A method for synthesizing a graded MOF material at room temperature and pressure

Abstract

This invention discloses a method for synthesizing hierarchical metal-organic framework (MOF) materials at room temperature and pressure. The method includes: providing a supersaturated reaction solution containing ligands, metal salts, and a solvent; mixing the supersaturated reaction solution with a poor solvent at room temperature and pressure, and reacting in one step to prepare the hierarchical metal-organic framework material. The method provided by this invention features mild reaction conditions, is energy-efficient and safe, and has a simple process route, offering one-step synthesis with high efficiency and strong controllability. The hierarchical metal-organic framework material prepared by the above method includes a metal center and organic ligands, and possesses a hierarchical structure, making it widely applicable in flexible devices or industrial catalysis.

Description

Technical Field

[0001] This invention belongs to the field of metal-organic framework materials technology, specifically relating to a method for synthesizing hierarchical MOF materials at room temperature and pressure. Background Technology

[0002] Metal-organic frameworks (MOFs) are a class of crystalline porous materials formed by the self-assembly of metal ions or clusters with organic ligands through coordination bonds. Due to their extremely high specific surface area, tunable pore structure, and diverse functionalization potential, they have attracted widespread attention in fields such as gas storage, separation, catalysis, sensing, and biomedicine. However, the single microstructure of traditional MOFs (typically uniform micropores and regular crystal morphology) often reveals problems such as low accessibility of active sites and limited mass transfer diffusion when dealing with processes involving macromolecular mass transfer, multi-step reactions, or interface-intensive processes, thus limiting the full realization of their macroscopic properties.

[0003] Hierarchical structures maximize functionality and efficiency by optimizing the transport, distribution, and mechanical stability of matter and energy at different scales. The construction of hierarchical structures through biomimicry has become a cutting-edge research direction in the field of MOFs.

[0004] Hierarchical MOFs refer to MOF materials that simultaneously possess ordered structural features at different scales (such as nanometer and submicrometer scales). This characteristic can manifest as a multi-level porous system (coexistence of micropores, mesopores, and macropores) or a multi-level morphological structure (such as three-dimensional hierarchical assemblies formed by primary nanostructural units, e.g., urchin-like, flower-like, core-shell-like structures). Hierarchical porosity provides rapid channels (mesopores / macropores) and highly selective adsorption sites (micropores) for molecular diffusion, while hierarchical morphology greatly increases the specific surface area and external active interfaces of the material, making internal active sites more easily accessible to reactants. Furthermore, the hierarchical structure effectively buffers volume change stresses during phase transitions or reactions, improving the structural robustness of the material. Its rich hierarchical space also provides an ideal site for loading functional nanoparticles, biomolecules, or other guest materials. Therefore, hierarchical MOFs exhibit significantly superior performance compared to traditional MOFs in many fields. In heterogeneous catalysis, its highly exposed active sites and unobstructed diffusion pathways can significantly improve reaction rates and selectivity; in electrochemical energy storage and conversion, its hierarchical structure facilitates rapid ion / electron transport and alleviates structural strain during cycling; and in the field of adsorption and separation, it can achieve synergistic and efficient removal of pollutants of different sizes.

[0005] Despite the significant advantages of hierarchical MOFs, efficient, controllable, and large-scale preparation remains a pressing issue. Existing synthetic strategies largely rely on hydrothermal / solvothermal methods, requiring reactions at high temperatures (typically >100°C) and autogenous pressure. While effective, these methods suffer from inherent drawbacks such as high energy consumption, demanding reaction conditions, complex equipment requirements, high safety risks, and difficulty in achieving continuous production. Furthermore, some strategies based on templates, post-synthetic etching, or complex ligand design also suffer from cumbersome procedures, high costs, or poor universality. For example, patent CN112480421A relies on high-temperature hydrothermal conditions to complete the transformation from a simple structure to a hierarchical structure resembling a sea urchin; patent CN117801307A is a typical combination of the "template method" and the "post-synthetic treatment method", which has limitations such as "cumbersome steps, template removal may damage the skeleton" or "complex process control". Although some steps are carried out at room temperature, the overall process route is lengthy, involving multiple centrifugation, washing and reaction steps, which is cumbersome to operate and uses an etchant; the method used in patent CN117327294A relies heavily on high-temperature processes, which not only require long-term solvothermal reactions, but also require subsequent high-temperature calcination treatment.

[0006] In summary, existing technologies suffer from the following drawbacks: First, they require stringent conditions, relying on high temperatures and pressures (such as hydrothermal / solvothermal or high-temperature calcination), resulting in high energy consumption, poor safety, and difficulty in large-scale production. Second, the processes are complex, requiring multiple post-processing steps (such as template methods and etching methods), which are cumbersome, difficult to control, costly, and inefficient. Third, they often use strong acids and bases, creating an environmental burden and failing to meet the requirements of green chemistry. Due to the limitations of existing technologies in terms of high energy consumption, complex processes, and environmental friendliness, the low-cost preparation and large-scale application of hierarchical MOF materials are severely restricted. Therefore, developing a universal, simple, green, and controllable method for directly synthesizing MOF materials with clearly defined hierarchical structures under ambient temperature and pressure and mild conditions is of great significance for promoting the basic research of hierarchical MOFs towards practical applications, reducing their preparation costs and energy consumption, and expanding their application scenarios in flexible devices, large-scale industrial catalysis, and other fields. Summary of the Invention

[0007] The main objective of this invention is to provide a method for synthesizing graded MOF materials at room temperature and pressure, so as to overcome the shortcomings of the prior art.

[0008] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0009] The first aspect of the present invention provides a method for synthesizing hierarchical MOF materials at room temperature and pressure, comprising:

[0010] Provide a supersaturated reaction solution containing ligands, metal salts, and solvents;

[0011] At room temperature and pressure, the supersaturated reaction solution is mixed with a poor solvent and reacted in one step to prepare fractional metal-organic framework materials.

[0012] A second aspect of the invention provides a hierarchical metal-organic framework material prepared by the method, comprising a metal center and an organic ligand, wherein the hierarchical metal-organic framework material has a hierarchical structure.

[0013] A third aspect of the invention provides the application of the hierarchical metal-organic framework material in flexible devices or industrial catalysis.

[0014] Compared with the prior art, the present invention has at least the following beneficial effects:

[0015] (1) The method provided by this invention has mild reaction conditions, is green and energy-saving, and has high safety. The entire process is carried out at room temperature and pressure, without relying on the harsh conditions such as hydrothermal / solventothermal or high-temperature calcination required in existing technologies. This fundamentally solves the inherent shortcomings of existing technologies, such as "high energy consumption, complex equipment requirements, and high safety risks". Moreover, it is easy to operate and has low equipment requirements, which greatly reduces production energy consumption and safety costs, and provides a feasible technical path for the large-scale, continuous and safe production of graded MOF materials.

[0016] (2) The method provided by this invention has a simple process route, is a one-step synthesis, and is highly efficient and controllable. This invention adopts a one-step strategy, driving the formation of hierarchical structures by controlling the slow diffusion of a poor solvent (ethanol). This method avoids the complex multi-step post-processing procedures in the prior art, such as "self-assembly-modification-etching-functionalization" or the introduction and removal of templates. The process flow is significantly simplified, with fewer steps, and is easy to operate, improving synthesis efficiency, reducing uncontrollable factors introduced by multi-step operations, and resulting in better product consistency.

[0017] (3) The method provided by this invention is environmentally friendly and does not use harmful reagents. This invention uses dimethyl sulfoxide (DMSO) and ethanol as the main solvents, and does not use strong acids, strong bases, etching agents, or toxic template agents that may be involved in the prior art during the reaction and post-processing. The entire synthesis and purification process is more green and environmentally friendly, reducing the generation and treatment burden of harmful waste liquids, which is in line with the development trend of green chemistry.

[0018] (4) The method provided by this invention has good universality and is applicable to different metal systems. The technical solution of this invention not only successfully synthesized hierarchical MOFs with cobalt (Co) as the metal center, but also prepared products with hierarchical structures with iron (Fe) as the metal center. It has a certain universality for different metal salts, rather than being limited to specific systems, and provides a general and mild synthesis platform for developing more types of hierarchical MOF materials.

[0019] (5) The method provided by this invention has a controllable structure and can effectively form a hierarchical morphology. This invention uses "static" to allow the poor solvent to diffuse slowly, thereby driving the assembly of the hierarchical structure and obtaining a hierarchical morphology that mimics gills. That is, this invention effectively induces the formation of a hierarchical structure through simple kinetic control (diffusion rate), realizing the controllable construction of material morphology. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 SEM image of the simulated gill-like graded MOF prepared in Example 1 of this invention;

[0022] Figure 2 This is a TEM image of the mycelial-gill-like graded MOF prepared in Example 1 of the present invention;

[0023] Figure 3 SEM image of the simulated gill-like graded MOF prepared in Example 2 of this invention;

[0024] Figure 4 This is a TEM image of the mycelial-gill-like graded MOF prepared in Example 3 of the present invention;

[0025] Figure 5 This is a TEM image of the MOF prepared in Comparative Example 1 of this invention;

[0026] Figure 6 This is a SEM image of the MOF prepared in Comparative Example 3 of this invention. Detailed Implementation

[0027] In view of the problems existing in the above-mentioned prior art, after in-depth research, a method for synthesizing hierarchical MOF materials at room temperature and pressure is provided, which mainly enables efficient and green synthesis of hierarchical MOF materials at room temperature and pressure.

[0028] The following will provide a further explanation of the technical solution, its implementation process, and its principles.

[0029] The first aspect of the present invention provides a method for synthesizing hierarchical MOF materials at room temperature and pressure, comprising:

[0030] Provide a supersaturated reaction solution containing ligands, metal salts, and solvents;

[0031] At room temperature and pressure, the supersaturated reaction solution is mixed with a poor solvent and reacted in one step to prepare fractional metal-organic framework materials.

[0032] In some embodiments, the metal salt includes cobalt salts or iron salts, but is not limited to these.

[0033] Furthermore, the cobalt salt includes, but is not limited to, Co(NO3)2·6H2O.

[0034] Furthermore, the iron salt includes, but is not limited to, Fe(NO3)3·9H2O.

[0035] In some embodiments, the ligand includes, but is not limited to, bis(p-carboxyphenylamino)phenylphosphine oxide (BNPO).

[0036] In some embodiments, the solvent includes, but is not limited to, dimethyl sulfoxide (DMSO).

[0037] In some implementations, the undesirable solvent includes, but is not limited to, ethanol or methanol.

[0038] In some embodiments, the molar ratio of the ligand to the metal salt is 1:1 to 1:1.2.

[0039] In some embodiments, the ratio of the amount of the ligand to the volume of the solvent is 0.025 to 0.042 mol / L.

[0040] In some embodiments, the volume ratio of the supersaturated reaction solution to the undesirable solvent is 1:1.7 to 1:2.

[0041] In some implementations, the reaction time is 60-90 hours.

[0042] In some embodiments, the method specifically includes: mixing the ligand, metal salt and solvent evenly, filtering or centrifuging the mixture to obtain the supersaturated reaction solution.

[0043] Furthermore, the pore size of the filter membrane is 0.2~0.45μm.

[0044] Furthermore, the centrifugation speed is 6000~10000 rpm, and the time is 2~10 min.

[0045] In some implementations, the method specifically includes: adding the undesirable solvent to a supersaturated reaction solution at room temperature and pressure, wherein the diffusion of the undesirable solvent drives the generation of a hierarchical structure, thereby obtaining the hierarchical metal-organic framework material in one step.

[0046] In some more specific implementations, the method specifically includes the following steps:

[0047] (1) At room temperature, the ligand and solvent are stirred until dissolved to obtain solution A; the metal salt and solvent are stirred until dissolved to obtain solution B.

[0048] (2) At room temperature, mix solution A and solution B, stir for 10 min, centrifuge at 6000~10000 rpm for 2~10 min, collect the supernatant, remove the tiny crystal nuclei formed by the reaction, and make the solution supersaturated to obtain the supersaturated reaction solution.

[0049] (3) Slowly add ethanol to the supersaturated reaction solution and let it stand at room temperature for 60-90 hours.

[0050] (4) Filter, collect the solid formed, wash with ethanol, repeat 3 times, dry at room temperature to obtain the graded metal-organic framework material.

[0051] Alternatively, the hierarchical metal-organic framework material can also be achieved by the following methods:

[0052] (1) At room temperature, the ligand and solvent are stirred until dissolved to obtain solution A; the metal salt and solvent are stirred until dissolved to obtain solution B.

[0053] (2) At room temperature, mix solution A and solution B, stir for 10-30 min, filter, clarify the filtrate, and obtain the supersaturated reaction solution.

[0054] (3) Slowly add ethanol to the supersaturated reaction solution and let it stand at room temperature for 60-90 hours.

[0055] (4) Filter, collect the solid formed, wash with ethanol, repeat 3 times, dry at room temperature to obtain the graded metal-organic framework material.

[0056] In step (3) above, ethanol is slowly added to the supersaturated reaction solution. Initially, ethanol and the supersaturated reaction solution are separated into layers. As ethanol diffuses in the solvent, the interface gradually disappears, and the two are mixed evenly. During this process, the solubility decreases, driving crystal growth. The purpose of this step is to use ethanol as a poor solvent to slowly diffuse into DMSO, driving the crystallization process.

[0057] A second aspect of the invention provides a hierarchical metal-organic framework material prepared by the method, comprising a metal center and an organic ligand, wherein the hierarchical metal-organic framework material has a hierarchical structure.

[0058] In some embodiments, the hierarchical metal-organic framework material has a hierarchical structure resembling mushroom folds.

[0059] In some implementations, the metal center includes, but is not limited to, at least one of cobalt and iron.

[0060] In some embodiments, the organic ligand includes, but is not limited to, bis(p-carboxyphenylamino)phenylphosphine oxide.

[0061] A third aspect of the invention provides the application of the hierarchical metal-organic framework material in flexible devices or industrial catalysis.

[0062] The technical solution of the present invention will be further described below with reference to the embodiments. Where specific experimental steps or conditions are not specified in the embodiments, they can be performed according to the conventional experimental steps or conditions described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available. Other unmentioned raw materials and instruments are all conventionally selected and do not involve the core technical means of the present invention.

[0063] Example 1

[0064] A method for synthesizing hierarchical MOF materials at room temperature and pressure specifically includes the following steps:

[0065] S1. At room temperature, add 0.40 g (1 mmol) bis(p-carboxyphenylamino)phenylphosphine oxide (BNPO) and 20 mL DMSO to reaction flask A and stir until dissolved; add 0.30 g (1 mmol) Co(NO3)2·6H2O and 20 mL DMSO to reaction flask B and stir until dissolved.

[0066] S2. At room temperature, mix the solutions in bottle A and bottle B, stir for 10 min, centrifuge at 8000 rpm, and collect the supernatant in conical flask C. The purpose of this operation is to remove the tiny crystal nuclei formed in the reaction and to bring the solution to a supersaturated state. Flask C contains 40 mL of supersaturated reaction solution.

[0067] S3. Slowly add 80 mL of ethanol along the wall of flask C and let it stand at room temperature for 72 hours. The purpose of this operation is to use ethanol as a poor solvent to slowly diffuse into DMSO, driving the crystallization process.

[0068] S4. Filter, collect the solid formed, wash with 40 mL of ethanol, repeat 3 times, dry at room temperature to obtain 0.42 g of product.

[0069] The SEM image of the mycelial-gill-like hierarchical MOF prepared in this embodiment is shown below. Figure 1 As shown; TEM image of the grading MOF with mushroom gilles. Figure 2 As shown.

[0070] Example 2

[0071] A method for synthesizing hierarchical MOF materials at room temperature and pressure specifically includes the following steps:

[0072] S1. At room temperature, add 2.0 g (5 mmol) BNPO and 60 mL DMSO to reaction flask A and stir until dissolved; add 1.5 g (5 mmol) Co(NO3)2·6H2O and 60 mL DMSO to reaction flask B and stir until dissolved.

[0073] S2. At room temperature, mix the solutions in bottle A and bottle B, stir for 30 min, filter, and use a filter membrane with a pore size of 0.45 μm. Collect the clear filtrate in conical flask C, which contains 120 mL of supersaturated reaction solution.

[0074] S3. Slowly add 200 mL of ethanol along the wall of bottle C and let it stand at room temperature for 72 hours.

[0075] S4. Filter, collect the solid formed, wash with 60 mL of ethanol, repeat 3 times, dry at room temperature to obtain 2.1 g of product.

[0076] The SEM image of the mycelial-gill-like hierarchical MOF prepared in this embodiment is shown below. Figure 3 As shown.

[0077] Example 3

[0078] A method for synthesizing hierarchical MOF materials at room temperature and pressure specifically includes the following steps:

[0079] S1. At room temperature, add 0.40 g (1 mmol) BNPO and 20 mL DMSO to reaction flask A and stir until dissolved; add 0.40 g (1 mmol) Fe(NO3)3·9H2O and 20 mL DMSO to reaction flask B and stir until dissolved.

[0080] S2. At room temperature, mix the solutions in bottle A and bottle B, stir for 10 min, centrifuge at 8000 rpm, and collect the supernatant in conical flask C. The purpose of this operation is to remove the tiny crystal nuclei formed in the reaction and to bring the solution to a supersaturated state. Flask C contains 40 mL of supersaturated reaction solution.

[0081] S3. Slowly add 80 mL of ethanol along the wall of flask C and let it stand at room temperature for 72 hours. The purpose of this operation is to use ethanol as a poor solvent to slowly diffuse into DMSO, driving the crystallization process.

[0082] S4. Filter, collect the solid formed, wash with 40 mL of ethanol, repeat 3 times, dry at room temperature to obtain 0.41 g of product.

[0083] TEM images of the mycelium-like hierarchical MOF prepared in this embodiment are shown below. Figure 4 As shown.

[0084] Example 4

[0085] A method for synthesizing hierarchical MOF materials at room temperature and pressure specifically includes the following steps:

[0086] S1. At room temperature, add 0.60 g (1.5 mmol) BNPO and 20 mL DMSO to reaction flask A and stir until dissolved; add 0.72 g (1.8 mmol) Fe(NO3)3·9H2O and 20 mL DMSO to reaction flask B and stir until dissolved.

[0087] S2. At room temperature, mix the solutions in bottle A and bottle B, stir for 20 min, centrifuge at 10,000 rpm, and collect the supernatant in conical flask C. The purpose of this operation is to remove the tiny crystal nuclei formed in the reaction and to bring the solution to a supersaturated state. Flask C contains 40 mL of supersaturated reaction solution.

[0088] S3. Slowly add 70 mL of methanol along the wall of flask C and let it stand at room temperature for 72 hours. The purpose of this operation is to use ethanol as a poor solvent to slowly diffuse into DMSO, driving the crystallization process.

[0089] S4. Filter, collect the solid formed, wash with 40 mL of ethanol, repeat 3 times, dry at room temperature to obtain 0.6 g of product.

[0090] Example 5

[0091] The difference between this embodiment and Embodiment 1 is that:

[0092] S1. The amount of cobalt salt used is 0.33g (1.1 mmol) Co(NO3)2·6H2O.

[0093] The remaining steps are the same as in Example 1, and the resulting gradation MOF (mushroom-like pleats) is prepared.

[0094] Example 6

[0095] The difference between this embodiment and Embodiment 1 is that:

[0096] S3. Slowly add 80 mL of ethanol along the wall of bottle C and let it stand at room temperature for 90 h.

[0097] The remaining steps are the same as in Example 1, and the resulting gradation MOF (mushroom-like pleats) is prepared.

[0098] Example 7

[0099] The difference between this embodiment and Embodiment 1 is that:

[0100] S3. Slowly add 80 mL of ethanol along the wall of bottle C and let it stand at room temperature for 60 h.

[0101] The remaining steps are the same as in Example 1, and the resulting gradation MOF (mushroom-like pleats) is prepared.

[0102] Comparative Example 1

[0103] S1. At room temperature, add 0.40 g (1 mmol) BNPO and 20 mL DMSO to reaction flask A and stir until dissolved; add 0.30 g (1 mmol) Co(NO3)2·6H2O and 20 mL DMSO to reaction flask B and stir until dissolved.

[0104] S2. At room temperature, mix the solutions in bottle A and bottle B, stir for 10 min, centrifuge at 8000 rpm, and collect the supernatant in conical flask C.

[0105] S3. Add 80 mL of ethanol to bottle C and stir for 72 h.

[0106] S4. Filter, collect the solids formed, and wash with ethanol.

[0107] TEM images of the MOF prepared in this comparative example are shown below. Figure 5 As shown.

[0108] Comparative Example 2

[0109] S1. At room temperature, add 0.40 g (1 mmol) bis(p-carboxyphenylamino)phenylphosphine oxide (BNPO) and 20 mL DMSO to reaction flask A and stir until dissolved; add 0.30 g (1 mmol) Co(NO3)2·6H2O and 20 mL DMSO to reaction flask B and stir until dissolved.

[0110] S2. At room temperature, mix the solutions in bottle A and bottle B, stir for 10 min, centrifuge at 8000 rpm, and collect the supernatant in conical flask C. The purpose of this operation is to remove the tiny crystal nuclei formed in the reaction and bring the solution to a supersaturated state.

[0111] S3. Let stand at room temperature for 72 hours.

[0112] No solid was formed in this comparative example.

[0113] Comparative Example 3

[0114] The difference between this comparative example and Example 1 is as follows:

[0115] S2. At room temperature, mix the solutions in bottle A and bottle B, stir for 10 min, and do not centrifuge.

[0116] The remaining steps are the same as in Example 1.

[0117] SEM images of the MOF prepared in this comparative example are shown below. Figure 6 As shown.

[0118] As demonstrated in Examples 1-3, the technical solution of this invention not only successfully synthesized hierarchical MOFs using cobalt (Co) as the metal center (Examples 1 and 2), but also prepared products with hierarchical structures using iron (Fe) as the metal center (Example 3). This preliminarily proves that the method has a certain degree of universality for different metal salts, rather than being limited to specific systems, providing a general and mild synthetic platform for developing more types of hierarchical MOF materials.

[0119] Furthermore, a comparison of Examples 1-3 with Comparative Example 1 reveals that the key to this invention lies in employing a "static" process to allow the undesirable solvent to diffuse slowly, thereby driving the assembly of the hierarchical structure and obtaining a hierarchical morphology resembling fungal gills (e.g., Figure 1-4 As shown). If "stirring" is used instead (Comparative Example 1), only ordinary nanoparticles without hierarchical characteristics can be obtained (as shown). Figure 5 If centrifugation in step S2 is missing, the graded morphology of the simulated gills cannot be obtained either. Figure 6 This indicates that the method of the present invention can effectively induce the formation of hierarchical structures through simple kinetic control (diffusion rate), thus achieving controllable construction of material morphology.

[0120] In addition, the present invention has also conducted experiments with other raw materials, process operations and process conditions described in this specification, with reference to the foregoing embodiments, and has obtained relatively ideal results.

[0121] Although the invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions, and / or additions can be made without departing from the spirit and scope of the invention, and that elements of the described embodiments can be substituted with substantially equivalents. Furthermore, many modifications can be made without departing from the scope of the invention to adapt particular situations or materials to the teachings of the invention. Therefore, this invention is not intended to be limited to the specific embodiments disclosed for carrying out the invention, but rather is intended to encompass all embodiments falling within the scope of the appended claims.

Claims

1. A method of ambient pressure synthesis of a hierarchical MOF material, characterized in that, include: Provide a supersaturated reaction solution containing ligands, metal salts, and solvents; At room temperature and pressure, the supersaturated reaction solution is mixed with a poor solvent and reacted in one step to prepare fractional metal-organic framework materials.

2. The method of claim 1, wherein: The metal salt includes cobalt salt or iron salt; And / or, the ligand comprises bis(p-carboxyphenylamino)phenylphosphine oxide; And / or, the solvent includes dimethyl sulfoxide; And / or, the undesirable solvent includes ethanol or methanol.

3. The method of claim 2, wherein: The cobalt salt includes Co(NO3)2·6H2O; And / or, the iron salt includes Fe(NO3)3·9H2O.

4. The method of claim 1, wherein: The molar ratio of the ligand to the metal salt is 1:1 to 1:1.2; And / or, the ratio of the amount of the ligand to the volume of the solvent is 0.025 ~ 0.042 mol / L; And / or, the volume ratio of the supersaturated reaction solution to the unsuitable solvent is 1:1.7 to 1:2; And / or, the reaction time is 60-90 h.

5. The method of claim 1, wherein, Specifically, it includes: The ligand, metal salt, and solvent are mixed evenly, and the mixture is filtered or centrifuged to obtain the supersaturated reaction solution.

6. The method of claim 1, wherein: The filter membrane has a pore size of 0.2~0.45 μm; And / or, the centrifugation speed is 6000~10000 rpm, and the time is 2~10 min.

7. The method of claim 1, wherein, Specifically, it includes: At room temperature and pressure, the undesirable solvent is added to a supersaturated reaction solution to generate a hierarchical structure, thereby obtaining the hierarchical metal-organic framework material in one step.

8. The hierarchical metal-organic framework material produced by the method of any one of claims 1-7, characterized by: The hierarchical metal-organic framework material includes a metal center and an organic ligand, and the hierarchical metal-organic framework material has a hierarchical structure.

9. The hierarchical metal-organic framework material according to claim 8, characterized in that: The hierarchical metal-organic framework material has a hierarchical structure that mimics the gills of a mushroom. And / or, the metal center includes at least one of cobalt and iron; And / or, the organic ligand comprises bis(p-carboxyphenylamino)phenylphosphine oxide.

10. The application of the hierarchical metal-organic framework material of claim 8 or 9 in the fields of flexible devices or industrial catalysis.

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