Method for synthesizing metal organic framework material by aqueous phase one-pot method

Abstract

The invention belongs to the field of environmental protection, and discloses a method for synthesizing a metal organic framework material by a water-phase one-pot method. The method comprises the following steps: mixing a pyrazolyl derivative containing an amino group or an aldehyde group, a linker containing the aldehyde group or the amino group, a copper salt and pyruvic acid, adding an acid solution of water into the mixture, and performing ultrasonic treatment or stirring at room temperature to obtain the high-crystalline-state metal organic framework material, the dosage of the pyruvic acid being 0 or not 0; when the pyrazolyl derivative containing the amino group is selected as the raw material, the corresponding linker is a linker containing an aldehyde group; when a pyrazolyl derivative containing an aldehyde group is selected as a raw material, a corresponding linker containing an amino group is selected. When the water-phase one-pot synthesis method provided by the invention is used for preparing the metal organic framework material, the use of an organic solvent is eliminated, so that the influence on the environment is greatly reduced. Meanwhile, batch amplification synthesis can be achieved, repeatability is good, the synthesis process is simple, operability is high, and wide application prospects are achieved.

Description

Technical Field

[0001] The invention belongs to the field of environmental protection, and particularly relates to a method for synthesizing a metal organic framework material in an aqueous phase one-pot process. Background Art

[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 widely studied in various fields such as energy storage, sensing, and drug delivery. The synthesis of MOFs usually requires the use of large amounts of high-boiling organic solvents such as N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO), which can have serious environmental impacts when scaling up production. In addition, current practices for functionalizing MOFs usually require pre-installation or post-modification strategies, which may greatly increase the complexity of the synthetic process. In addition, although mixed-metal or mixed-ligand strategies provide an alternative approach to construct 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] In order to overcome the shortcomings and deficiencies of the above-mentioned prior art, the primary purpose of the present invention is to provide a method for synthesizing metal organic framework materials in one pot in an aqueous phase. The preparation method is simple and does not require complicated post-modification or pre-synthesis. It is based on the introduction of cyclotrinuclear copper as a metal node, and the construction of rhombic channels and hexagonal channels with di-linked, tri-linked, and tetra-linked building blocks to achieve the structural diversity of copper-based metal organic frameworks.

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

[0005] Another object of the present invention is to provide applications of the above metal organic framework materials in the fields of energy storage, sensing, drug delivery, etc.

[0006] The purpose of the present invention is achieved through the following solutions:

[0007] A method for synthesizing a metal organic framework material in an aqueous phase one-pot process comprises the following steps:

[0008] A pyrazolyl derivative containing an amino group or an aldehyde group, a linker containing an aldehyde group or an amino group, a copper salt and pyruvic acid are mixed, and an acid solution of water is added thereto, and a highly crystalline metal organic framework material is obtained after ultrasonic or stirring reaction at room temperature, and the amount of pyruvic acid used is 0 or not 0;

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

[0010] The structure of the pyrazolyl derivative containing an amino group or an aldehyde group is shown below:

[0011]

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

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

[0014]

[0015] The linker containing an aldehyde group or an amino group includes at least one of a bidentate linker, a tridentate linker, and a tetradentate linker, wherein the bidentate 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, cupric nitrate, cuprous bromide, cuprous iodide, copper sulfate, etc., preferably at least one of cuprous oxide and cupric nitrate.

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

[0024] The aqueous acid solution can also be referred to as an acid aqueous solution, wherein the acid is at least one of acetic acid and trifluoroacetic acid, wherein the acid concentration is 1.0M-17.5M, and the amount of the aqueous acid solution is such that 1.0-18mL of aqueous acid solution is added for every 0.20mmol of copper salt.

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

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

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

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

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] The mechanism of the present invention is:

[0038] We propose a linker removal strategy to address the solubility issue in aqueous MOF synthesis. Specifically, decomposing the organic linker into amine and aldehyde can increase its solubility in water, thereby enabling the co-assembly of MOFs with imine organic linkers via both dynamic covalent and coordination bonds. This synthetic strategy can also improve the efficiency of MOF formation and simplify the reaction steps by eliminating the necessity of 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 by the present invention has high crystallinity and porosity according to powder X-ray diffraction and nitrogen adsorption-desorption.

[0041] 2. When preparing metal organic framework materials using the aqueous one-pot synthesis method provided by the present invention, the use of organic solvents is eliminated to greatly reduce the impact on the environment.

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

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

[0044] 5. The ultrasonic method used in the present invention greatly reduces the time of the traditional solvent thermal synthesis method, and can obtain a highly crystalline copper-based metal organic framework in a shorter time. It can be synthesized in batches with good repeatability. At the same time, the synthesis process is simple and highly operable, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 The following are the powder XRD diffraction comparison spectra of the compound 1 prepared in Example 1 and its raw material (a), the PXRD pattern of the compound 1 prepared in Example 1 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 1 prepared in Example 1 (c);

[0046] Figure 2 The following are the powder XRD diffraction comparison spectra of the compound 2 prepared in Example 2 and its raw material (a), the PXRD spectrum of the compound 2 prepared in Example 2 and the comparison of the PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 2 prepared in Example 2 (c);

[0047] Figure 3 The following are the powder XRD diffraction comparison spectra of compound 3 prepared in Example 3 and its raw materials (a), the PXRD spectrum of compound 3 prepared in Example 3 and the comparison of PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 3 prepared in Example 3 (c);

[0048] Figure 4 The following are the powder XRD diffraction comparison spectra of compound 4 prepared in Example 4 and its raw materials (a), the PXRD spectrum of compound 4 prepared in Example 4 and the comparison of PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 4 prepared in Example 4 (c);

[0049] Figure 5The following are the powder XRD diffraction comparison spectra of compound 5 prepared in Example 5 and its raw materials (a), the comparison diagram of PXRD spectrum of compound 5 prepared in Example 5 and PXRD spectrum of different simulated stacking structures (b), and nitrogen adsorption isotherm of compound 5 prepared in Example 5 (c);

[0050] Figure 6 The following are the powder XRD diffraction comparison spectra of compound 6 prepared in Example 6 and its raw materials (a), the PXRD spectrum of compound 6 prepared in Example 6 and the comparison of PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 6 prepared in Example 6 (c);

[0051] Figure 7 The following are the powder XRD diffraction comparison spectra of compound 7 prepared in Example 7 and its raw materials (a), the PXRD spectrum of compound 7 prepared in Example 7 and the comparison of PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 7 prepared in Example 7 (c);

[0052] Figure 8 The following are the powder XRD diffraction comparison spectra of compound 8 prepared in Example 8 and its raw materials (a), the comparison diagram of PXRD spectrum of compound 8 prepared in Example 8 and PXRD spectrum of different simulated stacking structures (b), and nitrogen adsorption isotherm of compound 8 prepared in Example 8 (c);

[0053] Fig. 9 The following are the powder XRD diffraction comparison spectra of compound 9 prepared in Example 9 and its raw materials (a), the PXRD spectrum of compound 9 prepared in Example 9 and the comparison of PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 9 prepared in Example 9 (c);

[0054] Fig.10 The following are the powder XRD diffraction comparison spectra of the compound 10 prepared in Example 10 and its raw materials (a), the PXRD pattern of the compound 10 prepared in Example 10 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 10 prepared in Example 10 (c);

[0055] Fig.11 The following are the powder XRD diffraction comparison spectra of the compound 11 prepared in Example 11 and its raw materials (a), the PXRD pattern of the compound 11 prepared in Example 11 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 11 prepared in Example 11 (c);

[0056] Fig.12The following are the powder XRD diffraction comparison spectra of the compound 12 prepared in Example 12 and its raw materials (a), the PXRD pattern of the compound 12 prepared in Example 12 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 12 prepared in Example 12 (c);

[0057] Fig.13 The following are the powder XRD diffraction comparison spectra of the compound 13 prepared in Example 13 and its raw materials (a), the PXRD pattern of the compound 13 prepared in Example 13 and the comparison of the PXRD patterns of different simulated stacking structures, and the nitrogen adsorption isotherm of the compound 13 prepared in Example 13 (c);

[0058] Fig.14 The following are the powder XRD diffraction comparison spectra of compound 14 prepared in Example 14 and its raw materials (a), the PXRD pattern of compound 14 prepared in Example 14 and the comparison of PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 14 prepared in Example 14 (c);

[0059] Fig.15 The following are the powder XRD diffraction comparison spectra of compound 15 prepared in Example 15 and its raw materials (a), the PXRD pattern of compound 15 prepared in Example 15 and the comparison of PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 15 prepared in Example 15 (c);

[0060] Fig.16 The following are the powder XRD diffraction comparison spectra of compound 16 prepared in Example 16 and its raw materials (a), the PXRD spectrum of compound 16 prepared in Example 16 and the comparison of PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 16 prepared in Example 16 (c);

[0061] Fig.17 The following are the powder XRD diffraction comparison spectra of compound 17 prepared in Example 17 and its raw materials (a), the PXRD pattern of compound 17 prepared in Example 17 and the comparison of PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 17 prepared in Example 17 (c);

[0062] Fig.18 The powder XRD diffraction comparison spectrum of compound 18 prepared in Example 18 and its raw material (a), the comparison diagram of PXRD spectrum of compound 18 prepared in Example 18 and PXRD spectrum of different simulated stacking structures (b), and nitrogen adsorption isotherm of compound 18 prepared in Example 18 (c);

[0063] Fig.19The following are the powder XRD diffraction comparison spectra of compound 19 prepared in Example 19 and its raw materials (a), the PXRD pattern of compound 19 prepared in Example 19 and the comparison of PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 19 prepared in Example 19 (c);

[0064] Fig. 20 The following are the powder XRD diffraction comparison spectra of the compound 20 prepared in Example 20 and its raw materials (a), the PXRD pattern of the compound 20 prepared in Example 20 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 20 prepared in Example 20 (c);

[0065] Fig.21 The following are the powder XRD diffraction comparison spectra of the compound 21 prepared in Example 21 and its raw material (a), the PXRD pattern of the compound 21 prepared in Example 21 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 21 prepared in Example 21 (c);

[0066] Fig. 22 The following are the powder XRD diffraction comparison spectra of the compound 22 prepared in Example 22 and its raw materials (a), the PXRD pattern of the compound 22 prepared in Example 22 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 22 prepared in Example 22 (c);

[0067] Fig.23 The following are the powder XRD diffraction comparison spectra of the compound 23 prepared in Example 23 and its raw materials (a), the PXRD pattern of the compound 23 prepared in Example 23 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 23 prepared in Example 23 (c);

[0068] Fig.24 The following are the powder XRD diffraction comparison spectra of the compound 24 prepared in Example 24 and its raw materials (a), the PXRD pattern of the compound 24 prepared in Example 24 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 24 prepared in Example 24 (c);

[0069] Fig.25 The following are the powder XRD diffraction comparison spectra of the compound 25 prepared in Example 25 and its raw material (a), the PXRD pattern of the compound 25 prepared in Example 25 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 25 prepared in Example 25 (c);

[0070] Fig.26The following are the powder XRD diffraction comparison spectra of the compound 26 prepared in Example 26 and its raw materials (a), the PXRD pattern of the compound 26 prepared in Example 26 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 26 prepared in Example 26 (c);

[0071] Fig. 27 The following are the powder XRD diffraction comparison spectra of the compound 27 prepared in Example 27 and its raw materials (a), the PXRD pattern of the compound 27 prepared in Example 27 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 27 prepared in Example 27 (c);

[0072] Fig.28 The powder XRD diffraction comparison spectrum of the compound 28 prepared in Example 28 and its raw material (a), the PXRD pattern of the compound 28 prepared in Example 28 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 28 prepared in Example 28 (c);

[0073] Fig.29 The following are the powder XRD diffraction comparison spectra of the compound 29 prepared in Example 29 and its raw materials (a), the PXRD pattern of the compound 29 prepared in Example 29 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 29 prepared in Example 29 (c);

[0074] Fig.30 The following are the powder XRD diffraction comparison spectra of the compound 30 prepared in Example 30 and its raw materials (a), the PXRD spectrum of the compound 30 prepared in Example 30 and the comparison of the PXRD spectrum of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 30 prepared in Example 30 (c);

[0075] Fig.31 The following are the powder XRD diffraction comparison spectra of the compound 31 prepared in Example 31 and its raw material (a), the PXRD pattern of the compound 31 prepared in Example 31 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 31 prepared in Example 31 (c);

[0076] Fig.32 The following are the powder XRD diffraction comparison spectra of the compound 32 prepared in Example 32 and its raw material (a), the PXRD pattern of the compound 32 prepared in Example 32 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 32 prepared in Example 32 (c);

[0077] Fig.33The following are the powder XRD diffraction comparison spectra of the compound 33 prepared in Example 33 and its raw material (a), the PXRD pattern of the compound 33 prepared in Example 33 and the comparison of the PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of the compound 33 prepared in Example 33 (c);

[0078] Fig.34 The following are the powder XRD diffraction comparison spectra of compound 34 prepared in Example 34 and its raw materials (a), the PXRD pattern of compound 34 prepared in Example 34 and the comparison of PXRD patterns of different simulated stacking structures (b), and the nitrogen adsorption isotherm of compound 34 prepared in Example 34 (c);

[0079] Fig.35 Powder XRD diffraction comparison spectrum of compound 35 prepared in Example 35 and its raw material (a), comparison of PXRD spectrum of compound 35 prepared in Example 35 and PXRD spectrum of different simulated stacking structures (b), nitrogen adsorption isotherm of compound 35 prepared in Example 35 (c). DETAILED DESCRIPTION

[0080] The present invention is further described in detail below in conjunction with the examples and drawings, but the embodiments of the present invention are not limited thereto. If specific conditions are not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0081] Unless otherwise specified, the reagents used in the examples can be purchased from the market.

[0082] In the present 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 framework materials of different structures. For the sake of convenience, the copper-based metal organic framework materials prepared in different reaction processes are marked with different names. Among them, the model of the ultrasonic instrument used in the embodiment is a 250W BransonSonifier SFX250 cell disruptor, and the "ultrasound" in the embodiment refers to the power of the ultrasonic instrument used being 200W and the amplitude rod of 3 mm.

[0083] Example 1: Preparation of Compound 1

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

[0085] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with it, and dried to obtain a metal organic framework material, which was recorded as compound 1.

[0086] The crystallinity of 35 copper-based metal organic frameworks was characterized by X-ray powder diffraction (PXRD) and the structures were simulated and refined using Materials Studio software. Figure 1 The PXRD patterns of 1 and its raw material are compared, as well as the experimental PXRD patterns of 1 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 1 at 77 K using a gas adsorption instrument. Figure 1 It can be seen that 1 has obvious porosity, and its specific surface area (BET) is 525m 2 g -1 .

[0087] Example 2: Preparation of Compound 2

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

[0089] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with it, and dried to obtain a metal organic framework material, which was recorded as compound 2.

[0090] Figure 2 The figure shows the comparison of the PXRD patterns of compound 2 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 2 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 2 was carried out at 77K using a gas adsorption instrument. Figure 2 It can be seen that 2 has obvious porosity, and its specific surface area (BET) is 817m 2 g -1 .

[0091] Example 3: Preparation of Compound 3

[0092] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (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) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0093] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 3.

[0094] Figure 3 The PXRD patterns of 3 and its raw materials are compared, as well as the experimental PXRD patterns of 3 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to perform nitrogen adsorption test on 3 at 77K. Figure 3 It can be seen that compound 3 has obvious porosity, and its specific surface area (BET) is 336m 2 g -1 .

[0095] Example 4: Preparation of Compound 4

[0096] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (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) were mixed in 6 mL of 4 M aqueous acetic acid solution;

[0097] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with it, and dried to obtain a metal organic framework material, which was recorded as compound 4.

[0098] Figure 4 The figure shows the comparison of the PXRD patterns of compound 4 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 4 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 4 at 77K using a gas adsorption instrument. Figure 4 It can be seen that compound 4 has obvious porosity, and its specific surface area (BET) is 605m 2 g -1 .

[0099] Example 5: Preparation of Compound 5

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

[0101] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with it, and dried to obtain a metal organic framework material, which was recorded as compound 5.

[0102] Figure 5 The PXRD patterns of 5 and its raw materials are compared, as well as the experimental PXRD patterns of 5 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 5 at 77K using a gas adsorption instrument. Figure 5 It can be seen that compound 5 has obvious porosity, and its specific surface area (BET) is 584m 2 g -1 .

[0103] Example 6: Preparation of Compound 6

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

[0105] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 6.

[0106] Figure 6 The PXRD patterns of 6 and its raw materials are compared, as well as the experimental PXRD patterns of 6 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test the nitrogen adsorption of 6 at 77K. Figure 6 It can be seen that compound 6 has obvious porosity, and its specific surface area (BET) is 817m 2 g -1 .

[0107] Example 7: Preparation of Compound 7

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

[0109] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 7.

[0110] Figure 7 The PXRD patterns of 7 and its raw materials are compared, as well as the experimental PXRD patterns of 7 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 7 at 77 K using a gas adsorption instrument. Figure 7 It can be seen that compound 7 has obvious porosity, and its specific surface area (BET) is 864m 2 g -1 .

[0111] Example 8: Preparation of Compound 8

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

[0113] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 8.

[0114] Figure 8 The PXRD spectra of 8 and its raw material are compared, as well as the experimental PXRD spectra of 8 and the PXRD spectra of different simulated stacking structures. The nitrogen adsorption test of 1 was carried out at 77K using a gas adsorption instrument. Figure 8 It can be seen that compound 8 has obvious porosity, and its specific surface area (BET) is 832m 2 g -1 .

[0115] Example 9: Preparation of Compound 9

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

[0117] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 9.

[0118] Fig. 9 The figure shows the comparison of the PXRD patterns of compound 9 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 9 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 9 was carried out at 77K using a gas adsorption instrument. Fig. 9 It can be seen that compound 9 has obvious porosity, and its specific surface area (BET) is 835m 2 g -1 .

[0119] Example 10: Preparation of Compound 10

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

[0121] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 10.

[0122] Fig.10 The figure shows the comparison of the PXRD patterns of compound 10 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 10 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 10 was carried out at 77K using a gas adsorption instrument. Fig.10 It can be seen that compound 10 has obvious porosity, and its specific surface area (BET) is 120m 2 g -1 .

[0123] Example 11: Preparation of Compound 11

[0124] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (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 was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 11.

[0126] Fig.11 The figure shows the comparison of the PXRD patterns of compound 11 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 11 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 11 was carried out at 77K using a gas adsorption instrument. Fig.11 It can be seen that compound 11 has obvious porosity, and its specific surface area (BET) is 829m 2 g -1 .

[0127] Example 12: Preparation of Compound 12

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

[0129] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 12.

[0130] Fig.12 The figure shows the comparison of the PXRD patterns of compound 12 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 12 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test the nitrogen adsorption of 12 at 77K. Fig.12 It can be seen that compound 12 has obvious porosity, and its specific surface area (BET) is 83m 2 g -1 .

[0131] Example 13: Preparation of Compound 13

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

[0133] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 13.

[0134] Fig.13 The figure shows the comparison of the PXRD patterns of compound 13 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 13 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 13 at 77K using a gas adsorption instrument. Fig.13 It can be seen that compound 13 has obvious porosity, and its specific surface area (BET) is 936m 2 g -1 .

[0135] Example 14: Preparation of Compound 14

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

[0137] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 14.

[0138] Fig.14 The figure shows the comparison of the PXRD patterns of compound 14 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 14 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 14 was carried out at 77K using a gas adsorption instrument. Fig.14 It can be seen that compound 14 has obvious porosity, and its specific surface area (BET) is 1339m 2 g -1 .

[0139] Example 15: Preparation of Compound 15

[0140] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (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) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0141] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 15.

[0142] Fig.15 The figure shows the comparison of the PXRD patterns of compound 15 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 15 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 1 was carried out at 77K using a gas adsorption instrument. Fig.15 It can be seen that compound 15 has obvious porosity, and its specific surface area (BET) is 1367m 2 g -1 .

[0143] Example 16: Preparation of Compound 16

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

[0145] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 16.

[0146] Fig.16 The figure shows the comparison of the PXRD patterns of compound 16 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 16 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 1 was carried out at 77K using a gas adsorption instrument. Fig.16 It can be seen that compound 16 has obvious porosity, and its specific surface area (BET) is 1137m 2 g -1 .

[0147] Example 17: Preparation of Compound 17

[0148] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (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 was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 17.

[0150] Fig.17 The figure shows the comparison of the PXRD patterns of compound 17 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 17 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 17 at 77K using a gas adsorption instrument. Fig.17 It can be seen that compound 17 has obvious porosity, and its specific surface area (BET) is 149m 2 g -1 .

[0151] Example 18: Preparation of Compound 18

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

[0153] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 18.

[0154] Fig.18 The figure shows the comparison of the PXRD patterns of compound 18 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 18 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test the nitrogen adsorption of 18 at 77K. Fig.18 It can be seen that compound 18 has obvious porosity, and its specific surface area (BET) is 816m 2 g -1 .

[0155] Example 19: Preparation of Compound 19

[0156] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (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 aqueous acetic acid solution;

[0157] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 19.

[0158] Fig.19 The figure shows the comparison of the PXRD patterns of compound 19 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 19 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 19 at 77K using a gas adsorption instrument. Fig.19 It can be seen that compound 19 has obvious porosity, and its specific surface area (BET) is 1567m 2 g -1 .

[0159] Example 20: Preparation of Compound 20

[0160] (1) Cu2O (10.7 mg, 0.075 mmol), 4-formylpyrazole (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 aqueous acetic acid solution;

[0161] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 20.

[0162] Fig. 20 The figure shows the comparison of the PXRD patterns of compound 20 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 20 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to perform nitrogen adsorption test on 20 at 77K. Fig. 20 It can be seen that compound 20 has obvious porosity, and its specific surface area (BET) is 712 m 2 g -1 .

[0163] Example 21: Preparation of Compound 21

[0164] (1) Cu2O (10.7 mg, 0.075 mmol), 4-formylpyrazole (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 aqueous acetic acid solution;

[0165] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 21.

[0166] Fig.21 The figure shows the comparison of the PXRD patterns of compound 21 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 21 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to perform nitrogen adsorption test on 21 at 77K. Fig.21 It can be seen that compound 21 has obvious porosity, and its specific surface area (BET) is 1300m 2 g -1 .

[0167] Example 22: Preparation of Compound 22

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

[0169] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 22.

[0170] Fig. 22 The figure shows the comparison of the PXRD patterns of compound 22 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 22 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test 22 for nitrogen adsorption at 77K. Fig. 22 It can be seen that compound 22 has obvious porosity, and its specific surface area (BET) is 997m 2 g -1 .

[0171] Example 23: Preparation of Compound 23

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

[0173] (2) Then, the cell wall was disrupted by ultrasound for one hour; centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 23.

[0174] Fig.23 The figure shows the comparison of the PXRD patterns of compound 23 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 23 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 23 at 77K using a gas adsorption instrument. Fig.23 It can be seen that compound 23 has obvious porosity, and its specific surface area (BET) is 430m 2 g -1 .

[0175] Example 24: Preparation of Compound 24

[0176] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4-amino-2-methoxybenzohydrazide (AMBH, 40.8 mg, 0.225 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0177] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 24.

[0178] Fig.24 The figure shows the comparison of the PXRD patterns of compound 24 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 24 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 24 was carried out at 77K using a gas adsorption instrument. Fig.24 It can be seen that compound 24 has obvious porosity, and its specific surface area (BET) is 301m 2 g -1 .

[0179] Example 25: Preparation of Compound 25

[0180] (1) Cu2O (32.2 mg, 0.225 mmol), 3-methyl-pyrazole-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) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0181] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 25.

[0182] Fig.25 The figure shows the comparison of the PXRD patterns of compound 25 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 25 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test nitrogen adsorption of 25 at 77K. Fig.25 It can be seen that compound 25 has obvious porosity, and its specific surface area (BET) is 616m 2 g -1 .

[0183] Example 26: Preparation of Compound 26

[0184] (1) 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) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0185] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 26.

[0186] Fig.26 The figure shows the comparison of the PXRD patterns of compound 26 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 26 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption isotherm of 26 at 77K was tested by a gas adsorption instrument. Fig.26 It can be seen that compound 26 has obvious porosity, and its specific surface area (BET) is 927m 2 g -1 .

[0187] Example 27: Preparation of Compound 27

[0188] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (Pz-CHO, 43.2 mg, 0.45 mmol) and 4-aminopyrazole (Pz-NH2, 37.4 mg, 0.45 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0189] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 27.

[0190] Fig. 27 The figure shows the comparison of the PXRD patterns of compound 27 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 27 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 27 at 77K using a gas adsorption instrument. Fig. 27 It can be seen that compound 27 has obvious porosity, and its specific surface area (BET) is 574m 2 g -1 .

[0191] Example 28: Preparation of Compound 28

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

[0193] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 28.

[0194] Fig.28 The figure shows the comparison of the PXRD patterns of compound 28 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 28 and the PXRD patterns of different simulated stacking structures. The nitrogen adsorption test of 28 was carried out at 77K using a gas adsorption instrument. Fig.28 It can be seen that compound 28 has obvious porosity, and its specific surface area (BET) is 391m 2 g -1 .

[0195] Example 29: Preparation of Compound 29

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

[0197] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 29.

[0198] Fig.29 The figure shows the comparison of the PXRD patterns of compound 29 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 29 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 29 at 77K using a gas adsorption instrument. Fig.29 It can be seen that compound 29 has obvious porosity, and its specific surface area (BET) is 1192m 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 aqueous acetic acid solution;

[0201] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 30.

[0202] Fig.30 The figure shows the comparison of the PXRD patterns of compound 30 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 30 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test nitrogen adsorption of 30 at 77K. Fig.30 It can be seen that compound 30 has obvious porosity, and its specific surface area (BET) is 1030m 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-tri(4-formylphenyl)benzene (TFPB, 58.6 mg, 0.15 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0205] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 31.

[0206] Fig.31 The figure shows the comparison of the PXRD patterns of compound 31 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 31 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 31 at 77K using a gas adsorption instrument. Fig.31 It can be seen that compound 31 has obvious porosity, and its specific surface area (BET) is 1056m 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 aqueous acetic acid solution;

[0209] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 32.

[0210] Fig.32 The figure shows the comparison of the PXRD patterns of compound 32 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 32 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to perform nitrogen adsorption test on 32 at 77K. Fig.32 It can be seen that compound 32 has obvious porosity, and its specific surface area (BET) is 1033m 2 g -1 .

[0211] Example 33: Preparation of Compound 33

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

[0213] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 33.

[0214] Fig.33 The figure shows the comparison of the PXRD patterns of compound 33 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 33 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test nitrogen adsorption of 33 at 77K. Fig.33 It can be seen that compound 33 has obvious porosity, and its specific surface area (BET) is 1093m 2 g -1 .

[0215] Example 34: Preparation of Compound 34

[0216] (1) Cu2O (21.5 mg, 0.15 mmol), 4-formylpyrazole (Pz-CHO, 28 mg, 0.30 mmol) and gold trinuclear triamine (Au-CTC, 95.7 mg, 0.10 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0217] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 34.

[0218] Fig.34 The figure shows the comparison of the PXRD patterns of compound 34 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 34 and the PXRD patterns of different simulated stacking structures. A gas adsorption instrument was used to test nitrogen adsorption of 34 at 77K. Fig.34 It can be seen that compound 34 has obvious porosity, and its specific surface area (BET) is 534m 2 g -1 .

[0219] Example 35: Preparation of Compound 35

[0220] (1) Cu2O (32.2 mg, 0.225 mmol), 4-formylpyrazole (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 uL, 0.45 mmol) were mixed in 6 mL of 4 M acetic acid aqueous solution;

[0221] (2) Then, the cell wall was disrupted by ultrasound for one hour; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain a metal organic framework material, which was recorded as compound 35.

[0222] Fig.35 The figure shows the comparison of the PXRD patterns of compound 35 and its raw material, as well as the comparison of the experimentally measured PXRD patterns of 35 and the PXRD patterns of different simulated stacking structures. A nitrogen adsorption test was performed on 35 at 77K using a gas adsorption instrument. Fig.35 It can be seen that compound 35 has obvious porosity, and its specific surface area (BET) is 348m 2 g -1 .

[0223] Example 36: Preparation of Compound 16

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

[0225] (2) Then, the mixture was stirred at room temperature for 7 days (500 rpm); centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain compound 16. The PXRD pattern of the obtained compound also proved that compound 16 was successfully synthesized.

[0226] Example 37: Preparation of Compound 16

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

[0228] (2) Then, the mixture was ultrasonically treated for one hour using a cell wall disruptor; the mixture was centrifuged, washed with anhydrous ethanol, extracted with ethanol, and dried to obtain compound 16. The PXRD pattern of the obtained compound 16 can also be compared to prove that compound 16 was successfully synthesized.

[0229] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for synthesizing metal organic framework materials in one pot in water, characterized in that The following steps are involved: A pyrazolyl derivative containing an amino group or an aldehyde group, a linker containing an aldehyde group or an amino group, a copper salt and pyruvic acid are mixed, and an acid solution of water is added thereto, and a metal organic framework material is obtained after ultrasonic or stirring reaction at room temperature, and the amount of pyruvic acid used is 0 or not 0; When a pyrazolyl derivative containing an amino group is selected as a raw material, the corresponding linker is selected as a linker containing an aldehyde group; when a pyrazolyl derivative containing an aldehyde group is selected as a raw material, the corresponding linker is selected as a linker containing an amino group.

2. The method for synthesizing metal organic framework materials in an aqueous one-pot process according to claim 1, characterized in that: The structure of the pyrazolyl derivative containing an amino group or an aldehyde group is shown below: In the pyrazolyl derivative containing an amino group or an aldehyde group, R1 is one of H and -CH3; R2 is one of H and -CH3; and R3 is one of -CHO, -NH2, and -CON2H3.

3. 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 group or an aldehyde group is one of the following structures:

4. The method for synthesizing metal organic framework materials in one pot in water according to claim 1, characterized in that: The linker containing an aldehyde group or an amino group includes at least one of a bidentate linker, a tridentate linker, and a tetradentate linker, wherein the bidentate 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:

5. The method for synthesizing metal organic framework materials in one pot in water according to claim 1, characterized in that: The copper salt is at least one of cuprous oxide, cupric nitrate, cuprous bromide, cuprous iodide, copper sulfate, etc., preferably at least one of cuprous oxide and cupric 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 group or an aldehyde group, the linker containing an aldehyde group or an amino group, and the 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 aqueous acid solution, wherein the acid is at least one of acetic acid and trifluoroacetic acid, wherein the acid concentration is 1.0M-17.5M, and the amount of the aqueous acid solution is such that 1.0-18mL of aqueous acid solution is added for every 0.20mmol of copper salt.

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

9. The method for synthesizing metal organic framework materials in an aqueous phase one-pot process according to claim 1, characterized in that: The ultrasonic treatment also includes a purification step, which is as follows: centrifugation after ultrasonic treatment, then washing with anhydrous ethanol, and then 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 to 9, wherein the structural formula is one of the following structures:

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