Preparation method and application of HKUST-1 metal-organic framework material with controllable micro / nano particle size

Abstract

The application discloses a preparation method of controllable micro-nano-particle-size metal organic framework HKUST-1 material, and comprises the following steps: slowly adding a copper acetate solution into a solution of trimesic acid, stirring the solution at room temperature to obtain a suspension; centrifuging the suspension to obtain a precipitate as a crude product of HKUST-1; and purifying the crude product of HKUST-1 through an organic or inorganic reagent, and obtaining the controllable micro-nano-particle-size metal organic framework HKUST-1 material after removing the purification reagent. The preparation method can be used to prepare the HKUST-1 material with controllable particle size through a simple process, and the HKUST-1 material with nanometer size can be applied to nanometer biomaterials.

Description

Technical Field

[0001] This invention belongs to the field of materials preparation technology, specifically, it relates to a method for preparing and applying a controllable micro-nano particle size metal-organic framework HKUST-1 material. Background Technology

[0002] Metal-organic frameworks (MOFs), also known as porous coordination polymers, are a new type of organic-inorganic hybrid material that typically consists of metal ions or metal clusters as nodes and organic ligands as connectors, forming a periodic structure through coordination bonds under certain conditions [You Jiayong, Zhang Tianyong, Liu Yanfeng, Li Bin, Zhao Zhendong, Huang Junhao. Rapid synthesis of metal-organic framework compound HKUST-1 [J]. Journal of Chemical Engineering of Chinese Universities, 2015, 29(05): 1126-1132.]. Due to their large specific surface area, high porosity, and tunable structure, MOFs have attracted great interest from researchers in various fields at home and abroad since they were first reported in the 1990s, and have been widely used in gas separation and adsorption, catalysis, drug delivery, sensing, etc. [Li Chong, Li Na, Chang Limei, Gu Zhigang, Zhang Jian. Research progress of metal-organic framework HKUST-1 membrane in gas separation [J]. Acta Chimica Sinica, 2022, 80(03): 340-358.]. The chemical and physical properties of metal elements (MOFs) can be tuned depending on the choice of metal nodes and organic linkers, making them suitable for the storage and release of metal ions. Furthermore, their low toxicity, excellent biodegradability, and ease of functionalization have expanded their applications to the medical and biological fields. Copper is an essential trace element naturally found in plant and animal tissues, playing a crucial role in activating cell energy production, forming nerves, and synthesizing elastin. In addition, copper ions have a certain bactericidal effect and are relatively cheaper than metals such as gold and silver. Therefore, in recent years, copper-based biomaterials have begun to be widely used in biomedical fields such as sterilization and wound repair. However, the toxicity of excessive copper ions to cells limits their further application in the biomedical field. HKUST-1 is a classic copper-based MOF structure, first reported by Williams' research group in Science in 1999. It is a coordination polymer prepared from copper ions and trimesic acid through a coordination reaction. Currently, HKUST-1 is widely used in gas adsorption, fluorescence, and the preparation of antibacterial materials. Due to its ability to release copper ions, it also has great potential in the biomedical field.

[0003] Currently, the main methods for synthesizing HKUST-1 include solvothermal synthesis, ultrasonic synthesis, microwave synthesis, electrochemical synthesis, and in-situ growth. Solvothermal synthesis involves dissolving a measured amount of reaction mixture in a specially designed sealed container or high-pressure reactor under specific conditions. The sealed apparatus is then placed in a high-temperature oven for recrystallization under relatively high temperature (less than 250°C) and high pressure (less than 10 MPa). While solvothermal synthesis of HKUST-1 offers lower raw material costs and higher product yields, the reaction conditions are mostly under high temperature and pressure, and it easily leads to the formation of the byproduct Cu2O. Ultrasonic synthesis primarily utilizes ultrasound to accelerate chemical reactions or trigger new reactions, thereby increasing the chemical reaction yield or obtaining new chemical products. Compared to solvothermal synthesis, ultrasonic synthesis can achieve higher yields of the target product in a very short reaction time, but its cost is relatively high. Microwave synthesis, also known as microwave synthesis, offers advantages such as rapid heating of the reaction system, accelerated reaction rate, and improved reaction selectivity, making it superior to traditional solvothermal synthesis. Currently, research on microwave synthesis of HKUST-1 is limited. Seo et al. obtained HKUST-1 using a microwave method at a reaction temperature of 120℃. The electrochemical method involves placing a metal electrode (providing the metal cations required by the corresponding MOFs) as the anode in a solution containing organic ligands. Campagnol et al. synthesized HKUST-1 by electrodeposition at different temperatures; the HKUST-1 film deposited at room temperature had an octahedral crystal structure, while at 200℃, the crystal structure became a cross-linked three-dimensional structure. The in-situ growth method involves preparing a specific MOF reactant solvent according to the experimental protocol, adding one or more supports to the mother liquor, and maintaining the reaction temperature consistent with the heating conditions of the corresponding MOFs, thus achieving a solvothermal reaction. Therefore, although there are currently various methods for preparing HKUST-1, these methods all require relatively harsh preparation conditions (such as high temperature and high pressure, or the need for ultrasound), and the particle size of the prepared HKUST-1 is uncontrollable, basically at the micrometer level. This limits its application in nanobiomaterials.

[0004] Therefore, there is an urgent need to develop a simple, mild, and adjustable method for preparing HKUST-1 material. Summary of the Invention

[0005] The first objective of this invention is to provide a method for preparing HKUST-1 material with controllable micro- and nano-sized metal-organic frameworks.

[0006] The second objective of this invention is to provide an application of the controllable micro / nano particle size metal-organic framework HKUST-1 material prepared by the method described above in the preparation of nanobiomaterials, gas adsorption and storage materials, and catalytic materials.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] The first aspect of this invention provides a method for preparing a controllable micro / nano-sized metal-organic framework HKUST-1 material, comprising the following steps:

[0009] Slowly add a copper acetate solution with a concentration of 10-20 mg / mL (preferably 15 mg / mL) to a pyromellitic acid solution with a concentration of 5-15 mg / mL (preferably 10 mg / mL). After the addition is complete, seal the container and stir for 5-30 minutes. The molar ratio of copper acetate to pyromellitic acid is (1.5-3):1.

[0010] Add triethanolamine (TEA) dropwise to the above solution, stir for 5–20 min, and sonicate for 5–20 min to obtain a suspension; the molar ratio of copper acetate to triethanolamine is 1:1.

[0011] The above suspension was centrifuged to obtain the precipitate as the crude product HKUST-1;

[0012] The crude HKUST-1 product was purified sequentially by ultrapure water, dimethylformamide (DMF), dichloromethane, and anhydrous ethanol. After removing the purification reagents, the controllable micro-nano particle size metal-organic framework HKUST-1 material was obtained.

[0013] The controllable micro / nano particle size metal-organic framework HKUST-1 material has a particle size ≤500nm.

[0014] The preparation method of the trimellitic acid solution includes the following steps: dissolving trimellitic acid in a mixed solution of anhydrous ethanol and dimethylformamide with a volume ratio of 2:1 to make the solution concentration 5-15 mg / mL, and sonicating for 5-30 min to obtain the trimellitic acid solution.

[0015] The preparation method of the copper acetate solution includes the following steps: dissolving copper acetate monohydrate and polyvinylpyrrolidone in a mass ratio of 1:3 in a mixed solution of dimethylformamide and ultrapure water to make the concentration of copper acetate solution 10-20 mg / mL, the volume ratio of ultrapure water to dimethylformamide 3:1, and sonicating for 5-30 min to obtain the copper acetate solution.

[0016] The ultrapure water purification method includes the following steps: adding an equal volume of ultrapure water to the centrifuge tube containing the HKUST-1 crude product, balancing the liquid, stirring and shaking the tube with a turbine to uniformly disperse the crude product into a suspension, sonicating, centrifuging, and separating the HKUST-1 crude product; repeating this step twice to obtain the HKUST-1 crude product after ultrapure water replacement.

[0017] The method for purifying dimethylformamide includes the following steps: adding an equal volume of DMF to the centrifuge tube containing the crude HKUST-1 product obtained above, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, centrifuging to separate the crude HKUST-1 product; repeating this step once, adding an equal volume of DMF to the original supernatant volume, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, shaking the centrifuge tube, centrifuging to obtain the crude HKUST-1 product after DMF replacement.

[0018] The method for purifying dichloromethane includes the following steps: adding an equal volume of dichloromethane to the centrifuge tube containing the crude HKUST-1 product obtained above, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, centrifuging to separate the crude HKUST-1 product; repeating this step once, adding an equal volume of dichloromethane to the liquid, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, shaking the centrifuge tube, centrifuging to obtain the crude HKUST-1 product after dichloromethane replacement.

[0019] The method for purifying anhydrous ethanol includes the following steps: adding an equal volume of anhydrous ethanol to the centrifuge tube containing the crude HKUST-1 product, balancing the volume, stirring and shaking the tube to uniformly disperse the crude product into a suspension, centrifuging to separate the crude HKUST-1 product; repeating this step once, adding an equal volume of anhydrous ethanol to the original supernatant volume, stirring and shaking the tube to uniformly disperse the crude product into a suspension, and sonicating.

[0020] A second aspect of the present invention provides a method for preparing a controllable micro / nano-sized metal-organic framework HKUST-1 material, comprising the following steps:

[0021] Slowly add a copper acetate solution with a concentration of 10-20 mg / mL (preferably 15 mg / mL) to a pyromellitic acid solution with a concentration of 5-15 mg / mL (preferably 10 mg / mL). After the addition is complete, seal the container and stir for 5-30 minutes. The molar ratio of copper acetate to pyromellitic acid is (1.5-3):1.

[0022] Add triethanolamine (TEA) dropwise to the above solution, stir for 5–20 min, and sonicate for 5–20 min to obtain a suspension; the molar ratio of copper acetate to triethanolamine is 1:1.

[0023] The above suspension was centrifuged to obtain the precipitate as the crude product HKUST-1;

[0024] The crude HKUST-1 product was purified sequentially by ultrapure water, dimethylformamide (DMF), dichloromethane, and anhydrous ethanol, then filtered and dried to obtain the controllable micro-nano particle size metal-organic framework HKUST-1 material.

[0025] The particle size of the controllable micro / nano particle size metal-organic framework HKUST-1 material is: 500nm < particle size ≤ 2μm.

[0026] The preparation method of the trimellitic acid solution includes the following steps: dissolving trimellitic acid in a mixed solution of anhydrous ethanol and dimethylformamide with a volume ratio of 2:1 to make the solution concentration 5-15 mg / mL, and sonicating for 5-30 min to obtain the trimellitic acid solution.

[0027] The preparation method of the copper acetate solution includes the following steps: dissolving copper acetate monohydrate in a mixed solution of dimethylformamide (DMF) and ultrapure water to make the concentration of copper acetate solution 10-20 mg / mL, the volume ratio of ultrapure water to dimethylformamide 3:1, and sonicating for 5-30 min to obtain the copper acetate solution.

[0028] The ultrapure water purification method includes the following steps: adding an equal volume of ultrapure water to the centrifuge tube containing the HKUST-1 crude product, balancing the liquid, stirring and shaking the tube with a turbine to uniformly disperse the crude product into a suspension, sonicating, centrifuging, and separating the HKUST-1 crude product; repeating this step twice to obtain the HKUST-1 crude product after ultrapure water replacement.

[0029] The method for purifying dimethylformamide includes the following steps: adding an equal volume of DMF to the centrifuge tube containing the crude HKUST-1 product obtained above, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, centrifuging to separate the crude HKUST-1 product; repeating this step once, adding an equal volume of DMF to the original supernatant volume, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, shaking the centrifuge tube, centrifuging to obtain the crude HKUST-1 product after DMF replacement.

[0030] The method for purifying dichloromethane includes the following steps: adding an equal volume of dichloromethane to the centrifuge tube containing the crude HKUST-1 product obtained above, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, centrifuging to separate the crude HKUST-1 product; repeating this step once, adding an equal volume of dichloromethane to the liquid, balancing the liquid, stirring and shaking the liquid with a turbine to uniformly disperse the crude product into a suspension, shaking the centrifuge tube, centrifuging to obtain the crude HKUST-1 product after dichloromethane replacement.

[0031] The method for purifying anhydrous ethanol includes the following steps: adding an equal volume of anhydrous ethanol to the centrifuge tube containing the crude HKUST-1 product, balancing the volume, and stirring and shaking the tube to uniformly disperse the crude product into a suspension. Centrifuging is then performed to separate the crude HKUST-1 product. This step is repeated once, and then an equal volume of anhydrous ethanol is added again, and the tube is stirred and shaken to uniformly disperse the crude product into a suspension. The suspension is then stirred and sonicated.

[0032] A third aspect of the present invention provides a method for preparing a controllable micro / nano-sized metal-organic framework HKUST-1 material, comprising the following steps:

[0033] Slowly add a copper acetate solution with a concentration of 10-20 mg / mL (preferably 15 mg / mL) to a pyromellitic acid solution with a concentration of 5-15 mg / mL (preferably 10 mg / mL). After the addition is complete, seal the container and stir for 5-30 minutes. The molar ratio of copper acetate to pyromellitic acid is (1.5-3):1.

[0034] Centrifugation was performed to purify the crude HKUST-1 product with 50% ethanol. The product was then filtered and dried to obtain the controllable micro-nano particle size metal-organic framework HKUST-1 material.

[0035] The particle size of the controllable micro / nano-sized metal-organic framework HKUST-1 material is >2 μm.

[0036] The preparation method of the trimellitic acid solution includes the following steps: dissolving trimellitic acid in anhydrous ethanol to make the solution concentration 5-15 mg / ml, and sonicating for 5-30 min to obtain the trimellitic acid solution.

[0037] The preparation method of the copper acetate solution includes the following steps: dissolving copper acetate monohydrate in ultrapure water to make the solution concentration 10-20 mg / mL, and sonicating for 5-30 min to obtain the copper acetate solution.

[0038] The method for purifying with 50% ethanol includes the following steps: adding an equal volume of 50% ethanol to the centrifuge tube containing the crude HKUST-1 product, balancing the liquid, stirring and shaking the tube with a turbine to uniformly disperse the crude product into a suspension, sonicating, centrifuging, and separating the crude HKUST-1 product; repeating this step twice to obtain the crude HKUST-1 product after replacement with 50% ethanol.

[0039] A fourth aspect of the present invention provides an application of the controllable micro / nano particle size metal-organic framework HKUST-1 material prepared by the method described above in the preparation of nanobiomaterials, gas adsorption and storage materials, and catalytic materials.

[0040] By adopting the above technical solution, the present invention has the following advantages and beneficial effects:

[0041] The method for preparing controllable micro / nano-sized metal-organic framework HKUST-1 materials provided by this invention can prepare HKUST-1 materials with controllable particle size using a simple process at room temperature and pressure. For the prepared nano-sized HKUST-1, it can be applied to nanobiomaterials; for the prepared micron-sized HKUST-1, it can be used in fields such as gas adsorption and storage, catalysis, etc. Attached Figure Description

[0042] Figure 1 This is a transmission electron microscope (TEM) image of the HKUST-1 metal-organic framework material with controllable micro / nano particle size.

[0043] Figure 2 This is the particle size distribution of HKUST-1 material.

[0044] Figure 3 This is the XPS analysis chart of HKUST-1 material.

[0045] Figure 4 This is the XRD analysis diagram of HKUST-1 material. Detailed Implementation

[0046] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.

[0047] Example 1

[0048] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: an inorganic-organic phase synthesis method activated by polyvinylpyrrolidone (PVP), wherein the molar ratio of copper acetate to trimesic acid is 3:1 (product particle size ~310 nm).

[0049] Step 1, prepare the solution:

[0050] 1.1 Preparation of copper acetate solution: Dissolve copper acetate monohydrate and PVP in a mixed solution of dimethylformamide (DMF) and ultrapure water at a mass ratio of 1:3. The concentration of copper acetate solution is 15 mg / mL, and the volume ratio of ultrapure water to DMF is 3:1. Sonicate for 10 min. Note that DMF should be added in the fume hood.

[0051] 1.2 Preparation of pyromellitic acid solution: Dissolve pyromellitic acid in a mixture of anhydrous ethanol and DMF in a volume ratio of 2:1 to make the solution concentration 10 mg / mL, and sonicate for 10 min. Note that DMF should be added in the fume hood.

[0052] Step 2, synthesis reaction:

[0053] 1.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0054] Place 42 mL of 10 mg / mL trimellitic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 80 mL of 15 mg / mL copper acetate-PVP solution at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0055] 1.4 Add 0.76 mL of triethanolamine (TEA) dropwise to the above solution, stir magnetically for 10 min, and sonicate for 10 min to obtain a turquoise suspension; the molar ratio of copper acetate to triethanolamine is 1:1.

[0056] 1.5 Centrifugation to obtain crude product: Pour the above turquoise suspension into a high-speed centrifuge tube, balance it, and centrifuge at 3000G for 5 min to obtain the precipitate as HKUST-1 crude product.

[0057] Step 3, purification:

[0058] 1.6 Replacement with ultrapure water: Add an equal volume of ultrapure water to the centrifuge tube containing the HKUST-1 crude product, balance the volume, and use a turbine to stir and shake to evenly disperse the crude product into a suspension. Sonicate for 10 min, centrifuge at 10000G for 15 min to separate the HKUST-1 crude product. Repeat this step twice to obtain the HKUST-1 crude product after ultrapure water replacement. Note that the supernatant should be poured into a waste container.

[0059] 1.7 Replacement and soaking with DMF: Add an equal volume of DMF to the centrifuge tube containing the crude HKUST-1 product obtained above, balance the liquid, and use a turbine to stir and shake to evenly disperse the crude product into a suspension. Centrifuge at 10000G for 15 min to separate the crude HKUST-1 product. Repeat this step once, adding an equal volume of DMF to the original supernatant, balancing the liquid, and using a turbine to stir and shake to evenly disperse the crude product into a suspension. Place the centrifuge tube in a shaking incubator for 2 h, and centrifuge at 10000G for 15 min to obtain the crude HKUST-1 product after DMF replacement. Note that the supernatant should be poured into a waste container, and DMF should be added to the fume hood.

[0060] 1.8 Replacement and soaking with dichloromethane: Add an equal volume of dichloromethane to the centrifuge tube containing the crude HKUST-1 product obtained above, balance the liquid, and use a turbine to stir and shake to evenly disperse the crude product into a suspension. Centrifuge at 10000G for 15 min to separate the crude HKUST-1 product. Repeat this step once, adding an equal volume of dichloromethane to the original supernatant, balancing the liquid, and using a turbine to stir and shake to evenly disperse the crude product into a suspension. Place the centrifuge tube in a shaking incubator for 2 h, and centrifuge at 1000G for 15 min to obtain the crude HKUST-1 product after dichloromethane replacement. Note that the supernatant should be poured into a waste container, and dichloromethane should be added to the fume hood.

[0061] 1.9 Displacement and dispersion with anhydrous ethanol: Add an equal volume of anhydrous ethanol to the centrifuge tube containing the crude HKUST-1 product obtained above, balance the volume, and use a turbine to stir and shake to uniformly disperse the crude product into a suspension. Centrifuge at 10000G for 15 min to separate the crude HKUST-1 product. Repeat this step once, and add an equal volume of anhydrous ethanol to the same volume as the original supernatant. Use a turbine to stir and shake to uniformly disperse the crude product into a suspension, and sonicate for 10 min.

[0062] 1.10 Rotary evaporation to remove anhydrous ethanol. Specific process: The suspension in the centrifuge tube above is transferred to a round-bottom flask. Under the conditions of water bath temperature of 40℃ and rotation speed of 100rpm, the anhydrous ethanol is removed by rotary evaporation for 20min to obtain a dry powder product. This product is a controllable micro-nano particle size metal-organic framework HKUST-1 material.

[0063] Figure 1 The image shows a transmission electron microscope (TEM) image of the controllable micro / nano particle size metal-organic framework HKUST-1 material. In the image, a is a schematic TEM image of the HKUST-1 material prepared in Example 1. As can be seen from the image, the material has a MOF framework.

[0064] Figure 2 This is a particle size distribution diagram of HKUST-1 material. In the diagram, 'a' represents the particle size distribution diagram of the HKUST-1 material prepared in Examples 1-4. As can be seen from the diagram, the average particle size of the HKUST-1 nanomaterial prepared in Example 1 is 308.6 nm.

[0065] Table 1 is the XPS analysis table for HKUST-1.

[0066] Table 1

[0067] BindingEnergy(eV) 935 570 530 284 Elements (atomic electron orbitals / spins) Cu2p CuLM2 O1s C1s

[0068] Figure 3The image shows the XPS analysis results of HKUST-1 material. The electron orbitals of copper atoms are Cu 2p and Cu LM2, the electron orbitals of oxygen atoms are 1s, and the electron orbitals of carbon atoms are 1s. This result is similar to the XPS results of HKUST-1 material prepared by Loera-Serna S et al. [Loera-Serna, S., et al. "Electrochemical behavior of [Cu 3(BTC)2] metal–organic framework: The effect of the method of synthesis." Journal of Alloys and Compounds 540. none(2012):113-120.], which proves that the preparation of HKUST-1 in Example 1 was successful.

[0069] Table 2 is the XRD analysis table of HKUST-1.

[0070] Table 2

[0071]

[0072] Figure 4 The image shows the XRD pattern of HKUST-1 material. The diffraction peaks obtained by scanning in the 10-40° range are similar to the XRD results of HKUST-1 material prepared by Loera-Serna S et al., which also proves that HKUST-1 was successfully prepared in Example 1.

[0073] Example 2

[0074] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: an inorganic-organic phase synthesis method activated by polyvinylpyrrolidone (PVP), wherein the molar ratio of copper acetate to trimesic acid is 2.5:1 (product particle size ~340nm).

[0075] The first step is to prepare the solution. Steps 2.1 to 2.2 are the same as steps 1.1 to 1.2 in Example 1.

[0076] Step 2, synthesis reaction:

[0077] 2.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0078] Place 42 mL of a 10 mg / mL pyromellitic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 66.7 mL of a 15 mg / mL copper acetate-PVP solution at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0079] 2.4 Add 0.64 mL of LTEA dropwise to the above solution, stir magnetically for 10 min, and sonicate for 10 min to obtain a turquoise suspension; the molar ratio of copper acetate to triethanolamine is 1:1.

[0080] 2.5 Same as 1.5 in Example 1.

[0081] The third step is purification, with 2.6 to 2.10 being the same as 1.6 to 1.10 in Example 1.

[0082] Depend on Figure 2 As shown in the particle size distribution diagram, the average particle size of the HKUST-1 material prepared in Example 2 is 335.8 nm. The decrease in the molar ratio of copper acetate and pyromellitic acid leads to an increase in the particle size of the HKUST-1 material.

[0083] Depend on Figure 3 and Figure 4 It can be seen that HKUST-1 was successfully prepared in Example 2, and the adjustment of the molar ratio of copper acetate and pyromellitic acid does not affect the atomic electron orbitals of the elements, nor does it affect the crystal state of the material.

[0084] Example 3

[0085] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: an inorganic-organic phase synthesis method activated by polyvinylpyrrolidone (PVP), wherein the molar ratio of copper acetate to trimesic acid is 2:1 (product particle size ~450nm).

[0086] The first step is to prepare the solution. Steps 3.1 to 3.2 are the same as steps 1.1 to 1.2 in Example 1.

[0087] Step 2, synthesis reaction:

[0088] 3.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0089] Place 42 mL of a 10 mg / mL pyromellitic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 53.3 mL of a 15 mg / mL copper acetate-PVP solution at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0090] 3.4 Add 0.51 mL of triethanolamine to the above solution, stir magnetically for 10 min, and sonicate for 10 min to obtain a turquoise suspension; the molar ratio of copper acetate to triethanolamine is 1:1.

[0091] 3.5 Same as 1.5 in Example 1.

[0092] The third step is purification, with 3.6 to 3.10 being the same as 1.6 to 1.10 in Example 1.

[0093] Depend on Figure 2 As shown in the particle size distribution diagram, the average particle size of the HKUST-1 material prepared in Example 3 is 446.1 nm. Figure 3 and Figure 4 It can be seen that HKUST-1 was successfully prepared in Example 3.

[0094] Example 4

[0095] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: an inorganic-organic phase synthesis method activated by polyvinylpyrrolidone (PVP), wherein the molar ratio of copper acetate to trimesic acid is 1.5:1 (product particle size ~500nm).

[0096] The first step is to prepare the solution. Steps 4.1 to 4.2 are the same as steps 1.1 to 1.2 in Example 1.

[0097] Step 2, synthesis reaction:

[0098] 4.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0099] Place 42 mL of 10 mg / mL trimellitic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 40 mL of 15 mg / mL copper acetate-PVP solution at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0100] 4.4 Add 0.38 mL of triethanolamine to the above solution, stir magnetically for 10 min, and sonicate for 10 min to obtain a turquoise suspension; the molar ratio of copper acetate to triethanolamine is 1:1.

[0101] 4.5 Same as 1.5 in Example 1.

[0102] The third step is purification, with 4.6 to 3.10 being the same as 4.6 to 1.10 in Example 1.

[0103] Depend on Figure 2 As shown in the particle size distribution diagram, the average particle size of the HKUST-1 material prepared in Example 4 is 500.4 nm. Figure 3 and Figure 4 It can be seen that HKUST-1 was successfully prepared in Example 4.

[0104] Example 5

[0105] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: inorganic-organic phase synthesis method, wherein the molar ratio of copper acetate to trimesic acid is 3:1 (product particle size ~780nm).

[0106] Step 1, prepare the solution:

[0107] 5.1 Preparation of copper acetate solution: Dissolve copper acetate monohydrate in a mixed solution of dimethylformamide (DMF) and ultrapure water. The concentration of copper acetate solution is 15 mg / mL. The volume ratio of ultrapure water to DMF is 3:1. Sonicate for 10 min. Note that DMF should be added in the fume hood.

[0108] 5.2 Same as 1.2 in Example 1.

[0109] Step 2, synthesis reaction:

[0110] 5.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0111] Place 42 mL of 10 mg / mL triphenyl benzoic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 80 mL of 15 mg / mL copper acetate solution dropwise at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0112] 5.4-5.5 are the same as 1.4-1.5 in Example 1. The molar ratio of copper acetate to triethanolamine is 1:1.

[0113] Step 3, purification:

[0114] 5.6 to 5.8 are the same as 1.6 to 1.8 in Example 1.

[0115] 5.9 Displacement and dispersion with anhydrous ethanol: Add an equal volume of anhydrous ethanol to the centrifuge tube containing the crude HKUST-1 product obtained above, balance the volume, and use a turbine to stir and shake to uniformly disperse the crude product into a suspension. Centrifuge at 10000G for 5 min to separate the crude HKUST-1 product. Repeat this step once, and add an equal volume of anhydrous ethanol to the centrifuge tube again, stir and shake to uniformly disperse the crude product into a suspension. Transfer the suspension to a beaker, stir magnetically at 400 rpm for 15 min, and sonicate for 10 min.

[0116] 5.10 Filtration to remove anhydrous ethanol: Set up a filtration apparatus (from top to bottom: filter paper, Buchner funnel, rubber pad, filtration flask, rubber tubing connecting the filtration flask and the double-water circulating vacuum pump; before filtration, soak the filter paper with ultrapure water, and use a spatula to transfer the sample during filtration). Pour the suspension in the beaker into the Buchner funnel for filtration to remove anhydrous ethanol, and obtain solid HKUST-1 product.

[0117] 5.11 Drying the product: The HKUST-1 product obtained above was placed in a round petri dish and dried at 40°C until it became a grindable solid. The product was then ground and returned to the dish for further drying. The grinding and drying process was repeated three times to obtain the controllable micro-nano particle size metal-organic framework HKUST-1 material.

[0118] Figure 1 Image b is a transmission electron microscope (TEM) schematic of the HKUST-1 nanomaterials prepared in Example 5, showing that it has a MOF framework; (Comparison) Figure 1 As can be seen from a, the HKUST-1 material prepared by PVP activation has a spherical structure, while that without PVP activation has a rod-like structure.

[0119] Figure 2 This is a particle size distribution diagram of HKUST-1 material. Among them, b is a particle size distribution diagram of HKUST-1 material prepared in Examples 5 to 8. As can be seen from the figure, the average particle size of HKUST-1 nanomaterial prepared in Example 5 is 782.2 nm. Compared with Example 1, it can be seen that the activation effect of PVP can reduce the particle size of HKUST-1 material.

[0120] Depend on Figure 3 and Figure 4 It can be seen that HKUST-1 was successfully prepared in Example 4, and the activation effect of PVP does not affect the elemental electron orbitals of the material, nor does it affect the crystalline state of the material.

[0121] Example 6

[0122] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: inorganic-organic phase synthesis method, wherein the molar ratio of copper acetate and trimesic acid is 2.5:1 (product particle size ~1μm).

[0123] The first step is to prepare the solution. Steps 6.1 to 6.2 are the same as steps 5.1 to 5.2 in Example 5.

[0124] Step 2, synthesis reaction:

[0125] 6.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0126] Place 42 mL of a 10 mg / mL pyromellitic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 66.7 mL of a 15 mg / mL copper acetate solution at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0127] 6.4-6.5 are the same as 5.4-5.5 in Example 5. The molar ratio of copper acetate to triethanolamine is 1:1.

[0128] The third step is purification, 6.6 to 6.11 are the same as 5.6 to 5.11 in Example 5.

[0129] Depend on Figure 2 As shown in the particle size distribution diagram, the average particle size of the HKUST-1 material prepared in Example 6 is 1027 nm. That is, without the activation of PVP, the molar ratio of copper acetate to trimesic acid is 2.5:1 to prepare micron-sized HKUST-1 material.

[0130] Example 7

[0131] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: inorganic-organic phase synthesis method, wherein the molar ratio of copper acetate and trimesic acid is 2:1 (product particle size ~1.7μm).

[0132] The first step is to prepare the solution. Steps 7.1 to 7.2 are the same as steps 5.1 to 5.2 in Example 5.

[0133] Step 2, synthesis reaction:

[0134] 7.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0135] Place 42 mL of a 10 mg / mL pyromellitic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 53.3 mL of a 15 mg / mL copper acetate solution at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0136] 7.4-7.5 are the same as 5.4-5.5 in Example 5. The molar ratio of copper acetate to triethanolamine is 1:1.

[0137] The third step is purification, 7.6 to 7.11, which are the same as 5.6 to 5.11 in Example 5.

[0138] Depend on Figure 2 As shown in the schematic diagram of particle size distribution in Example 7, the average particle size of the HKUST-1 material prepared in Example 7 is 1723 nm.

[0139] Example 8

[0140] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: inorganic-organic phase synthesis method, wherein the molar ratio of copper acetate and trimesic acid is 1.5:1 (product particle size ~2μm).

[0141] Step 1: Prepare the solution. Steps 8.1-8.2 are the same as steps 5.1-5.2.

[0142] Step 2, synthesis reaction:

[0143] 8.3 Add copper acetate solution dropwise to trimesic acid solution, specific process:

[0144] Place 42 mL of a 10 mg / mL pyromellitic acid solution in a beaker, stir magnetically at 400 rpm, and slowly add 53.3 mL of a 15 mg / mL copper acetate solution at a rate of 30 drops / min using a separatory funnel. After the addition is complete, seal the beaker with a sealing film and stir magnetically for 15 min.

[0145] 8.4-8.5 are the same as 5.4-5.5, and the molar ratio of copper acetate to triethanolamine is 1:1.

[0146] The third step is purification, 8.6 to 8.11, which are the same as 5.6 to 5.11 in Example 5.

[0147] Depend on Figure 2 As shown in the particle size distribution diagram, the average particle size of the HKUST-1 material prepared in Example 8 is 2005 nm.

[0148] Example 9

[0149] A method for preparing a controllable micro / nano particle size metal-organic framework HKUST-1 material includes the following steps: water-ethanol phase synthesis method, with a molar ratio of copper acetate and trimesic acid of 3:1 (product particle size > 2 μm).

[0150] Step 1, prepare the solution:

[0151] Preparation of pyromellitic acid solution: Dissolve pyromellitic acid in anhydrous ethanol to a concentration of 10 mg / ml, and sonicate for 15 min to obtain the pyromellitic acid solution.

[0152] Preparation of copper acetate solution: Dissolve copper acetate monohydrate in ultrapure water to a concentration of 15 mg / mL, and sonicate for 15 min to obtain the copper acetate solution.

[0153] Step 2, synthesis reaction:

[0154] 9.3 The addition step is the same as step 5.3 in Example 5, except that triethanolamine does not need to be added. 9.4 Centrifuge to obtain the crude product, the step is the same as step 1.5 in Example 1.

[0155] Step 3, purification:

[0156] 9.5 Replace with 50% ethanol: Add an equal volume of 50% ethanol to the centrifuge tube containing the crude HKUST-1 product, balance the volume, and use a turbine to stir and shake to evenly disperse the crude product into a suspension. Sonicate for 10 min, centrifuge at 10000G for 15 min to separate the crude HKUST-1 product. Repeat this step twice to obtain the crude HKUST-1 product after replacement with 50% ethanol.

[0157] 9.6 The step of removing ethanol by filtration is the same as 5.10 in Example 5, and 9.7 The step of drying the product is the same as 5.11 in Example 5.

[0158] Figure 1 Figure c is a transmission electron microscope schematic diagram of the HKUST-1 material prepared in Example 9, which shows that it has a MOF framework and the structure is rod-shaped.

[0159] Figure 2 This is the particle size distribution diagram of HKUST-1 material. In the diagram, c represents the particle size distribution diagram of the HKUST-1 material prepared in Example 9. As can be seen from the diagram, the average particle size is 2291 nm. Compared with Example 5, it can be seen that the inorganic-organic phase synthesis method increased the particle size of the HKUST-1 material.

[0160] Depend on Figure 3 and Figure 4 It can be seen that HKUST-1 was successfully prepared in Example 9, and the activation of PVP and the purification of organic reagents do not affect the elemental electron orbitals of the material, nor do they affect the crystalline state of the material.

[0161] Comparative Example 1

[0162] Example 1 of publication number CN112341630A is used as Comparative Example 1.

[0163] A method for continuously preparing nanomaterials of metal-organic frameworks using supergravity technology includes the following steps:

[0164] 1.138 g (5.7 mmol) of copper acetate monohydrate was dissolved in 380 mL of solvent (ethanol:N,N'-dimethylformamide = 1:1) with stirring; 0.799 g (3.8 mmol) of 1,3,5-pyromellitic acid was dissolved in 380 mL of N,N'-dimethylformamide with stirring; the hypergravity reactor was turned on and the rotor speed was adjusted to 1500 rpm; the copper acetate monohydrate solution and the 1,3,5-pyromellitic acid solution were simultaneously pumped into the hypergravity reactor for rapid and thorough mixing. The precipitation and crystallization reaction was carried out, with the feed rate on both sides controlled at 100 mL / min. The reaction temperature was controlled at 45℃ using circulating water. After both feed streams were completed, the centrifugal reactor was shut down, and all the suspension collected from the centrifugal reactor outlet was transferred to a solvent filter for pressure filtration. The resulting filter cake was first washed three times with N,N'-dimethylformamide, and then washed three times with ethanol. The cleaned filter cake was placed in a vacuum drying oven at 120℃ for 12 hours. After the solvent evaporated, the sample was obtained.

[0165] Analysis and Testing

[0166] In this invention, a small number of samples are selected for XRD testing; Figure 1 The product obtained in Example 1 is compared with the simulated XRD phase diagram of HKUST-1 material. The XRD phase diagram shows that the product is HKUST-1 particles.

[0167] In this invention, a small amount of sample is selected, placed in about 2 mL of ethanol, dispersed by shaking in an ultrasonic cleaner, and then dropped onto a 300-mesh carbon support film for electron microscopy observation. The morphology, size and structure of the particles are observed using a transmission electron microscope. Figure 2 The image shows a transmission electron microscope (TEM) image of the product obtained in Example 1. As can be seen from the image, the particles of the obtained product are spherical with a size range of 2.8 ± 0.6 nm, exhibiting a narrow particle size distribution and uniform particle size and morphology.

[0168] Compared with Comparative Example 1, although Comparative Example 1 can synthesize HKUST-1 nanoparticles with smaller particle size, its particle size distribution is narrower, the synthesized particle size is uncontrollable, and its synthesis method requires a hypergravity reactor and a vacuum drying oven, which are more demanding in terms of synthesis conditions compared with this invention.

[0169] Comparative Example 2

[0170] Example 1 of publication number CN114479098A is used as Comparative Example 2.

[0171] A microporous metal-organic framework material, HKUST-1, was prepared by a method comprising the following steps:

[0172] S1. Add 0.25 mmol of organic ligand H3BTC (tristyric acid) and 1.50 mmol of 2-Cl-HBA to 15 mL of organic solvent N,N-dimethylformamide (DMF). Stir at room temperature until completely dissolved, then add 1.5 mmol of copper nitrate trihydrate (Cu(NO3)2·3H2O) and continue stirring until completely dissolved. Transfer the solution to a 25 mL polytetrafluoroethylene reactor liner, seal the reactor with a stainless steel metal shell, place the sealed reactor in an oven, and react at 80 °C for 15 h. Cool to room temperature (20-30 °C) to obtain the initial product.

[0173] S2. Transfer the initial product obtained in S1. to a centrifuge tube and centrifuge at 8000 r / min for 10 min to remove the liquid and obtain a solid initial product. Wash the solid initial product obtained after centrifugation with a 50% ethanol aqueous solution 4 times (washing can be repeated as needed until unreacted raw materials are completely removed). After washing, place it in a well-ventilated indoor area to air dry at room temperature to obtain HKUST-1 product powder (compound 1) containing the coordination regulator, with a yield of approximately 55 wt%.

[0174] S3. The compound 1 product powder obtained in S2. was subjected to vacuum treatment at 120°C (vacuum degree of about 10-3 mbar) to obtain the microporous metal-organic framework HKUST-1 material. The phase purity was characterized by powder XRD.

[0175] Compared with Comparative Example 2, which focuses on controlling the pore size of HKUST-1 but not the particle size, this invention cannot synthesize nano-sized HKUST-1. Furthermore, compared to this invention, Comparative Example 2 still requires a reaction vessel and an 80°C oven for synthesis, making it impossible to synthesize at room temperature and pressure.

[0176] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing controllable micro-nanoparticle size metal organic framework HKUST-1 material, characterized in that, The method comprises the following steps: adding a copper acetate solution with a concentration of 10-20 mg / mL into a solution of trimesic acid with a concentration of 5-15 mg / mL, sealing after the addition, stirring for 5-30 min, and the molar ratio of copper acetate to trimesic acid being (1.5-3):1; adding triethanolamine into the above solution, stirring for 5-20 min, and ultrasonic treatment for 5-20 min to obtain a suspension; the molar ratio of copper acetate to triethanolamine being 1:1; centrifuging the above suspension to obtain a precipitate as a crude product of HKUST-1; purifying the crude product of HKUST-1 by using ultrapure water, dimethylformamide, dichloromethane and anhydrous ethanol in sequence, performing suction filtration and drying to obtain the controllable micro-nano-particle-size metal organic framework HKUST-1 material; the particle size of the controllable micro-nano-particle-size metal organic framework HKUST-1 material is 500 nm≤particle size≤1.7 μm; the preparation method of the trimesic acid solution comprises the following steps: dissolving trimesic acid in a mixed solution of anhydrous ethanol and dimethylformamide with a volume ratio of 2:1, making the concentration of the solution be 5-15 mg / mL, and ultrasonic treatment for 5-30 min to obtain the trimesic acid solution; the preparation method of the copper acetate solution comprises the following steps: dissolving copper acetate monohydrate in a mixed solution of dimethylformamide and ultrapure water, making the concentration of the copper acetate solution be 10-20 mg / mL, the volume ratio of ultrapure water to dimethylformamide being 3:1, and ultrasonic treatment for 5-30 min to obtain the copper acetate solution.

2. The method of claim 1, wherein the controllable micro- and nano-particle size HKUST-1 material is prepared by the method of claim 1. the method steps of the ultrapure water purification comprise the following steps: adding ultrapure water with an amount equal to the volume of the original supernatant into a centrifuge tube containing the crude product of HKUST-1, making up, stirring and oscillating to uniformly disperse the crude product to form a suspension, ultrasonic treatment, centrifugation, and separation of the crude product of HKUST-1; the step is repeated twice to obtain the crude product of HKUST-1 after replacement by ultrapure water; the method steps of the dimethylformamide purification comprise the following steps: adding dimethylformamide (DMF) with an amount equal to the volume of the original supernatant into a centrifuge tube containing the crude product of HKUST-1 obtained above, making up, stirring and oscillating to uniformly disperse the crude product to form a suspension, centrifugation, and separation of the crude product of HKUST-1; the step is repeated once, and then DMF with an amount equal to the volume of the original supernatant is added, making up, stirring and oscillating to uniformly disperse the crude product to form a suspension, oscillating the centrifuge tube, and centrifugation to obtain the crude product of HKUST-1 after replacement by DMF.

3. The method for preparing the controllable micro / nano particle size metal-organic framework HKUST-1 material according to claim 1, characterized in that, the method steps of the dichloromethane purification comprise the following steps: adding dichloromethane with an amount equal to the volume of the original supernatant into a centrifuge tube containing the crude product of HKUST-1 after replacement by DMF, making up, stirring and oscillating to uniformly disperse the crude product to form a suspension, centrifugation, and separation of the crude product of HKUST-1; the step is repeated once, and then dichloromethane with an amount equal to the volume of the original supernatant is added, making up, stirring and oscillating to uniformly disperse the crude product to form a suspension, oscillating the centrifuge tube, and centrifugation to obtain the crude product of HKUST-1 after replacement by dichloromethane. The method steps of the anhydrous ethanol purification include the following steps: adding anhydrous ethanol in an amount equal to the volume of the original supernatant into the centrifuge tube containing the obtained HKUST-1 crude product, balancing, stirring and oscillating to uniformly disperse the crude product to form a suspension, centrifuging, and separating the HKUST-1 crude product; repeating the step once, adding anhydrous ethanol in an amount equal to the volume of the original supernatant again, stirring and oscillating to uniformly disperse the crude product to form a suspension, and stirring and ultrasonicating the suspension.

4. The application of the controllable micro-nanoparticle size metal organic framework HKUST-1 material prepared by the method of any one of claims 1 to 3 in the preparation of nanobiomaterials, gas adsorption and storage materials, and catalytic materials.

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