Multistage structure metal organic framework compound material and preparation method and application thereof
Multilevel MOF materials with hierarchical structures were prepared by a precursor self-assembly method mediated by microemulsion templates and surfactants, which solved the diffusion and utilization problems of traditional MOF materials and realized high specific surface area materials with controllable morphology and uniform size, suitable for catalysis and energy fields.
Patent Information
- Application Number
- CN202510830456.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-19
- Publication Date
- 2025-11-14
AI Technical Summary
Traditional MOF materials are mostly microporous, which makes mass diffusion difficult and the active sites are not fully utilized. Existing methods for constructing multi-level MOF materials are complex and not suitable for large-scale preparation, and there is a lack of universal synthesis strategies.
By employing a precursor self-assembly method mediated by microemulsion templates and surfactants, multi-level metal-organic framework compound materials can be prepared by controlling the emulsion type and the type and amount of surfactant. The morphology and pore structure of the materials can be tunable.
The prepared multi-level MOF materials have regular morphology, uniform size, high specific surface area, are simple to operate, are suitable for large-scale production, and can be applied in the fields of catalysis, energy utilization and conversion.
Smart Images
Figure CN120944121A_ABST
Abstract
Description
Technical Field
[0001] This application relates to a multi-level structure metal-organic framework compound material, its preparation method and application, belonging to the field of materials preparation technology. Background Technology
[0002] Metal-organic framework (MOF) nanoparticles have attracted widespread attention across numerous fields. This is because the remarkable diversity and richness of their crystal structures provide opportunities for synergistic effects between functional metal nodes / organic ligands and encapsulated guest species. However, traditional MOF materials are generally microporous, posing a significant challenge to mass diffusion and limiting the full utilization of active sites. Therefore, a large body of research has focused on constructing highly accessible hierarchical porous MOF nanomaterials to exhibit characteristics typically absent or irrelevant in microporous systems, such as accelerated adsorption / desorption kinetics, enhanced loading capacity for large guest species, and the directional introduction and precise spatial control of different metal components within the material.
[0003] Template methods are widely used to construct hierarchical MOF materials. For example, by utilizing the inherent coordination inhomogeneity of MOFs, self-templating selective etching with acids, bases, or gases can synthesize hierarchical MOFs. Alternatively, hard spheres such as silica or polystyrene can be used as hard templates, which can then be removed by HF / NaOH etching or high-temperature calcination to construct hierarchical MOF materials. However, these methods require harsh reaction conditions and complex processes, necessitating specific functionalization or coating modifications to obtain multifunctional composite nanomaterials. They involve multiple material synthesis and separation steps, making them unsuitable for large-scale material preparation. Furthermore, the morphology or structure of MOF materials constructed using the same method remains limited, lacking a universal synthetic strategy for preparing structurally diverse hierarchical MOF materials. Summary of the Invention
[0004] To address the aforementioned issues, this application provides a technical solution for preparing hierarchical metal-organic framework (MOF) compound materials. Utilizing the formation of microemulsion templates and surfactant-mediated precursor self-assembly, a series of hierarchical MOF compound materials with tunable structural parameters are obtained by precisely controlling the emulsion type and size, and the type and amount of surfactant. The prepared MOF compound materials possess tunable microstructures and pore structures. The preparation method is simple and highly flexible, and the prepared materials show promising applications in catalysis, energy utilization, and conversion.
[0005] The technical solution adopted in this application is as follows:
[0006] According to a first aspect of this application, a method for preparing a multi-level structured metal-organic framework compound material is provided, characterized by comprising the following steps:
[0007] S1. Add catalyst, auxiliary agent and solvent II to a solution containing surfactant and solvent I, and react I to obtain a microemulsion template;
[0008] S2. Add a metal precursor and an organic ligand precursor to the microemulsion template, and react in reaction II to obtain the multi-level structured metal-organic framework compound material.
[0009] Optionally, in step S1, the surfactant is selected from at least one of dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, sodium lauryl sulfate, fluorocarbon surfactants, Pluronic F127, P123, F108, and F68.
[0010] Optionally, in step S1, solvent I is selected from at least one of methanol, ethanol, n-propanol, water, n-octane, and cyclohexane.
[0011] Optionally, in step S1, the catalyst is selected from at least one of ammonia (concentration of 25-28 wt%), sodium hydroxide, potassium hydroxide, hydrochloric acid, acetic acid, and sulfuric acid.
[0012] Optionally, in step S1, the auxiliary agent is selected from at least one of sodium chloride, sodium sulfate, sodium carbonate, potassium chloride, potassium sulfate, and potassium carbonate.
[0013] Optionally, in step S1, solvent II is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, toluene, p-xylene, mesitylene, nitrobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, styrene, and phenylacetylene.
[0014] Optionally, in step S1, the ratio of solvent I, surfactant, catalyst, auxiliary agent, and solvent II is 1 mL: 0.005–0.01 g: 0.005–0.025 mL: 0.005–0.015 g: 0.05–2.5 mL;
[0015] The ratio of solvent I, metal precursor, and organic ligand precursor is 1 mL: 2–2.5 mg: 6.5–7.5 mg.
[0016] Optionally, in step S2, the metal precursor is selected from at least one of zirconium tetrachloride, ferric chloride, zinc acetate, cerium ammonium nitrate, and zinc acetate.
[0017] Optionally, in step S2, the organic ligand precursor is selected from at least one of 2-aminoterephthalic acid, 2-bromoterephthalic acid, 2-iodoterephthalic acid, and terephthalic acid.
[0018] Optionally, the conditions for reaction I and reaction II independently include: being carried out under stirring conditions, with a stirring speed of 50 to 1000 rpm, a reaction temperature of 0 to 100°C, and a reaction time of 0.5 to 24 h.
[0019] Optionally, step S2 further includes surface loading and metallization of the multi-level structure metal-organic framework compound material.
[0020] The modified metal is selected from at least one of palladium, platinum, scandium, yttrium, lanthanum, praseodymium, neodymium, and indium.
[0021] The method of loading modified metal in this application is not strictly limited. Those skilled in the art can choose from the prior art as needed. For example, it can be obtained by impregnating a solution of modified metal salt and then calcining.
[0022] According to a second aspect of this application, a multi-level structure metal-organic framework compound material obtained by the above preparation method is provided, wherein the metal-organic framework compound is selected from at least one of the ZIF (Zeolitic imidazolate framework), UiO (University of Oslo), HKUST (Hong Kong University of Science and Technology), and MIL (Materiel Institut Lavoisier) series;
[0023] The multi-level structured metal-organic framework compound material includes micropores and mesopores;
[0024] The pore size of the micropores is 1–2 nm;
[0025] The pore size of the mesopore is 5–50 nm;
[0026] The morphology of the multi-level structure metal-organic framework compound material is spherical or flower-shaped.
[0027] Optionally, the particle size of the hierarchical metal-organic framework compound material is 100–1000 nm;
[0028] Optionally, the specific surface area of the hierarchical metal-organic framework compound material is 5–1000 m². 2 / g.
[0029] According to a third aspect of this application, at least one of the above-described hierarchical metal-organic framework compound materials and the hierarchical metal-organic framework compound materials obtained according to the above preparation method is provided for use in the fields of catalysis, adsorption or drug release.
[0030] The beneficial effects of this application include:
[0031] The multi-level metal-organic framework compound material provided in this application has the characteristics of regular morphology, uniform size, and high specific surface area. The preparation technology of this multi-level metal-organic framework compound material is novel, simple to operate, and versatile. By adjusting the synthesis time, surfactant addition amount or catalyst amount, the morphology of the MOF material can be controllably modified from a spherical multi-level porous structure to a flower-like multi-level structure. The adjustment space is large and it is easy to carry out large-scale production and utilization. Attached Figure Description
[0032] Figure 1 The images shown are transmission electron microscope (TEM) images of the multi-level metal-organic framework material in Example 2 of this application, where a is a TEM image at the 200 nm scale and b is a TEM image at the 50 nm scale.
[0033] Figure 2 The X-ray diffraction pattern of the multi-level metal-organic framework material in Example 2 of this application is shown.
[0034] Figure 3 This is an adsorption performance test in Example 2 of this application, where a is the nitrogen adsorption curve of the multi-level metal-organic framework material and b is the pore size distribution diagram.
[0035] Figure 4 For the multi-level metal-organic framework material in Example 4 of this application, a is a scanning electron microscope image at the 500 nm scale, b is a scanning electron microscope image at the 200 nm scale, c is a transmission electron microscope image at the 500 nm scale, and d is a transmission electron microscope image at the 200 nm scale.
[0036] Figure 5 The images shown are transmission electron microscope (TEM) images of the multi-level metal-organic framework material in Example 6 of this application, where a is a TEM image at the 500 nm scale and b is a TEM image at the 200 nm scale.
[0037] Figure 6 The image shown is a transmission electron microscope (TEM) image of the metal-organic framework material prepared without the microemulsion method in Comparative Example 1 of this application. The image is a TEM image with a size of 200 nm.
[0038] Figure 7 The images shown are transmission electron microscope (TEM) images of metal-organic framework materials prepared without the microemulsion method in Comparative Example 2 of this application, where a is a TEM image at the 200 nm scale and b is a TEM image at the 100 nm scale. Detailed Implementation
[0039] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0040] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.
[0041] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.
[0042] Scanning electron microscopy (SEM) was performed using a Hitachi S-4800 instrument (Japan); transmission electron microscopy (TEM) was performed using a Hitachi 7800 instrument (Japan); X-ray diffraction (XRD) was performed using an Empyrean instrument from Panaco (Netherlands); and nitrogen adsorption-desorption tests were performed using a Micromeritics 3-Flex instrument from Micromeritics (USA).
[0043] Example 1
[0044] Under stirring conditions of 30℃ and 400 rpm, surfactant P123 (0.1 g), fluorocarbon surfactant (0.05 g), glacial acetic acid (0.1 mL), and potassium chloride (0.2 g) were added to an aqueous solution (20 mL). After dissolution, 1 mL of trimethylbenzene (trimethylbenzene) was added, and the reaction was carried out for 10 min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457 g) and terephthalic acid (0.1383 g) were added, and the reaction was carried out for 120 min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12 h to obtain a multi-level metal-organic framework compound material. The material has a flower-like morphology, with porous irregular spheres inside and thin nanosheets on the outside, and the material size is approximately 650 nm.
[0045] Comparative Example 1
[0046] Under the stirring conditions of 30℃ and 400rpm, surfactant P123 (0.1g), fluorocarbon surfactant (0.05g), glacial acetic acid (0.1mL), and potassium chloride (0.2g) were added to an aqueous solution (20mL). After dissolution, (NH4)2Ce(NO3)6 (0.0457g) and terephthalic acid (0.1383g) were added. After reacting for 120min, the mixture was centrifuged, washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12h to obtain the metal-organic framework material.
[0047] Figure 6 The image shows a transmission electron microscope (TEM) image of the metal-organic framework material prepared under the comparative conditions, at a scale of 500 nm. This material was not prepared using a microemulsion method; the image shows that the nanomaterial exhibits irregular aggregates.
[0048] Example 2
[0049] Under the stirring conditions of 30℃ and 400rpm, surfactant P123 (0.1g), fluorocarbon surfactant (0.05g), glacial acetic acid (0.2mL), and potassium chloride (0.2g) were added to an aqueous solution (20mL). After dissolution, the organic solvent mesitylene (1mL) was added and the reaction was carried out for 10min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457g) and terephthalic acid (0.1383g) were added and the reaction was carried out for 120min. After centrifugation, the mixture was washed three times with ethanol and N,N-dimethylformamide and dried in a vacuum oven for 12h to obtain a multi-level metal-organic framework compound material.
[0050] Figure 1 The image shown is a transmission electron microscope (TEM) image of the multi-level metal-organic framework material prepared in this embodiment. It can be seen that the material has a diameter of approximately 350 nm and abundant mesoporous channels.
[0051] Figure 2 This is the X-ray diffraction pattern of the material prepared in this embodiment. This pattern confirms that this MOF belongs to UiO-66(Ce).
[0052] Figure 3 The figures show the nitrogen adsorption curve (a) and pore size distribution (b) of the multi-level metal-organic framework material prepared under the conditions described in this application. The figures show that the nanomaterial exhibits a typical type IV isotherm and a distinct type H1 hysteresis loop, indicating that the material possesses highly regular micropores and mesopores. Its specific surface area is 169.8 m². 2 / g, with a relatively concentrated pore size distribution of 1.1, 1.3 and 20.1 nm.
[0053] Comparative Example 2
[0054] Under the stirring conditions of 30℃ and 400rpm, surfactant P123 (0.1g), fluorocarbon surfactant (0.05g), glacial acetic acid (0.2mL), and potassium chloride (0.2g) were added to an aqueous solution (20mL). After dissolution, (NH4)2Ce(NO3)6 (0.0457g) and terephthalic acid (0.1383g) were added. After reacting for 120min, the mixture was centrifuged, washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12h to obtain the metal-organic framework material.
[0055] Figure 7 The images show transmission electron microscopy (TEM) images of the metal-organic framework material prepared under the comparative conditions, where a is a TEM image at the 200 nm scale and b is a TEM image at the 100 nm scale. This material was not prepared using a microemulsion method; the images show that the nanomaterials are irregularly spherical with non-uniform particle sizes.
[0056] Example 3
[0057] Under stirring conditions of 30℃ and 400rpm, surfactant P123 (0.1g), fluorocarbon surfactant (0.05g), glacial acetic acid (0.5mL), and potassium chloride (0.2g) were added to an aqueous solution (20mL). After dissolution, 1mL of trimethylbenzene (trimethylbenzene) was added, and the reaction was carried out for 10min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457g) and terephthalic acid (0.1383g) were added, and the reaction was carried out for 120min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12h to obtain a hierarchical metal-organic framework compound material. The material has a flower-like morphology, no core, and is composed of thin nanosheets with a size of approximately 900nm and a regular morphology.
[0058] Example 4
[0059] Under the conditions of reaction temperature of 30℃ and stirring speed of 400 rpm, surfactant P123 (0.1 g), fluorocarbon surfactant (0.05 g), glacial acetic acid (0.2 mL), and potassium chloride (0.2 g) were added to an aqueous solution (20 mL). After dissolution, the organic solvent mesitylene (2 mL) was added and the reaction was carried out for 10 min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457 g) and terephthalic acid (0.1383 g) were added and the reaction was carried out for 120 min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide and dried in a vacuum oven for 12 h to obtain a multi-level metal-organic framework compound material.
[0060] Figure 4 The images show scanning electron microscope (SEM) images a and b, and transmission electron microscope (TEM) images c and d, of the multi-level metal-organic framework material prepared under the conditions described in the embodiments of this application. As can be seen from the images, the nanomaterial has uniform particle size, regular morphology, a spherical shape, and a rough surface with abundant regular mesoporous structures.
[0061] Example 5
[0062] Under stirring conditions of 30℃ and 400 rpm, surfactant P123 (0.1 g), fluorocarbon surfactant (0.05 g), glacial acetic acid (0.2 mL), and potassium chloride (0.2 g) were added to an aqueous solution (20 mL). After dissolution, 10 mL of trimethylbenzene organic solvent was added, and the reaction was carried out for 10 min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457 g) and terephthalic acid (0.1383 g) were added, and the reaction was carried out for 120 min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12 h to obtain a multi-level metal-organic framework compound material. This material was uniformly dispersed and consisted of regularly shaped spheres with abundant mesoporous structures, with a size of approximately 350 nm.
[0063] Example 6
[0064] Under the stirring conditions of 30℃ and 400rpm, surfactant P123 (0.1g), fluorocarbon surfactant (0.05g), glacial acetic acid (0.2mL), and potassium chloride (0.2g) were added to an aqueous solution (20mL). After dissolution, the organic solvent mesitylene (50mL) was added and the reaction was carried out for 10min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457g) and terephthalic acid (0.1383g) were added and the reaction was carried out for 120min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide and dried in a vacuum oven for 12h to obtain a multi-level metal-organic framework compound material.
[0065] Figure 5 This is a transmission electron microscope (TEM) image of the hierarchical metal-organic framework material prepared under the conditions described in the embodiments of this application. The image shows that the material has a flower-like morphology, consisting of porous spheres internally and thin nanosheets externally. Furthermore, the material has a uniform size (approximately 700 nm) and a regular morphology.
[0066] Example 7
[0067] Under stirring conditions of 30℃ and 400rpm, surfactant P123 (0.13g), fluorocarbon surfactant (0.02g), glacial acetic acid (0.1mL), and potassium chloride (0.2g) were added to an aqueous solution (20mL). After dissolution, 1mL of trimethylbenzene (trimethylbenzene) was added, and the reaction was carried out for 10min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457g) and terephthalic acid (0.1383g) were added, and the reaction was carried out for 120min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12h to obtain a multi-level metal-organic framework compound material. The material has a flower-like morphology, with irregular porous spheres inside and numerous thin nanosheets on the outside.
[0068] Example 8
[0069] Under stirring conditions of 30℃ and 400 rpm, surfactant P123 (0.1 g), fluorocarbon surfactant (0.05 g), glacial acetic acid (0.2 mL), and potassium chloride (0.2 g) were added to an aqueous solution (20 mL). After dissolution, 4-methylstyrene organic solvent (1 mL) was added, and the reaction was carried out for 10 min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457 g) and terephthalic acid (0.1383 g) were added, and the reaction was carried out for 120 min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12 h to obtain a multi-level metal-organic framework compound material. This nanomaterial has a uniform particle size (approximately 250 nm), regular morphology, and is spherical with abundant regular mesoporous structures.
[0070] Example 9
[0071] Under stirring conditions of 30℃ and 400rpm, surfactant P123 (0.1g), fluorocarbon surfactant (0.05g), glacial acetic acid (0.2mL), and potassium chloride (0.2g) were added to an aqueous solution (20mL). After dissolution, benzyl alcohol (1mL) was added, and the reaction was carried out for 10min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457g) and terephthalic acid (0.1383g) were added, and the reaction was carried out for 120min. After centrifugation, the mixture was washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12h to obtain a multi-level metal-organic framework compound material. This nanomaterial has a uniform particle size (approximately 270nm), a regular morphology, and is a rough-surfaced sphere.
[0072] Example 10
[0073] Under stirring conditions of 30℃ and 400 rpm, surfactant P123 (0.1 g), fluorocarbon surfactant (0.05 g), glacial acetic acid (0.2 mL), and potassium chloride (0.2 g) were added to an aqueous solution (20 mL). After dissolution, 1,2,4-trichlorobenzene (1 mL) was added, and the reaction was carried out for 10 min to obtain a microemulsion template. Then, (NH4)2Ce(NO3)6 (0.0457 g) and terephthalic acid (0.1383 g) were added, and the reaction was carried out for 120 min. After centrifugation, the material was washed three times with ethanol and N,N-dimethylformamide, and dried in a vacuum oven for 12 h to obtain a hierarchical metal-organic framework compound material. This material is uniformly dispersed, regularly shaped spheres with a size of approximately 700 nm.
[0074] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing a multi-level structured metal-organic framework compound material, characterized in that, Includes the following steps: S1. Add catalyst, auxiliary agent and solvent II to a solution containing surfactant and solvent I, and react I to obtain a microemulsion template; S2. Add a metal precursor and an organic ligand precursor to the microemulsion template, and react in reaction II to obtain the multi-level structured metal-organic framework compound material.
2. The preparation method according to claim 1, characterized in that, In step S1, the surfactant is selected from at least one of dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, sodium laurylate, sodium dodecyl sulfate, fluorocarbon surfactants, Pluronic F127, P123, F108, and F68; Preferably, in step S1, solvent I is selected from at least one of methanol, ethanol, n-propanol, water, n-octane, and cyclohexane.
3. The preparation method according to claim 1, characterized in that, In step S1, the catalyst is selected from at least one of ammonia, sodium hydroxide, potassium hydroxide, hydrochloric acid, acetic acid, and sulfuric acid; Preferably, in step S1, the auxiliary agent is selected from at least one of sodium chloride, sodium sulfate, sodium carbonate, potassium chloride, potassium sulfate, and potassium carbonate; Preferably, in step S1, solvent II is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, toluene, p-xylene, mesitylene, nitrobenzene, m-dichlorobenzene, 1,2,4-trichlorobenzene, styrene, and phenylacetylene.
4. The preparation method according to claim 1, characterized in that, The ratio of solvent I, surfactant, catalyst, auxiliary agent, and solvent II is 1 mL : 0.005–0.01 g : 0.005–0.025 mL : 0.005–0.015 g : 0.05–2.5 mL; Preferably, the ratio of solvent I, metal precursor, and organic ligand precursor is 1 mL: 2-2.5 mg: 6.5-7.5 mg.
5. The preparation method according to claim 1, characterized in that, In step S2, the metal precursor is selected from at least one of zirconium tetrachloride, ferric chloride, zinc acetate, cerium ammonium nitrate, and zinc acetate; Preferably, in step S2, the organic ligand precursor is selected from at least one of 2-aminoterephthalic acid, 2-bromoterephthalic acid, 2-iodoterephthalic acid, and terephthalic acid.
6. The preparation method according to claim 1, characterized in that, The conditions for reactions I and II independently include: being carried out under stirring conditions, with a stirring speed of 50–1000 rpm, a reaction temperature of 0–100 °C, and a reaction time of 0.5–24 h.
7. The preparation method according to claim 1, characterized in that, Step S2 further includes surface loading and metallization of the multi-level structure metal-organic framework compound material; The modified metal is selected from at least one of palladium, platinum, scandium, yttrium, lanthanum, praseodymium, neodymium, and indium.
8. The multi-level structured metal-organic framework compound material obtained by the preparation method according to any one of claims 1 to 7, characterized in that, The metal-organic framework compound is selected from at least one of the ZIF, UiO, HKUST, and MIL series; The multi-level structured metal-organic framework compound material includes micropores and mesopores; The pore size of the micropores is 1–2 nm; The pore size of the mesopore is 5–50 nm; The morphology of the multi-level structure metal-organic framework compound material is spherical or flower-shaped.
9. The multi-level structured metal-organic framework compound material according to claim 8, characterized in that, The particle size of the multi-level structure metal-organic framework compound material is 100–1000 nm; Preferably, the specific surface area of the hierarchical metal-organic framework compound material is 5–1000 m². 2 / g.
10. The use of at least one of the hierarchical metal-organic framework compound materials obtained by the preparation method according to any one of claims 1 to 7, the hierarchical metal-organic framework compound materials according to claim 8 or 9, in the fields of catalysis, adsorption, or drug release.