Metal-organic framework cluster body, composite cluster body, and method of making

Abstract

The application discloses a metal-organic framework cluster body, a composite material cluster body and a preparation method, the metal-organic framework cluster body is composed of metal-organic framework particles, the particle size of the metal-organic framework cluster body is 1-10 mu m, and the whole is spherical or approximately spherical; the inter-particle pore size of the metal-organic framework cluster body is 2-80 nm, and the total pore volume is 0.5-5.0 cm 3 / g. The application can obtain most of the metal-organic framework cluster bodies by spray drying the metal-organic framework particles with different particle size distribution ranges which are synthesized in advance, and the particles are closely arranged, the morphology is relatively uniform, and the metal-organic framework cluster bodies are suitable for large-scale preparation and production.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of metal-organic framework cluster body and preparation technology; more particularly, to a metal-organic framework cluster body, a composite material cluster body and a preparation method. BACKGROUND

[0002] Metal-organic framework (MOFs) material is a periodic network framework crystalline material formed by self-assembly of metal ions or metal ion clusters as nodes and organic bridging ligands containing carboxylic acid or nitrogen through coordination bonds. Due to the diversity of its structural composition, high specific surface area and porosity, and controllable pore structure and size, it has wide application prospects in the fields of gas storage and separation, luminescence and detection, catalysis and drug delivery and controlled release.

[0003] In the past two decades, the research direction of MOFs material has undergone a series of changes. From the research of bulk MOFs material to nanoscale or two-dimensional form, from the exploration of the pores of MOFs material itself to the construction of hierarchical pores, from the preparation of single MOFs material to the synthesis of MOFs composite material. Overall, it is a process from bulk to miniaturization, nanoscale or further construction; from single to diversification. The superstructure of nanoscale MOFs material assembly, MOFs cluster body, not only has its bulk properties, but also has the size and surface effect of nanomaterials, and different from the original, uniform layered pores, which can greatly improve the diffusion and mass transfer limitations of the original pore size, to enhance the application performance in some fields involving macromolecules, and is easy to separate and recover; and the introduction of other materials / particles can further endow the MOFs cluster body with other characteristics, which is conducive to realizing the multifunctionality of the MOFs cluster body in practical application.

[0004] Arnau Carné-Sánchez et al. once adopted spray-drying technology to in-situ synthesize several common MOF materials with hollow structure (ACarné-Sánchez, Imaz I, Cano-Sarabia M, et al. A spray-drying strategy for synthesis of nanoscale metal-organic frameworks and their assembly into hollow superstructures [J]. Nature Chemistry, 2013, 5(3): 203-211.). Through the increase of the precursor concentration at the edge to the critical concentration in the evaporation process of metal salt and ligand, the crystallization self-assembly of nanoscale MOFs at the edge of the MOFs cluster body with hollow structure is obtained. But for most MOFs materials, the synthesis of nanoscale requires high reaction temperature and long reaction time, or involves the addition of some adjusting agents, and the process of direct spray-drying or pre-heating is difficult to provide enough reaction energy and time. Therefore, although this method has the simple characteristics of one-step synthesis of MOFs material superstructure, due to the limitation of the temperature, concentration and reaction time of the material itself synthesis, it does not have wide applicability.

[0005] In order to solve the limitation of the reaction conditions of MOFs material itself in the preparation of metal-organic framework and its composite cluster body by spray-drying, it is necessary to provide a method for preparing metal-organic framework and its composite cluster body which is not limited by synthesis conditions, simple process and uniform product particle size and morphology. SUMMARY

[0006] The first technical problem to be solved by the present application is to provide a metal-organic framework cluster body.

[0007] The second technical problem to be solved by the present application is to provide a metal-organic framework composite cluster body.

[0008] The third technical problem to be solved by the present application is to provide a preparation method of metal-organic framework cluster body. The method can be used by pre-synthesized metal-organic framework particles to remove the limitation of temperature, concentration and reaction time of spray-drying synthesis of metal-organic framework particles, and has wider applicability. Also, by controlling the size of the pre-synthesized metal-organic framework particles, the metal-organic framework cluster body with adjustable pores can be obtained through spray-drying assembly.

[0009] The fourth technical problem to be solved by the present application is to provide a preparation method of a metal-organic framework composite cluster body. The method can realize the compounding of various metal-organic framework particles, the introduction of characteristic inorganic nanoparticles, the construction of a multi-level structure and the loading / embedding of drug molecules by introducing other materials for mixing and spray drying during the spray drying process of the metal-organic framework particles.

[0010] To solve the first technical problem, the present application adopts the following technical solution:

[0011] A metal-organic framework cluster body is composed of metal-organic framework particles, the particle size of the metal-organic framework cluster body is 1-10 μm, and the whole is spherical or approximately spherical; the inter-particle pore size of the metal-organic framework cluster body is 2-80 nm, and the total pore volume is 0.5-5.0 cm 3 / g.

[0012] Preferably, the metal ions in the metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, Hf ions of various valences.

[0013] Preferably, the organic ligand in the metal-organic framework particles is selected from one or more of 2-methyl imidazole, 2-amino imidazole, benzimidazole, amino benzimidazole, 2-imidazole formaldehyde, benzene-1,3,5-tricarboxylic acid, 2-amino benzene-1,3,5-tricarboxylic acid, terephthalic acid, amino terephthalic acid, 2-nitro terephthalic acid, 2-sulfonic acid terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid and 2,5-dihydroxy terephthalic acid.

[0014] Preferably, the metal-organic framework particles are wet solids and do not need to be dried.

[0015] To solve the second technical problem, the present application adopts the following technical solution:

[0016] A metal-organic framework composite cluster body is composed of first metal-organic framework particles and auxiliary materials, the particle size of the metal-organic framework composite cluster body is 1-10 μm, and the whole is spherical or approximately spherical; the inter-particle pore size of the metal-organic framework composite cluster body is 0-80 nm, and the total pore volume is 0-2.0 cm 3 / g.

[0017] Preferably, the auxiliary materials are one or more of second metal-organic framework particles, inorganic nanoparticles, polymer colloidal particles and drug molecules which are different from the first metal-organic framework particles.

[0018] Preferably, the metal ions in the first and second metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, Hf ions of each valence state.

[0019] Preferably, the organic ligands in the first and second metal-organic framework particles are selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino trimesic acid, terephthalic acid, amino terephthalic acid, 2-nitro terephthalic acid, 2-sulfonic terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, 2,5-dihydroxy terephthalic acid.

[0020] To solve the third technical problem described above, the present application adopts the following technical solution:

[0021] A preparation method of a metal-organic framework cluster body, comprising the following steps:

[0022] S11, adding metal-organic framework particles into a solvent, stirring and dispersing to form a metal-organic framework material spray-drying precursor;

[0023] S12, pumping the metal-organic framework material spray-drying precursor into a spray dryer for spray drying to obtain a metal-organic framework cluster body.

[0024] Preferably, in the step S11, the metal ions in the metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, Hf ions of each valence state.

[0025] Preferably, in the step S11, the organic ligands in the metal-organic framework particles are selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino trimesic acid, terephthalic acid, amino terephthalic acid, 2-nitro terephthalic acid, 2-sulfonic terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, 2,5-dihydroxy terephthalic acid.

[0026] Preferably, in the step S11, the particle size of the metal-organic framework particles is 1-500 nm; more preferably, the particle size of the metal-organic framework particles is 1-100 nm; most preferably, the particle size of the metal-organic framework particles is 1-80 nm.

[0027] Preferably, in step S11, the solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, cyclohexane, tetrahydrofuran, N,N'-dimethylformamide, N,N'-diethylformamide, dimethyl sulfoxide.

[0028] Preferably, in step S11, the solid content of the metal-organic framework spray-dried precursor is 0.1-10%.

[0029] Preferably, in step S12, the inlet temperature of the spray drying is 80-180°C; more preferably, the inlet temperature of the spray drying is 100-180°C.

[0030] Preferably, in step S12, the feed flow rate of the spray drying is 1-20 mL / min; more preferably, the feed flow rate of the spray drying is 10-20 mL / min.

[0031] Preferably, in step S12, the compressed air flow rate of the spray drying is 414-742 L / h; more preferably, the compressed air flow rate of the spray drying is 536-742 L / h.

[0032] To solve the above-mentioned fourth technical problem, the present application adopts the following technical scheme:

[0033] A preparation method of a metal-organic framework composite cluster body, comprising the following steps:

[0034] S21, adding first metal-organic framework particles into a solvent, and then adding an auxiliary material to stir and disperse or dissolve, to form a metal-organic framework composite spray-dried precursor;

[0035] S22, pumping the metal-organic framework composite spray-dried precursor into a spray dryer to perform spray drying, to obtain a metal-organic framework composite cluster body.

[0036] Preferably, in step S21, the auxiliary material is one or more of second metal-organic framework particles, inorganic nano-particles, polymeric colloidal particles, and drug molecules, which are different from the first metal-organic framework particles.

[0037] Preferably, in step S21, the mass ratio of the first metal-organic framework particles to the auxiliary material is 1:(0.1-1).

[0038] Preferably, in step S21, the metal ions in the first metal-organic framework particles and the second metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, and Hf ions in various valence states.

[0039] Preferably, in step S21, the organic ligand in the first metal-organic framework particles and the second metal-organic framework particles is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino trimesic acid, terephthalic acid, amino terephthalic acid, 2-nitro terephthalic acid, 2-sulfonic terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, 2,5-dihydroxy terephthalic acid.

[0040] Preferably, in step S21, the first metal-organic framework particles and the second metal-organic framework particles have a particle size of 1-500 nm; more preferably, the first metal-organic framework particles and the second metal-organic framework particles have a particle size of 1-100 nm; most preferably, the first metal-organic framework particles and the second metal-organic framework particles have a particle size of 1-80 nm.

[0041] Preferably, in step S21, the solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, cyclohexane, tetrahydrofuran, N,N'-dimethylformamide, N,N'-diethylformamide, dimethyl sulfoxide.

[0042] Preferably, in step S21, the metal-organic framework material spray-drying precursor has a solid content of 0.1-10%; more preferably, the metal-organic framework material spray-drying precursor has a solid content of 2-10%.

[0043] Preferably, in step S22, the spray-drying has an inlet temperature of 80-180°C; more preferably, the spray-drying has an inlet temperature of 100-180°C.

[0044] Preferably, in step S22, the spray-drying has a feed flow rate of 1-20 mL / min; more preferably, the spray-drying has a feed flow rate of 10-20 mL / min.

[0045] Preferably, in step S22, the spray-drying has a compressed air flow rate of 414-742 L / h; more preferably, the spray-drying has a compressed air flow rate of 536-742 L / h.

[0046] Any range recited in the present application includes the end values and any intervening value and any sub-range therein as well as the explicit endpoints.

[0047] Unless otherwise defined, all terms used in the present application, especially of the prior art, can be those commonly used in the art. The equipment used in the present application can be conventional equipment in the art or according to the prior art.

[0048] Compared with the prior art, the present application has the following beneficial effects:

[0049] 1) The present application can obtain spherical metal-organic framework cluster bodies with a particle size of 1-10 μm by spray drying pre-synthesized metal-organic framework particles with different particle size distribution ranges, without being limited by the temperature, concentration and reaction time required for the synthesis of metal-organic framework materials, and the particles are closely arranged and have a relatively uniform morphology, which is suitable for large-scale preparation and production.

[0050] 2) By selecting the particle size of pre-synthesized metal-organic framework particles with different particle size distribution ranges, metal-organic framework cluster bodies with different inter-particle pore diameters of 2-80 nm and total pore volumes of 0.5-5.0 cm 3 / g can be obtained.

[0051] 3) By adding auxiliary materials before spray drying, the auxiliary materials can be compounded with the metal-organic framework materials, including the compounding of various metal-organic framework particles, the introduction of characteristic inorganic nanoparticles, the construction of multi-level structures and the loading / embedding of drug molecules, and each material can be uniformly distributed / arranged in the entire structure. BRIEF DESCRIPTION OF DRAWINGS

[0052] The specific embodiments of the present application will be further described in detail below with reference to the accompanying drawings

[0053] Figure 1 A scanning electron microscope photograph of ZIF-8 cluster bodies with an initial particle size of 20 nm prepared by spray drying in Example 1;

[0054] Figure 2 A scanning electron microscope photograph of ZIF-8 cluster bodies with an initial particle size of 30 nm prepared by spray drying in Example 1;

[0055] Figure 3 A scanning electron microscope photograph of ZIF-8 cluster bodies with an initial particle size of 40 nm prepared by spray drying in Example 1;

[0056] Figure 4 A scanning electron microscope photograph of ZIF-8 cluster bodies with an initial particle size of 70 nm prepared by spray drying in Example 1;

[0057] Figure 5 A mesopore size distribution comparison of ZIF-8 cluster bodies with initial particle sizes of 20 / 30 / 40 / 70 nm prepared by spray drying in Example 1;

[0058] Figure 6 A scanning electron microscope photograph of HKUST-1 cluster bodies prepared by spray drying in Example 2;

[0059] Figure 7 Scanning electron microscope photo of MIL-101(Cr) cluster body prepared by spray drying in Example 3;

[0060] Figure 8 Scanning electron microscope photo of UiO-66 cluster body prepared by spray drying in Example 4;

[0061] Figure 9 Scanning electron microscope photo of ZIF-8&MIL-101(Cr) cluster body prepared by spray drying in Example 5;

[0062] Figure 10 Scanning electron microscope photo of ZIF-8&Fe3O4 cluster body prepared by spray drying in Example 6;

[0063] Figure 11 Practical photo of magnetic separation effect of ZIF-8&Fe3O4 cluster body prepared by spray drying in Example 6 when it is redispersed in water for 10 min;

[0064] Figure 12 Scanning electron microscope photo of ZIF-8&PS cluster body prepared by spray drying in Example 7;

[0065] Figure 13 Scanning electron microscope photo of DOX@ZIF-8 cluster body prepared by spray drying in Example 8;

[0066] Figure 14 Electronic microscope photo of DOX@ZIF-8 cluster body prepared by spray drying in Example 8;

[0067] Figure 15 Scanning electron microscope photo of ZIF-8 cluster body prepared by spray drying in Comparative Example 3;

[0068] Figure 16 Scanning electron microscope photo of ZIF-8 cluster body prepared by spray drying in Comparative Example 5. DETAILED DESCRIPTION

[0069] In order to make the present application clearer, further description will be made to the present application with reference to the preferred embodiments. It should be understood by those skilled in the art that the following description is illustrative rather than limiting and should not be construed to limit the scope of the present application.

[0070] As one aspect of the present application, the present application provides a metal-organic framework cluster body, which is composed of metal-organic framework particles, the particle size of the metal-organic framework cluster body is 1-10 μm, and the whole is spherical or approximately spherical; the inter-particle pore size of the metal-organic framework cluster body is 2-80 nm, and the total pore volume is 0.5-5.0 cm 3 / g.

[0071] According to some embodiments of the present application, the metal ions in the metal-organic framework particles are selected from one or more of the ions of each valence state of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, and Hf.

[0072] According to some embodiments of the present application, the organic ligand in the metal-organic framework particles is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino-trimesic acid, terephthalic acid, amino-terephthalic acid, 2-nitro-terephthalic acid, 2-sulfonic acid-terephthalic acid, hydroxy-terephthalic acid, 2-bromo-terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, and 2,5-dihydroxy-terephthalic acid.

[0073] According to some embodiments of the present application, the metal-organic framework particles are wet solids and are not dried.

[0074] As another aspect of the present application, the present application provides a metal-organic framework composite cluster body, which is composed of first metal-organic framework particles and auxiliary materials, the particle size of the metal-organic framework composite cluster body is 1-10 μm, and the whole is spherical or approximately spherical; the inter-particle pore size of the metal-organic framework composite cluster body is 0-80 nm, and the total pore volume is 0-5.0 cm 3 / g.

[0075] According to some embodiments of the present application, the auxiliary materials are one or more of second metal-organic framework particles, inorganic nanoparticles, polymeric colloidal particles, and drug molecules that are different from the first metal-organic framework particles.

[0076] According to some embodiments of the present application, the metal ions in the first metal-organic framework particles and the second metal-organic framework particles are selected from one or more of the ions of each valence state of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, and Hf.

[0077] According to some embodiments of the present application, the organic ligand in the first and second metal-organic framework particles is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazolecarboxaldehyde, trimesic acid, 2-amino-trimesic acid, terephthalic acid, aminoterephthalic acid, 2-nitroterephthalic acid, 2-sulfonatoterephthalic acid, hydroxyterephthalic acid, 2-bromoterephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, 2,5-dihydroxyterephthalic acid.

[0078] As yet another aspect of the present application, the above method for preparing a metal-organic framework cluster body includes the following steps:

[0079] S11, adding metal-organic framework particles into a solvent and stirring to disperse to form a metal-organic framework material spray-drying precursor; in this step, the metal-organic framework particles can be activated / unactivated wet solid (e.g. obtained after filtration or centrifugation), and if the material is not activated before spray-drying, the final obtained cluster body is activated; if the dried metal-organic framework particles are used as raw materials, the agglomeration of the particles themselves can result in poor dispersion of the spray-drying precursor, and the uniform morphology of the cluster body cannot be formed in the spray-drying process; since the solid content of the dispersion has a great influence on the morphology and size of the cluster body, when adding the solvent, as little solvent as possible is added to ensure a high initial solid content, which facilitates the adjustment of the solid content during use.

[0080] S12, pumping the above metal-organic framework material spray-drying precursor into a spray-drying machine for spray-drying to obtain a metal-organic framework cluster body; in this step, the spray-drying parameters, including the inlet temperature, the feed flow rate and the compressed gas flow rate, have a great influence on whether the metal-organic framework cluster body can be formed and the morphology and size of the formed cluster body, and therefore, selecting appropriate parameters is of great significance for obtaining a metal-organic framework cluster body with uniform particle size and morphology.

[0081] According to some embodiments of the present application, in the step S11, the metal ions in the metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, Hf ions of various valence states.

[0082] According to some embodiments of the present application, in step S11, the organic ligand in the metal-organic framework particles is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino trimesic acid, terephthalic acid, amino terephthalic acid, 2-nitro terephthalic acid, 2-sulfonic terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, 2,5-dihydroxy terephthalic acid.

[0083] According to some embodiments of the present application, in step S11, the metal-organic framework particles have a particle size of 1-500 nm; more preferably, the metal-organic framework particles have a particle size of 1-100 nm; most preferably, the metal-organic framework particles have a particle size of 1-80 nm. If not within the above range, due to the fixed size of the droplets formed by spray drying atomization, too large particle size can result in too few metal-organic framework particles in a single droplet, making it difficult to form clusters during solvent evaporation, and ultimately resulting in the inability to obtain metal-organic framework cluster bodies.

[0084] According to some embodiments of the present application, in step S11, the solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, cyclohexane, tetrahydrofuran, N,N'-dimethylformamide, N,N'-diethylformamide, dimethyl sulfoxide. If not selected from one or more of these solvents, the metal-organic framework particles can flocculate or coagulate when forming the spray drying precursor, or the surface tension of the solvent can result in the inability to obtain metal-organic framework cluster bodies with regular and uniform morphology; improper selection of the solvent can also result in the collapse and destruction of the structure of the metal-organic framework particles themselves, and thus the selection of a suitable solvent is critical to whether the cluster body structure can ultimately be obtained.

[0085] According to some embodiments of the present application, in step S11, the solid content of the metal-organic framework material spray dried precursor is 0.1-10%. If the solid content is too small, it can result in too few metal-organic framework particles in a single droplet formed by spray drying atomization, making it difficult to form metal-organic framework cluster bodies; if the solid content is too large, there can be too many metal-organic framework particles in a single droplet formed by spray drying atomization, which can result in clogging of the spray drying nozzle and the formation of metal-organic framework cluster bodies with a particle size distribution that is too large and not uniform.

[0086] According to some embodiments of the present application, in step S12, the inlet temperature of the spray drying is 80-180°C; more preferably, the inlet temperature of the spray drying is 100-180°C. If the inlet temperature is too low, the solvent is not completely evaporated during the spray drying, and the high solvent residue leads to the failure of the metal-organic framework particles to form a compact arrangement, so that the metal-organic framework cluster body cannot be obtained; if the inlet temperature is too high, the solvent is evaporated too quickly during the spray drying, and the internal moisture of the droplets is removed instantaneously, which easily leads to the formation of irregular, concave and broken metal-organic framework aggregates, and again the metal-organic framework cluster body with uniform particle size and morphology cannot be obtained.

[0087] According to some embodiments of the present application, in step S12, the feed flow rate of the spray drying is 1-20 mL / min; more preferably, the feed flow rate of the spray drying is 10-20 mL / min. If the feed flow rate is too slow, the number of metal-organic framework particles subjected to the spray drying per unit time is too small, and it is difficult to form the metal-organic framework cluster body; if the feed flow rate is too fast, the amount of solvent that needs to be evaporated per unit time is too large, which exceeds the drying capacity under the spray drying conditions, and again it is difficult to obtain the metal-organic framework cluster body.

[0088] According to some embodiments of the present application, in step S12, the compressed air flow rate of the spray drying is 414-742 L / h; more preferably, the compressed air flow rate of the spray drying is 536-742 L / h. If it is not within this range, a too low compressed air flow rate can not be able to effectively dry the precursor, and a too high compressed air flow rate can lead to the breakage and concave of the final metal-organic framework cluster body.

[0089] As still another aspect of the present application, the above method for preparing a metal-organic framework composite cluster body comprises the following steps:

[0090] S21, adding the first metal-organic framework particles into a solvent, and then adding an auxiliary material to stir, disperse or dissolve, to form a metal-organic framework composite spray drying precursor; the auxiliary material can be added in the form of a dispersion / powder thereof, and if a dispersion is used, the solid content needs to be calibrated in advance;

[0091] S22, pumping the above metal-organic framework composite spray drying precursor into a spray dryer to perform spray drying, to obtain a metal-organic framework composite cluster body.

[0092] According to some embodiments of the present application, in step S21, the auxiliary material is one or more of a second metal-organic framework particle different from the first metal-organic framework particle, an inorganic nanoparticle, a polymer colloidal particle and a drug molecule; the drug molecule can be dissolved or dispersed in the solvent.

[0093] According to some embodiments of the present application, in step S21, the mass ratio of the first metal-organic framework particles and the auxiliary material is 1:(0.1-1). If the mass ratio of the auxiliary material is too high, the characteristics of the metal-organic framework material itself are difficult to reflect; and if the mass ratio of the other material is too low, the unique performance of the composite material is difficult to reflect.

[0094] According to some embodiments of the present application, in step S21, the metal ions in the first metal-organic framework particles and the second metal-organic framework particles are selected from one or more of the valence state ions of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, and Hf.

[0095] According to some embodiments of the present application, in step S21, the organic ligand in the first metal-organic framework particles and the second metal-organic framework particles is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino trimesic acid, terephthalic acid, amino terephthalic acid, 2-nitro terephthalic acid, 2-sulfonic terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, mesotetracarboxylic acid, fumaric acid, and 2,5-dihydroxy terephthalic acid.

[0096] According to some embodiments of the present application, in step S21, the particle size of the first metal-organic framework particles and the second metal-organic framework particles is 1-500 nm; more preferably, the particle size of the first metal-organic framework particles and the second metal-organic framework particles is 1-100 nm; and most preferably, the particle size of the first metal-organic framework particles and the second metal-organic framework particles is 1-80 nm. If the particle size of the auxiliary material is not within the range, the number of other material particles in the single mist droplet formed by the atomization of the spray drying may be too small, the metal-organic framework particles and the other material cannot be compounded, and a cluster body composed of metal-organic framework particles only may be produced. If the drug molecules selected cannot be dissolved or dispersed in the solvent, large irregular drug powders may appear in the spray drying process, and even the process of forming clusters of metal-organic framework particles may be affected, and the embedding / loading of the material cannot be achieved by spray drying.

[0097] According to some embodiments of the present application, in step S21, the solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, cyclohexane, tetrahydrofuran, N,N’-dimethylformamide, N,N’-diethylformamide, and dimethyl sulfoxide.

[0098] According to some embodiments of the present application, in step S21, the solid content of the metal-organic framework material spray-dried precursor is 0.1-10%; more preferably, the solid content of the metal-organic framework material spray-dried precursor is 2-10%.

[0099] According to some embodiments of the present application, in step S22, the inlet temperature of the spray drying is 80-180℃; more preferably, the inlet temperature of the spray drying is 100-180℃.

[0100] According to some embodiments of the present application, in step S22, the feed flow rate of the spray drying is 1-20 mL / min; more preferably, the feed flow rate of the spray drying is 10-20 mL / min.

[0101] According to some embodiments of the present application, in step S22, the compressed air flow rate of the spray drying is 414-742 L / h; more preferably, the compressed air flow rate of the spray drying is 536-742 L / h.

[0102] In the preparation method of the present application, the selection of raw materials, the selection of various parameters, etc. constitute a whole technical solution, which cooperate with each other to obtain the metal-organic framework and composite cluster body prepared by the present application. Any condition beyond the scope will result in the failure to achieve the purpose of the present application.

[0103] Example 1

[0104] In this embodiment, ZIF-8 particles (porous crystalline material self-assembled by coordination of zinc ions and 2-methyl imidazole) with particle sizes of 20 / 30 / 40 / 70 nm are used as raw materials to prepare ZIF-8 cluster bodies by spray drying, including the following steps:

[0105] Step 1: Preparation of ZIF-8 aqueous spray-dried precursor

[0106] The pre-synthesized ZIF-8 wet solid is dispersed in water, the solid content is determined and adjusted to 2 wt%, forming a ZIF-8 aqueous spray-dried precursor, ready for use;

[0107] Step 2: Spray drying preparation of ZIF-8 cluster body

[0108] The inlet temperature of the spray drying is set to 100℃, the feed flow rate is 15.2 mL / min, and the compressed air flow rate is 536 L / h. After the inlet temperature is stabilized at the set value, the ZIF-8 aqueous spray-dried precursor is pumped into the spray dryer for spray drying, and the obtained ZIF-8 cluster body product is taken out in the collection chamber.

[0109] Figure 1The scanning electron microscope picture of ZIF-8 cluster body with initial particle size of 20 nm, under the condition, the ZIF-8 cluster particle size is 1-6 μm, the body morphology is regular, it is uniform spherical, the surface is smooth and no recess is found, and the particles are arranged closely.

[0110] Figure 2 The scanning electron microscope picture of ZIF-8 cluster body with initial particle size of 30 nm, under the condition, the cluster body particle size is 1-6 μm, the morphology is regular, it is basically uniform spherical, the surface is smooth and no recess is found, and the particles are arranged closely.

[0111] Figure 3 The scanning electron microscope picture of ZIF-8 cluster body with initial particle size of 40 nm, under the condition, the cluster body particle size is 1-8 μm, the morphology is relatively regular, most of them are regular spherical, and a small amount of donut morphology appears, and the particles are arranged closely.

[0112] Figure 4 The scanning electron microscope picture of ZIF-8 cluster body with initial particle size of 70 nm, under the condition, the cluster body particle size is 1-8 μm, the morphology is relatively regular, most of them are regular spherical but donut morphology appears, and the particles are arranged closely, and a small amount of scattered particles do not form clusters.

[0113] From the above Figures 1-4 It can be seen that ZIF-8 particles with four kinds of particle size distribution can form ZIF-8 cluster body with relatively regular morphology and basically closely arranged particles, but with the increase of particle size, the morphology gradually tends to be intermediate recess (donut) from regular spherical, and the surface tends to be rough from smooth.

[0114] Figure 5 The comparison of the pore size distribution of the ZIF-8 cluster bodies with four different initial particle sizes shows that with the increase of particle size, the size of the formed pores also gradually increases, and the pore volume also increases.

[0115] Example 2

[0116] In this embodiment, HKUST-1 particles with a particle size of 2-3 nm (metal-organic framework material 1, 3, 5-copper of 1, 3, 5-benzenetricarboxylic acid) are used as raw materials to prepare HKUST-1 cluster body by spray drying, including the following steps:

[0117] Step 1: Preparation of HKUST-1 ethanol phase spray drying precursor

[0118] The pre-synthesized HKUST-1 wet solid is dispersed in a certain amount of ethanol, the solid content is determined and adjusted to 2 wt%, and the HKUST-1 ethanol phase spray drying precursor is formed, which is ready for use;

[0119] Step 2: Spray drying preparation of HKUST-1 cluster body

[0120] The spray drying inlet temperature was set to 120°C, the feed flow rate was 15.2 mL / min, and the compressed gas flow rate was 536 L / h. After the inlet temperature was stabilized at the set value, the HKUST-1 ethanol phase spray-drying precursor was pumped into the spray dryer for spray drying, and the obtained HKUST-1 cluster body product was taken out in the collection chamber.

[0121] Figure 6 The scanning electron microscope picture of the HKUST-1 cluster body with an initial particle size of 2-3 nm, under the condition that the HKUST-1 cluster body particle size was 1-10 μm, the morphology was regular, and the surface was smooth without recesses and the particle arrangement was tight.

[0122] Example 3

[0123] In this embodiment, MIL-101(Cr) particles with a particle size of 300 nm were used as raw materials to prepare MIL-101(Cr) cluster bodies by spray drying, including the following steps:

[0124] Step 1: Preparation of MIL-101(Cr) aqueous phase spray-drying precursor

[0125] The pre-synthesized MIL-101(Cr) wet solid was dispersed in a certain amount of water, the solid content was determined and adjusted to 0.1 wt%, and the MIL-101(Cr) aqueous phase spray-drying precursor was formed for later use;

[0126] Step 2: Spray drying preparation of MIL-101(Cr) cluster body

[0127] The spray drying inlet temperature was set to 180°C, the feed flow rate was 1.9 mL / min, and the compressed gas flow rate was 536 L / h. After the inlet temperature was stabilized at the set value, the MIL-101(Cr) aqueous phase spray-drying precursor was pumped into the spray dryer for spray drying, and the obtained MIL-101(Cr) cluster body product was taken out in the collection chamber.

[0128] Figure 7 The scanning electron microscope picture of the MIL-101(Cr) cluster body with an initial particle size of 300 nm, under the condition that the MIL-101(Cr) cluster body particle size was 2-5 μm, the morphology was relatively regular, and the surface was basically spherical without recesses, and the particle arrangement was ordered.

[0129] Example 4

[0130] In this embodiment, UiO-66 particles with a particle size of 20 nm were used as raw materials to prepare UiO-66 cluster bodies by spray drying, including the following steps:

[0131] Step 1: Preparation of UiO-66 aqueous-ethanol mixed phase spray-drying precursor

[0132] The pre-synthesized UiO-66 wet solid was dispersed into a certain amount of solvent (water: ethanol volume ratio = 4:1), the solid content was determined and adjusted to 4wt%, forming the UiO-66 aqueous-ethanol mixed phase spray-drying precursor, ready for use;

[0133] Step 2: Spray-drying preparation of UiO-66 cluster body

[0134] The spray-drying inlet temperature was set to 120℃, the feed flow rate was 15.2mL / min, and the compressed gas flow rate was 601L / h. After the inlet temperature was stabilized at the set value, the UiO-66 aqueous-ethanol mixed phase spray-drying precursor was pumped into the spray-dryer for spray-drying. The obtained UiO-66 cluster body product was taken out in the collection chamber.

[0135] Figure 8 It is a scanning electron microscope picture of the UiO-66 cluster body with an initial particle size of 20nm. Under this condition, the UiO-66 cluster body has a particle size of 1-5μm, the morphology is relatively regular, and it is basically uniform spherical, the surface is slightly rough but no depression is seen, and the particle arrangement is relatively close.

[0136] Example 5

[0137] In this embodiment, ZIF-8 particles with a particle size of 40nm and MIL-101(Cr) with a particle size of 60nm were used as raw materials to prepare ZIF-8&MIL-101(Cr) cluster body by spray-drying, including the following steps:

[0138] Step 1: Preparation of ZIF-8 aqueous phase spray-drying precursor

[0139] The pre-synthesized ZIF-8 wet solid was dispersed into a certain amount of water, the solid content was determined and adjusted to 2wt%, forming the ZIF-8 aqueous phase spray-drying precursor;

[0140] The pre-synthesized MIL-101(Cr) wet solid was dispersed into a certain amount of water, the solid content was determined and adjusted to 2wt%, forming the MIL-101(Cr) aqueous phase spray-drying precursor;

[0141] The ZIF-8 aqueous phase spray-drying precursor and an equal amount of MIL-101(Cr) aqueous phase spray-drying precursor were mixed and stirred to form the ZIF-8&MIL-101(Cr) aqueous phase spray-drying precursor, ready for use;

[0142] Step 2: Spray-drying preparation of ZIF-8&MIL-101(Cr) cluster body

[0143] The spray drying inlet temperature was set to 120℃, the feed flow rate was 15.2 mL / min, and the compressed gas flow rate was 536 L / h. After the inlet temperature was stabilized at the set value, the ZIF-8&MIL-101(Cr) aqueous phase spray-drying precursor was pumped into the spray dryer for spray drying, and the obtained ZIF-8&MIL-101(Cr) cluster body product was taken out in the collection chamber.

[0144] Figure 9 The scanning electron microscope picture of the ZIF-8&MIL-101(Cr) cluster body is shown in Figure 1. Under the above conditions, the particle size of the ZIF-8&MIL-101(Cr) cluster body was 1-10 μm, was relatively regular, was basically spherical, the surface was slightly rough but no recess was seen, and the particle arrangement was relatively compact. Table 1 shows the mass and atomic percentage of Zn and Cr elements in the ZIF-8&MIL-101(Cr) cluster body, which was basically consistent with the initial feeding value.

[0145] Table 1

[0146]

[0147] Example 6

[0148] In this embodiment, ZIF-8 particles with a particle size of 20 nm and Fe3O4 with a particle size of 10 nm were used as raw materials to prepare ZIF-8&Fe3O4 cluster bodies by spray drying, including the following steps:

[0149] Step 1: Preparation of ZIF-8&Fe3O4 aqueous phase spray-drying precursor

[0150] The pre-synthesized ZIF-8 wet solid was dispersed in a certain amount of water, the solid content was determined and adjusted to 2 wt%, and the ZIF-8 aqueous phase spray-drying precursor was formed;

[0151] The pre-synthesized Fe3O4 wet solid was dispersed in a certain amount of water, the solid content was determined and adjusted to 2 wt%, and the Fe3O4 aqueous phase spray-drying precursor was formed;

[0152] The ZIF-8 aqueous phase spray-drying precursor was mixed with 1 / 10 mass ratio of Fe3O4 aqueous phase spray-drying precursor for stirring, and the ZIF-8&Fe3O4 aqueous phase spray-drying precursor was formed for later use;

[0153] Step 2: Spray drying preparation of ZIF-8&Fe3O4 cluster body

[0154] The spray drying inlet temperature was set to 100℃, the feed flow rate was 15.2 mL / min, and the compressed gas flow rate was 536 L / h. After the inlet temperature was stabilized at the set value, the ZIF-8&Fe3O4 aqueous phase spray-drying precursor was pumped into the spray dryer for spray drying, and the obtained ZIF-8&Fe3O4 cluster body product was taken out in the collection chamber.

[0155] Figure 10 The scanning electron microscope picture of the ZIF-8&Fe3O4 cluster body, the particle size of the ZIF-8&Fe3O4 cluster body under the condition was 2-5 μm, the morphology was uniform, it was a regular spherical shape, the surface was smooth, and the particles were arranged closely. From the electron microscope picture, it was difficult to distinguish the ZIF-8 and Fe3O4 particles according to the size. Table 2 was the mass and atomic percentage of Fe and Zn elements in the ZIF-8&Fe3O4 cluster body, which was basically consistent with the initial feeding value.

[0156] Table 2

[0157]

[0158] Figure 11 The magnetic separation effect of the ZIF-8&Fe3O4 cluster body when it was dispersed in water for 10 minutes showed that the cluster body had good magnetic effect, and the introduction of the Fe3O4 inorganic nanoparticles could make the cluster body have the magnetic separation characteristic.

[0159] Example 7

[0160] In this embodiment, ZIF-8 particles with a particle size of 20 nm and PS microspheres with a particle size of 400 nm were used as raw materials to prepare ZIF-8&PS cluster bodies by spray drying, including the following steps:

[0161] Step 1: Preparation of ZIF-8&PS aqueous phase spray-drying precursor

[0162] The pre-synthesized ZIF-8 wet solid was dispersed in a certain amount of water, the solid content was determined and adjusted to 2 wt%, and the ZIF-8 aqueous phase spray-drying precursor was formed;

[0163] The solid content of the pre-synthesized PS dispersion was determined and adjusted to 2 wt%, and the PS aqueous phase spray-drying precursor was formed;

[0164] The ZIF-8 aqueous phase spray-drying precursor was mixed with 1 / 4 mass ratio of the PS aqueous phase spray-drying precursor for stirring, and the ZIF-8&PS aqueous phase spray-drying precursor was formed for use;

[0165] Step 2: Spray drying preparation of ZIF-8&PS cluster body

[0166] The spray drying inlet temperature was set to 100°C, the feed flow rate was 20.9 mL / min, and the compressed gas flow rate was 601 L / h. After the inlet temperature was stabilized at the set value, the ZIF-8&PS aqueous phase spray drying precursor was pumped into the spray dryer for spray drying, and the obtained ZIF-8&PS cluster body product was taken out in the collection chamber.

[0167] Figure 12 The scanning electron microscope picture of the ZIF-8&PS cluster body is shown in the figure. Under the above conditions, the particle size of the ZIF-8&PS cluster body is 1-5 μm, and the morphology is relatively uniform, which is a spherical shape formed by the assembly of two different sizes of particles. The particles are arranged closely, and the ZIF-8 and PS particles can be distinguished according to the size of the surface particles.

[0168] Example 8

[0169] In this embodiment, ZIF-8 particles with a particle size of 20 nm and doxorubicin hydrochloride (DOX) were used as raw materials to prepare DOX@ZIF-8 cluster bodies by spray drying, including the following steps:

[0170] Step 1: Preparation of DOX@ZIF-8 aqueous phase spray drying precursor

[0171] The pre-synthesized ZIF-8 wet solid was dispersed in a certain amount of water, the solid content was determined and adjusted to 2 wt%, and the ZIF-8 aqueous phase spray drying precursor was formed;

[0172] The DOX raw material was weighed at 1 / 5 of the mass ratio of ZIF-8, and was added to the ZIF-8 aqueous phase spray drying precursor, and was stirred and ultrasonicated for 3 min to form the DOX@ZIF-8 aqueous phase spray drying precursor for use;

[0173] Step 2: Spray drying preparation of DOX@ZIF-8 cluster body

[0174] The spray drying inlet temperature was set to 100°C, the feed flow rate was 20.9 mL / min, and the compressed gas flow rate was 601 L / h. After the inlet temperature was stabilized at the set value, the ZIF-8&PS aqueous phase spray drying precursor was pumped into the spray dryer for spray drying, and the obtained ZIF-8&PS cluster body product was taken out in the collection chamber.

[0175] Figure 13 The scanning electron microscope picture of the DOX@ZIF-8 cluster body is shown in the figure. Under the above conditions, the particle size of the ZIF-8&PS cluster body is 1-10 μm, and the morphology is uniform, which is a regular spherical shape. The particles are arranged closely, and there is no difference in the morphology of the pure ZIF-8 cluster body. The particles can be observed to be adhered due to DOX on the surface of a small amount of cluster bodies.

[0176] Figure 14This is a microscopic image of the DOX@ZIF-8 clusters. It can be clearly seen that DOX (red) is evenly distributed in the DOX@ZIF-8 clusters, and no DOX is found in other places.

[0177] Example 9

[0178] Example 1 is repeated, except that: the metal ions of the selected 20nm metal-organic framework particles are selected from one or more of the following valence states of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, and Hf; the organic ligands in the metal-organic framework particles are selected from 2-methylimidazolium, 2-aminoimidazolium, benzimidazole, aminobenzimidazole, 2-imidazolium formaldehyde, trimellitic acid, 2-aminotriphenyl phthalic acid, terephthalic acid, aminoterephthalic acid, 2-nitroterephthalic acid, 2-sulfonic acid terephthalic acid, and hydroxyterephthalic acid. Formic acid, 2-bromoterephthalic acid, trimellitic acid, mesitylene benzoic acid, fumaric acid, and 2,5-dihydroxyterephthalic acid are used; including but not limited to ZIF-67, ZIF-90, MOF-5, MOF-74, MOF-801, MOF-100, MOF-53, UiO-66-NH2, UiO-66-SO3H, and UiO-66-COOH. The resulting metal-organic framework clusters have a regular spherical morphology, no surface depressions, and a dense particle arrangement; the effect obtained is similar to that of the 20nm ZIF-8 clusters in Example 1.

[0179] Comparative Example 1

[0180] The preparation method of HKUST-1 clusters with an initial particle size of 2-3 nm in Example 2 was repeated, with the only difference being that in step 1, the pre-synthesized HKUST-1 wet solid was dispersed in a certain amount of water; ultimately, HKUST-1 clusters could not be obtained in the collection chamber. This is because HKUST-1 is unstable in aqueous solution, which causes damage to its structure and collapse of its pores, thus preventing the acquisition of HKUST-1 clusters.

[0181] Comparative Example 2

[0182] The preparation method of ZIF-8 clusters with an initial particle size of 20 nm in Example 1 was repeated, with the only difference being that in step 1, the solid content of the ZIF-8 aqueous spray-dried precursor was 0.01 wt%; ultimately, no ZIF-8 clusters were collected in the collection chamber. Because the solid content of the spray-dried precursor was too low, it was difficult to provide enough ZIF-8 nanoparticles to form clusters, thus ZIF-8 clusters could not be obtained.

[0183] Comparative Example 3

[0184] The preparation method of ZIF-8 cluster body with initial particle size of 40 nm in Example 1 was repeated, with the only difference being that in step 1, the ZIF-8 particles were dried and then dispersed into a certain amount of water; Figure 15 The scanning electron microscope photos of the finally collected powder can be seen, and the product morphology is not uniform, the particle size distribution is wide, the surface is concave, and there are many unformed particles, and a uniform ZIF-8 cluster body cannot be obtained. Because the re-dispersion of dry powder is difficult to achieve the uniformity of wet solid in the solvent, the droplets formed by spray drying may contain aggregates of different particle sizes, resulting in uneven shrinkage during solvent evaporation, and finally a uniform ZIF-8 cluster body cannot be obtained.

[0185] Comparative Example 4

[0186] The preparation method of ZIF-8 cluster body with initial particle size of 40 nm in Example 1 was repeated, with the only difference being that in step 2, the inlet temperature of spray drying was set to 60°C; no ZIF-8 cluster body was collected in the collection chamber. Because the boiling point of water is 100°C, the set temperature of spray drying is much lower than the boiling point value, and a large number of water molecules are difficult to evaporate in a short spray drying process, and can only reach the collection chamber with the airflow, so ZIF-8 cluster body cannot be obtained.

[0187] Comparative Example 5

[0188] The preparation method of ZIF-8 cluster body with initial particle size of 40 nm in Example 1 was repeated, with the only difference being that in step 2, the inlet temperature of spray drying was set to 180°C; Figure 16 The scanning electron microscope photos of the finally collected powder can be seen, and the product morphology is not uniform, although the aggregates are formed by self-assembly of particles, but there are different degrees of concave, and a uniform ZIF-8 cluster body cannot be obtained. For ZIF-8 system, high drying temperature leads to rapid evaporation of solvent, which is easy to form hollow structure, but also easy to cause the inward concave of shell layer, and finally form a collapsed spherical structure.

[0189] Comparative Example 6

[0190] The preparation method of ZIF-8 cluster body with initial particle size of 40 nm in Example 1 was repeated, with the only difference being that in step 2, the inlet temperature of spray drying was set to 180°C;

[0191] Comparative Example 7

[0192] The preparation method of ZIF-8 cluster body with initial particle size of 40 nm in Example 1 was repeated, with the only difference being that in Step 2, the compressed gas flow rate for spray drying was set to 301 L / h; no ZIF-8 cluster body was collected in the collection chamber. Due to the lower compressed gas flow rate, the precursor could not be dried enough, resulting in residual moisture reaching the collection chamber with the gas flow, so no ZIF-8 cluster body could be obtained.

[0193] Obviously, the above embodiments of the present application are merely exemplary for clearly illustrating the present application, and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the embodiments cannot be exhausted. Any obvious changes or variations derived from the technical solutions of the present application are still within the protection scope of the present application.

Claims

1. A metal-organic framework cluster body, characterized by: is composed of metal-organic framework particles, the particle size of the metal-organic framework cluster body is 1-10 μm, and the whole is spherical or approximately spherical; the inter-particle pore size of the metal-organic framework cluster body is 2-80 nm, and the total pore volume is 0.5-5.0 cm³ / g; The preparation method of the metal-organic framework cluster body comprises the following steps: S11, the metal-organic framework wet solid particles are added into a solvent, and stirred and dispersed to form a metal-organic framework material spray-drying precursor; S12, the metal-organic framework material spray-drying precursor is pumped into a spray dryer for spray drying to obtain a metal-organic framework cluster body; In step S11, the metal ions in the metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, Hf ions of each valence state. In step S11, the organic ligand in the metal-organic framework particles is selected from one or more of 2-methyl imidazole, 2-amino imidazole, benzimidazole, amino benzimidazole, 2-imidazole formaldehyde, benzene-1,3,5-tricarboxylic acid, 2-amino benzene-1,3,5-tricarboxylic acid, terephthalic acid, amino terephthalic acid, 2-nitro terephthalic acid, 2-sulfonic acid terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, methyl benzene-1,3,5-tricarboxylic acid, fumaric acid, and 2,5-dihydroxy terephthalic acid. In step S11, the particle size of the metal-organic framework particles is 1-80 nm. In step S11, the solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, cyclohexane, tetrahydrofuran, N,N'-dimethylformamide, N,N'-diethylformamide, and dimethyl sulfoxide; when the metal-organic framework particles are HKUST-1, the solvent is ethanol; when the metal-organic framework particles are ZIF-8, the solvent is water; when the metal-organic framework particles are MIL-101(Cr), the solvent is water; and when the metal-organic framework particles are UiO-66, the solvent is a mixed solvent of water:ethanol in a volume ratio of 4:

1. In step S11, the solid content of the metal-organic framework material spray-drying precursor is 0.1-10%. In step S12, the inlet temperature of the spray drying is 100-180℃. In step S12, the feed flow rate of the spray drying is 10-20 mL / min. In step S12, the compressed air flow rate of the spray drying is 536-742 L / h.

2. The MOF cluster body of claim 1, wherein: The metal ions in the metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, Hf ions of each valence state.

3. The MOF cluster body of claim 1, wherein: The organic ligand in the metal-organic framework particles is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino-trimesic acid, terephthalic acid, amino-terephthalic acid, 2-nitro-terephthalic acid, 2-sulfonic acid-terephthalic acid, hydroxy-terephthalic acid, 2-bromo-terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, 2,5-dihydroxy-terephthalic acid.

4. A metal-organic framework composite cluster body, characterized by: The metal-organic framework composite cluster body is composed of the first metal-organic framework particles and the auxiliary material, has a particle size of 1-10 μm, and is spherical or approximately spherical as a whole; the metal-organic framework composite cluster body has an inter-particle pore size of 0-80 nm and a total pore volume of 0-5.0 cm³ / g; The preparation method of the metal-organic framework composite cluster body, characterized in that it comprises the following steps: S21, the first metal-organic framework wet solid particles are added into a solvent, and an auxiliary material is added to stir and disperse or dissolve, to form a metal-organic framework composite spray-drying precursor; S22, the metal-organic framework composite spray-drying precursor is pumped into a spray dryer to perform spray drying, to obtain the metal-organic framework composite cluster body; In step S21, the auxiliary material is one or more of second metal-organic framework particles, inorganic nano-particles, polymer colloidal particles, and drug molecules, which are different from the first metal-organic framework particles; In step S21, the mass ratio of the first metal-organic framework particles to the auxiliary material is 1:(0.1-1); In step S21, the metal ions in the first metal-organic framework particles and the second metal-organic framework particles are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, and Hf in various valence states; In step S21, the organic ligand in the first metal-organic framework particles and the second metal-organic framework particles is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino-trimesic acid, terephthalic acid, amino-terephthalic acid, 2-nitro-terephthalic acid, 2-sulfonic acid-terephthalic acid, hydroxy-terephthalic acid, 2-bromo-terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, and 2,5-dihydroxy-terephthalic acid; In step S21, the particle size of the first metal-organic framework particles and the second metal-organic framework particles is 1-80 nm; In step S21, the solvent is selected from one or more of water, methanol, ethanol, propanol, n-butanol, cyclohexane, tetrahydrofuran, N,N'-dimethylformamide, N,N'-diethylformamide, and dimethyl sulfoxide; In step S21, the solid content of the metal-organic framework material spray-drying precursor is 2-10%; In step S22, the inlet temperature of the spray drying is 100-180°C; In step S22, the feeding flow rate of the spray drying is 10-20 mL / min; In step S22, the compressed air flow rate of the spray drying is 536-742 L / h.

5. The metal-organic framework composite cluster body of claim 4, wherein: The adjuvant is one or more of a second metal-organic framework particle, an inorganic nanoparticle, a polymeric colloidal particle, and a drug molecule that is different from the first metal-organic framework particle.

6. The metal-organic framework composite cluster body of claim 4, wherein: The metal ions in the first metal-organic framework particle and the second metal-organic framework particle are selected from one or more of Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Ce, Hf ions in various valence states.

7. The metal-organic framework composite cluster body of claim 4, wherein: The organic ligand in the first metal-organic framework particle and the second metal-organic framework particle is selected from one or more of 2-methylimidazole, 2-aminoimidazole, benzimidazole, aminobenzimidazole, 2-imidazole formaldehyde, trimesic acid, 2-amino trimesic acid, terephthalic acid, aminoterephthalic acid, 2-nitro terephthalic acid, 2-sulfonic acid terephthalic acid, hydroxy terephthalic acid, 2-bromo terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, 2,5-dihydroxy terephthalic acid.

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