-aminophenyl)triazine (TAPT, 53.2 mg, 0.15 mmol) in a 20 mL glass bottle containing 6 mL of 4 M acetic acid aqueous solution, and seal tightly;

[0225] (2) Then stir at room temperature for 7 days (500 rpm); centrifuge, wash with anhydrous ethanol and extract with it and dry to obtain compound 16. The PXRD pattern of the obtained compound can also prove that compound 16 was successfully synthesized.

[0226] Example 37: Preparation of Compound 16

[0227] (1) Mix Cu2O (32.2 mg, 0.225 mmol), 4-aldehyde pyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 1,3,5-tris-(4-aminophenyl)triazine (TAPT, 53.2 mg, 0.15 mmol) in 6 mL of 4 M trifluoroacetic acid aqueous solution;

[0228] (2) Then, the cell wall disruptor was used to sonicate for one hour; centrifuged, washed with anhydrous ethanol and extracted with it and dried to obtain compound 16. The PXRD pattern of the obtained compound also proved that compound 16 was successfully synthesized.

[0229] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for the aqueous one-pot synthesis of metal-organic frameworks, characterized in that Includes the following steps: A metal-organic framework material is obtained by mixing a pyrazolyl derivative containing an amino or aldehyde group, a linker containing an aldehyde or amino group, a copper salt, and pyruvic acid, adding an acidic solution of water, and reacting the mixture with ultrasound or stirring at room temperature. The amount of pyruvic acid used is 0 or not 0. When an amino-containing pyrazolyl derivative is selected as the raw material, an aldehyde-containing linker is selected as the corresponding linker; when an aldehyde-containing pyrazolyl derivative is selected as the raw material, an amino-containing linker is selected as the corresponding linker. The structures of the pyrazolyl derivatives containing amino or aldehyde groups are shown below: ， In the pyrazolyl derivative containing an amino or aldehyde group, R1 is one of H or -CH3; R2 is one of H or -CH3; and R3 is one of -CHO, -NH2, or -CON2H3.

2. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The pyrazolyl derivative containing an amino or aldehyde group has one of the following structures: 。 3. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The aldehyde- or amino-containing linker includes at least one of a two-toothed linker, a three-toothed linker, and a four-toothed linker, wherein the two-toothed linker includes one of the following structures: ， The three-tooth connector includes one of the following structures: ， ， The four-tooth connector includes one of the following structures: 。 4. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The copper salt is at least one of cuprous oxide, copper nitrate, cuprous bromide, cuprous iodide, and copper sulfate.

5. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The copper salt is at least one of cuprous oxide and copper nitrate.

6. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The molar ratio of the copper salt, the pyrazolyl derivative containing an amino or aldehyde group, the linker containing an aldehyde or amino group, and pyruvic acid is (6-12):12:(3-12):(0-12).

7. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The acidic solution of water is wherein the acid is at least one of acetic acid and trifluoroacetic acid, wherein the concentration of the acid is 1.0 M–17.5 M, and the amount of acidic solution of water used is such that 1.0–18 mL of acidic solution of water is added for every 0.20 mmol of copper salt.

8. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The power of the ultrasound is 200W-650W, and the duration of the ultrasound is 1 min-120 min. The stirring mentioned refers to stirring at 200-1500 rpm for 1-7 days.

9. The method for synthesizing metal-organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The ultrasonic treatment is followed by a purification step, which is as follows: after ultrasonication, centrifugation is performed, followed by washing with anhydrous ethanol, followed by extraction and drying to obtain the purified copper-based metal-organic framework material; wherein extraction refers to extraction with ethanol.

10. A copper-based metal-organic framework material prepared by the method according to any one of claims 1-9, wherein the structural formula is one of the following: ， Compound 1 ， Compound 2 ， Compound 3 ， Compound 4 ， Compound 5 ， Compound 6 ， Compound 7 ， Compound 8 ， Compound 9 ， Compound 10 ， Compound 11 ， Compound 12 ， Compound 17 ， Compound 18 ， Compound 19 ， Compound 20 ， Compound 21 ， Compound 22 ， Compound 23 ， Compound 24 ， Compound 25 ， Compound 26 ， Compound 28 ， Compound 29 ， Compound 30 ， Compound 32 ， Compound 33 ， Compound 34 ， Compound 35.

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