An amorphous Zr-MOF material and a preparation method of a spherical nano ZrC derived therefrom
By using amorphous Zr-MOF materials as precursors, spherical nano-ZrC powder was prepared through solvothermal reaction and high-temperature pyrolysis. This solved the problem of the influence of the porosity of carbon fiber preforms on densification and strength in the existing technology, and realized ultra-high temperature ceramic matrix composite materials with high densification and high strength.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-20
- Publication Date
- 2026-03-31
AI Technical Summary
In the preparation of ultra-high temperature ceramic matrix composites, the porosity of the carbon fiber preform makes it difficult for large particles to penetrate, affecting the densification of the material. Furthermore, the sharp powder damages the carbon fiber matrix, leading to a decrease in strength.
Spherical nano-ZrC powder was prepared by using amorphous Zr-MOF material as a precursor through solvothermal reaction and high-temperature pyrolysis. The morphology and purity were controlled by adjusting the reaction ratio and solvent composition.
A high-density and high-strength ultra-high temperature ceramic matrix composite material was achieved. By adjusting the reaction ratio and solvent composition of Zr-MOF, the size and purity of ZrC were controlled, and the generation of layered carbon was avoided, thus obtaining spherical nano ZrC powder.
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Figure CN117402367B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of materials chemistry and relates to an amorphous Zr-MOF material and a method for preparing its derived spherical nano ZrC. Background Technology
[0002] ZrC possesses excellent ablation resistance and superior high-temperature performance, making it one of the ideal materials for preparing ultra-high temperature ceramic matrix composites. It plays an extremely important role in aerospace, especially in the field of hypersonic flight.
[0003] Slurry infiltration is a common method for preparing ultra-high temperature ceramic matrix composites. However, when using slurry infiltration to prepare ceramic matrix composites, the pore size of the carbon fiber preform varies from tens of nanometers to tens of micrometers, making it difficult for large particles to penetrate, affecting the densification of the material. Furthermore, powder with sharp edges can damage the carbon fiber matrix, affecting the material's strength. Therefore, to obtain composite materials with high densification and high strength, spherical morphology and nanoscale powder raw materials are crucial. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to provide an amorphous Zr-MOF material and a method for preparing the derived spherical nano ZrC, which addresses the shortcomings of the prior art.
[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:
[0006] This invention discloses a method for preparing amorphous Zr-MOF materials, comprising the following steps:
[0007] (1) The zirconium metal salt is mixed with organic ligands, modifiers and solvents, and ultrasonically mixed to obtain a metal-organic mixture; the metal-organic mixture is subjected to a solvothermal reaction to obtain an amorphous Zr-MOF suspension;
[0008] (2) The amorphous Zr-MOF suspension obtained in step (1) is centrifuged, washed and dried to obtain the amorphous Zr-MOF material.
[0009] In step (1), the solvent is a mixed solvent of N,N-dimethylformamide and deionized water in a volume ratio of 13 to 19:1 to 7.
[0010] In some embodiments, preferably, in step (1), the solvent is a mixed solvent of N,N-dimethylformamide and deionized water in a volume ratio of 15:5.
[0011] In some embodiments, in step (1), the zirconium metal salt is ZrCl4; the organic ligand is 2,3,6,7,10,11-hexahydroxytriphenylene hydrate; and the modulator is acetic acid.
[0012] In some embodiments, in step (1), the molar ratio of the zirconium metal salt to the organic ligand is 3 to 6:1; the molar ratio of the organic ligand to the modulator is 1:140 to 280; and the mass-volume ratio of the organic ligand to the solvent is 50 to 100 mg: 20 to 80 mL.
[0013] In some embodiments, preferably, in step (1), the molar ratio of the zirconium metal salt to the organic ligand is 6:1; the molar ratio of the organic ligand to the modulator is 1:140; and the mass-volume ratio of the organic ligand to the solvent is 60 mg: 20 mL.
[0014] In some embodiments, in step (1), the ultrasound has a frequency of 20 to 40 kHz and a temperature of 25 to 35 °C; the solvothermal reaction has a reaction temperature of 100 to 120 °C and a reaction time of 12 to 24 h.
[0015] In some embodiments, preferably, in step (1), the ultrasound has a frequency of 40 kHz and a temperature of 25 °C; the solvothermal reaction has a reaction temperature of 100 °C and a reaction time of 24 h.
[0016] In step (1), the ultrasound time is sufficient to completely dissolve the solid raw materials in the system.
[0017] In some embodiments, in step (2), the washing liquid used in the centrifugal washing process is ethanol; the drying method is vacuum drying at 70-90°C for 12-24 hours.
[0018] The amorphous Zr-MOF material prepared by the above method is also within the scope of protection of this invention.
[0019] The application of the aforementioned amorphous Zr-MOF material in the preparation of amorphous Zr-MOF material-derived spherical nano-ZrC is also within the scope of protection of this invention.
[0020] Furthermore, this invention discloses a method for preparing amorphous Zr-MOF material-derived spherical nano-ZrC. The amorphous Zr-MOF material prepared by the above method is placed in a graphite crucible and then placed in a vacuum carbon tube furnace. High-temperature pyrolysis is performed under a preset pyrolysis program to obtain the desired Zr-MOF material.
[0021] In some embodiments, the pyrolysis procedure is as follows: heating rate of 5-10℃ / min, holding at 600-800℃ for 3-6h, holding at 1300-1500℃ for 1-4h, and pyrolysis is carried out in a vacuum environment with 50-100 sccm of argon gas.
[0022] In some embodiments, preferably, the pyrolysis procedure is as follows: heating rate of 10℃ / min, holding at 800℃ for 3h, holding at 1500℃ for 1h, and pyrolysis is carried out in a vacuum environment with 100 sccm of argon gas.
[0023] The amorphous Zr-MOF material derived from the above preparation method is also within the scope of protection of this invention.
[0024] The particle size of the amorphous Zr-MOF material-derived spherical nano-ZrC is 10–100 nm, preferably 50–100 nm.
[0025] The application of the aforementioned amorphous Zr-MOF material or the aforementioned amorphous Zr-MOF material-derived spherical nano-ZrC in the preparation of ultra-high temperature ceramic matrix composites is also within the scope of protection of this invention.
[0026] The ultra-high temperature mentioned above is defined as 2000–2500℃.
[0027] Beneficial effects:
[0028] (1) In this invention, amorphous Zr-MOF material is used as a precursor. Since MOF material has the characteristic of easy size and morphology adjustment, its morphology can be adjusted by adjusting the reaction ratio of Zr-MOF synthesis, thereby adjusting the size and morphology of ZrC after pyrolysis.
[0029] (2) The present invention uses amorphous Zr-MOF material as a precursor. By adjusting the proportion of water in the solvent, the purity and size morphology of ZrC powder after pyrolysis can be easily adjusted.
[0030] (3) In this invention, using deionized water as a solvent to partially replace N,N-dimethylformamide can effectively prevent the generation of layered carbon during the pyrolysis of amorphous Zr-MOF materials, and can also modify the morphology of the generated amorphous Zr-MOF-derived nano ZrC powder. Attached Figure Description
[0031] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.
[0032] Figure 1 These are X-ray diffraction data from Examples 1-4 of the amorphous Zr-MOF.
[0033] Figure 2 These are X-ray diffraction data from examples 4-8 of the amorphous Zr-MOF.
[0034] Figure 3The image shows the microstructure of the amorphous Zr-MOF in Example 1 as obtained by scanning electron microscopy.
[0035] Figure 4 The image shows the microstructure of the amorphous Zr-MOF in Example 2 obtained by scanning electron microscopy.
[0036] Figure 5 The image shows the microstructure of the amorphous Zr-MOF in Example 3 as obtained by scanning electron microscopy.
[0037] Figure 6 The image shows the microstructure of the amorphous Zr-MOF in Example 4 as obtained by scanning electron microscopy.
[0038] Figure 7 The image shows the microstructure of the amorphous Zr-MOF in Example 5 obtained by scanning electron microscopy.
[0039] Figure 8 The image shows the microstructure of the amorphous Zr-MOF in Example 6 obtained by scanning electron microscopy.
[0040] Figure 9 The image shows the microstructure of the amorphous Zr-MOF in Example 7 obtained by scanning electron microscopy.
[0041] Figure 10 These are X-ray diffraction data from examples 1-4 of amorphous Zr-MOF-derived ZrC.
[0042] Figure 11 These are X-ray diffraction data from examples 4-8 of amorphous Zr-MOF-derived ZrC.
[0043] Figure 12 The image shows the microstructure of amorphous Zr-MOF-derived ZrC obtained in Example 1, as obtained by scanning electron microscopy.
[0044] Figure 13 The image shows the microstructure of amorphous Zr-MOF-derived ZrC obtained in Example 2, as obtained by scanning electron microscopy.
[0045] Figure 14 The image shows the microstructure of amorphous Zr-MOF-derived ZrC obtained in Example 3, as obtained by scanning electron microscopy.
[0046] Figure 15 The image shows the microstructure of amorphous Zr-MOF-derived ZrC obtained in Example 4, as obtained by scanning electron microscopy.
[0047] Figure 16 The image shows the microstructure of amorphous Zr-MOF-derived ZrC obtained in Example 5 using a scanning electron microscope.
[0048] Figure 17 The image shows the microstructure of amorphous Zr-MOF-derived ZrC obtained in Example 6 using a scanning electron microscope.
[0049] Figure 18 The image shows the microstructure of amorphous Zr-MOF-derived ZrC obtained in Example 7 using a scanning electron microscope. Detailed Implementation
[0050] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.
[0051] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.
[0052] Example 1
[0053] Preparation of amorphous Zr-MOF materials:
[0054] (1) ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate were dissolved in 20 mL of N,N-dimethylformamide at a molar ratio of 3:1 (wherein, the mass of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate was 60 mg). Acetic acid was then added to the solution (the molar ratio of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate to acetic acid was 1:140). The mixture was ultrasonically mixed at 40 kHz at 25 °C until completely dissolved. After mixing, a metal-organic mixture was obtained. The metal-organic mixture was transferred to a 50 mL polytetrafluoroethylene liner and then placed in a reaction vessel. The mixture was subjected to a solvothermal reaction at 100 °C for 24 h to obtain an amorphous Zr-MOF suspension.
[0055] (2) The amorphous Zr-MOF suspension obtained in step (1) was washed three times by centrifugation with ethanol and then vacuum dried at 70°C for 24 hours to obtain the flower-shaped amorphous Zr-MOF material.
[0056] Preparation of nano-ZrC derived from amorphous Zr-MOF materials:
[0057] The flower-shaped amorphous Zr-MOF material prepared in this embodiment was placed in a graphite crucible and then placed in a vacuum carbon tube furnace. Argon gas was passed through the furnace in a vacuum environment at 100 sccm. The furnace was heated at a rate of 10 °C / min and held at 800 °C for 3 h and then at 1500 °C for 1 h to obtain octahedral nano ZrC powder.
[0058] Example 2
[0059] Preparation of amorphous Zr-MOF materials:
[0060] (1) ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate were dissolved in 20 mL of N,N-dimethylformamide at a molar ratio of 4:1 (wherein, the mass of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate was 60 mg). Acetic acid was then added to the solution (the molar ratio of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate to acetic acid was 1:140). The mixture was ultrasonically mixed at 40 kHz at 25 °C until completely dissolved. After mixing, a metal-organic mixture was obtained. The metal-organic mixture was transferred to a 50 mL polytetrafluoroethylene liner and then placed in a reaction vessel. The mixture was subjected to a solvothermal reaction at 100 °C for 24 h to obtain an amorphous Zr-MOF suspension.
[0061] (2) The amorphous Zr-MOF suspension obtained in step (1) was washed three times by centrifugation with ethanol and then vacuum dried at 70°C for 24 hours to obtain the flower-shaped amorphous Zr-MOF material.
[0062] Preparation of nano-ZrC derived from amorphous Zr-MOF materials:
[0063] The flower-shaped amorphous Zr-MOF material prepared in this embodiment was placed in a graphite crucible and then placed in a vacuum carbon tube furnace. Argon gas was passed through the furnace in a vacuum environment at 100 sccm. The furnace was heated at a rate of 10 °C / min and held at 800 °C for 3 h and then at 1500 °C for 1 h to obtain octahedral nano ZrC powder.
[0064] Example 3
[0065] Preparation of amorphous Zr-MOF materials: The preparation method is the same as that in "Preparation of amorphous Zr-MOF materials" in Example 1. The difference is that in this example, ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate are dissolved in N,N-dimethylformamide at a molar ratio of 5:1 to finally prepare amorphous Zr-MOF materials.
[0066] Preparation of nano-ZrC derived from amorphous Zr-MOF material: The preparation method is the same as that in Example 1, “Preparation of nano-ZrC derived from amorphous Zr-MOF material”, except that the amorphous Zr-MOF material used is prepared in this example.
[0067] Example 4
[0068] Preparation of amorphous Zr-MOF materials: The preparation method is the same as that in Example 2, except that in this example, ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate are dissolved in N,N-dimethylformamide at a molar ratio of 6:1 to finally prepare amorphous Zr-MOF materials.
[0069] Preparation of nano-ZrC derived from amorphous Zr-MOF material: The preparation method is the same as that in Example 2, “Preparation of nano-ZrC derived from amorphous Zr-MOF material”, except that the amorphous Zr-MOF material used is prepared in this example.
[0070] Example 5
[0071] Preparation of amorphous Zr-MOF materials: The preparation method is the same as that in Example 1, except that in this example, ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate are dissolved in 20 mL of a mixed solvent containing N,N-dimethylformamide and deionized water at a molar ratio of 6:1 (wherein, the mass of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate is 60 mg, and the volume ratio of N,N-dimethylformamide to deionized water in the mixed solvent is 19:1), and the amorphous Zr-MOF material is finally prepared.
[0072] Preparation of nano-ZrC derived from amorphous Zr-MOF material: The preparation method is the same as that in Example 1, “Preparation of nano-ZrC derived from amorphous Zr-MOF material”, except that the amorphous Zr-MOF material used is prepared in this example.
[0073] Example 6
[0074] Preparation of amorphous Zr-MOF materials: The preparation method is the same as that in Example 2, except that in this example, ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate are dissolved in 20 mL of a mixed solvent containing N,N-dimethylformamide and deionized water at a molar ratio of 6:1 (wherein, the mass of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate is 60 mg, and the volume ratio of N,N-dimethylformamide to deionized water in the mixed solvent is 17:3), and the amorphous Zr-MOF material is finally prepared.
[0075] Preparation of nano-ZrC derived from amorphous Zr-MOF material: The preparation method is the same as that in Example 2, “Preparation of nano-ZrC derived from amorphous Zr-MOF material”, except that the amorphous Zr-MOF material used is prepared in this example.
[0076] Example 7
[0077] Preparation of amorphous Zr-MOF materials: The preparation method is the same as that in Example 1, except that in this example, ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate are dissolved in 20 mL of a mixed solvent containing N,N-dimethylformamide and deionized water at a molar ratio of 6:1 (wherein, the mass of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate is 60 mg, and the volume ratio of N,N-dimethylformamide to deionized water in the mixed solvent is 15:5), and the amorphous Zr-MOF materials are finally prepared.
[0078] Preparation of nano-ZrC derived from amorphous Zr-MOF material: The preparation method is the same as that in Example 1, “Preparation of nano-ZrC derived from amorphous Zr-MOF material”, except that the amorphous Zr-MOF material used is prepared in this example.
[0079] Example 8
[0080] Preparation of amorphous Zr-MOF materials: The preparation method is the same as that in Example 2, except that in this example, ZrCl4 and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate are dissolved in 20 mL of a mixed solvent containing N,N-dimethylformamide and deionized water at a molar ratio of 6:1 (wherein, the mass of 2,3,6,7,10,11-hexahydroxytriphenylene hydrate is 60 mg, and the volume ratio of N,N-dimethylformamide to deionized water in the mixed solvent is 13:7), and the amorphous Zr-MOF materials are finally prepared.
[0081] Preparation of nano-ZrC derived from amorphous Zr-MOF material: The preparation method is the same as that in Example 2, “Preparation of nano-ZrC derived from amorphous Zr-MOF material”, except that the amorphous Zr-MOF material used is prepared in this example.
[0082] Example 9: Product Measurement Results
[0083] (1) Figure 1The figures show X-ray diffraction data of amorphous Zr-MOFs in Examples 1-4. Specifically, aZM-3 was prepared in Example 1 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahedroxytriphenylene hydrate was 3:1), aZM-4 was prepared in Example 2 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahedroxytriphenylene hydrate was 4:1), aZM-5 was prepared in Example 3 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahedroxytriphenylene hydrate was 5:1), and aZM-6 was prepared in Example 4 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahedroxytriphenylene hydrate was 6:1). Figure 2 The figures show X-ray diffraction data of amorphous Zr-MOFs in Examples 4-8, where aZM-6 was prepared in Example 4, aZM-6-1DI in Example 5, aZM-6-3DI in Example 6, aZM-6-5DI in Example 7, and aZM-6-7DI in Example 8. Figure 1 , Figure 2 It can be seen that the amorphous Zr-MOF material samples prepared in the eight examples are all amorphous.
[0084] (2) Figures 3-9 The images shown are scanning electron microscope (SEM) images of the amorphous Zr-MOFs prepared in Examples 1 to 7. Figures 3-6 It can be seen that different morphologies of this amorphous Zr-MOF can be obtained by changing the ratio of ZrCl4 to 2,3,6,7,10,11-hexahydroxytriphenylene hydrate; Figures 7-9 It can be seen that the morphology and size of the obtained amorphous Zr-MOF can be affected by adjusting the proportion of deionized water in the mixed solvent.
[0085] (3) Figure 10 The images show X-ray diffraction data of amorphous Zr-MOF-derived nano-ZrC in Examples 1-4. ZrC-3 was prepared in Example 1 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahydroxytriphenylene hydrate was 3:1), ZrC-4 was prepared in Example 2 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahydroxytriphenylene hydrate was 4:1), ZrC-5 was prepared in Example 3 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahydroxytriphenylene hydrate was 5:1), and ZrC-6 was prepared in Example 4 (molar ratio of ZrCl4 to 2,3,6,7,10,11-hexahydroxytriphenylene hydrate was 6:1). Figure 11The images show X-ray diffraction data of amorphous Zr-MOF-derived nano-ZrC in Examples 4-8. ZrC-6 was prepared in Example 4, ZrC-6-1DI in Example 5, ZrC-6-3DI in Example 6, ZrC-6-5DI in Example 7, and ZrC-6-7DI in Example 8. ZrC JCPDS#89-4054 is a standard card data image from Jade 5.0.
[0086] Depend on Figure 10 , Figure 11 It can be seen that the amorphous Zr-MOF-derived nano-ZrC powders prepared in the six examples (except for Examples 5 and 8) are all pure-phase ZrC. The ZrC powder prepared in Example 5 contains more amorphous carbon, and the ZrC powder prepared in Example 8 contains the ZrO2 phase. Furthermore, from... Figure 11 As can be seen, the diffraction peaks of the prepared amorphous Zr-MOF-derived nano ZrC are strongest when the solvent is a mixture of 15 mL N,N-dimethylformamide and 5 mL deionized water (i.e., ZrC-6-5DI).
[0087] (4) Figures 12-18 These are scanning electron microscope images of the microstructures of amorphous Zr-MOF-derived nano-ZrC from Examples 1 to 7; Figures 12-15 As shown, in Examples 1 to 4, the amorphous Zr-MOF-derived nano-ZrC powder particles are uniformly dispersed in layered carbon, and the original amorphous Zr-MOF structure collapses. Most of the particles have a diameter between 10 and 50 nm, while a small number of large particles reach 80 nm, indicating that the prepared amorphous Zr-MOF-derived nano-ZrC powder has a narrow particle size distribution and basically exhibits an octahedral morphology. Figures 16-18 As shown, the amorphous Zr-MOF-derived nano-ZrC powder particles in Examples 5 to 7 are basically spherical in shape, and no layered carbon is observed. This indicates that deionized water, as a solvent, can effectively replace N,N-dimethylformamide to prevent the generation of layered carbon during the pyrolysis process, and can also modify the morphology of the generated amorphous Zr-MOF-derived nano-ZrC powder. Among them, the ZrC powder prepared in Example 7 has the closest morphology to spheres, and the particle size distribution is narrow, concentrated in the range of 50-100 nm. Its dispersibility is also better than that of the ZrC powder prepared in Examples 5 and 6.
[0088] This invention provides a concept and method for preparing amorphous Zr-MOF materials and their derived spherical nano-ZrC. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.
Claims
1. A method for preparing an amorphous Zr-MOF material, characterized in that, The preparation method comprises the following steps: (1) mixing a zirconium metal salt, an organic ligand, a modulator, and a solvent, and uniformly mixing them by ultrasonic waves to obtain a metal-organic mixed solution; and performing a solvothermal reaction on the metal-organic mixed solution to obtain an amorphous Zr-MOF suspension; (2) performing centrifugal washing and drying on the amorphous Zr-MOF suspension obtained in step (1) to obtain an amorphous Zr-MOF material. In step (1), the solvent is a mixed solvent of N,N-dimethylformamide and deionized water in a volume ratio of 13-19:1-7. In step (1), the organic ligand is 2,3,6,7,10,11-hexahydroxytriphenylamine hydrate; and the modulator is acetic acid. In step (1), the molar ratio of the zirconium metal salt to the organic ligand is 3-6:1; the molar ratio of the organic ligand to the modulator is 1:140-280; and the mass-volume ratio of the organic ligand to the solvent is 50-100 mg:20-80 mL.
2. The method for preparing amorphous Zr-MOF material according to claim 1, characterized in that, In step (1), the zirconium metal salt is ZrCl4.
3. The method for preparing amorphous Zr-MOF material according to claim 1, characterized in that, In step (1), the ultrasonic frequency is 20-40 kHz, and the ultrasonic temperature is 25-35℃; and the reaction temperature of the solvothermal reaction is 100-120℃, and the reaction time is 12-24 h.
4. The method for preparing amorphous Zr-MOF material according to claim 1, characterized in that, In step (2), the washing liquid used in the centrifugal washing is ethanol; and the drying method is vacuum drying at 70-90℃ for 12-24 h.
5. The amorphous Zr-MOF material prepared by the preparation method in any one of claims 1-4.
6. The application of the amorphous Zr-MOF material in claim 5 in the preparation of amorphous Zr-MOF material derived spherical nano-ZrC.
7. A method for preparing amorphous Zr-MOF material derived spherical nano-ZrC, characterized in that, The amorphous Zr-MOF material in claim 5 is placed in a graphite crucible and placed in a vacuum carbon tube furnace, and high-temperature pyrolysis is performed under a preset pyrolysis program, to obtain.
8. The method for preparing amorphous Zr-MOF material-derived spherical nano-ZrC according to claim 7, characterized in that, The pyrolysis program is: a heating rate of 5-10℃ / min, 600-800℃ for 3-6 h, 1300-1500℃ for 1-4 h, and pyrolysis in a vacuum environment with 50-100 sccm argon.
9. The amorphous Zr-MOF material derived spherical nano-ZrC prepared by the preparation method in any one of claims 7-8.
10. The application of the amorphous Zr-MOF material in claim 5 or the amorphous Zr-MOF material derived spherical nano-ZrC in claim 9 in the preparation of ultra-high-temperature ceramic matrix composites.