Preparation methods and applications of MOF-801 material, and methods for testing the water absorption rate of MOF-801 material.

Abstract

This invention provides a method for preparing MOF-801 material and its application, as well as a method for testing the water absorption rate of MOF-801 material, relating to the field of materials technology. The method for preparing MOF-801 material provided by this invention includes: mixing a zirconium source and an organic acid, followed by drying to obtain a pre-nucleation precursor product; mixing the obtained pre-nucleation precursor product with fumaric acid and water to obtain a mixture, then ball-milling the mixture to obtain a crude MOF-801 product; washing the crude MOF-801 product with water, then soaking it in methanol for 48 h, changing the methanol twice daily during the soaking period; and finally drying the soaked product at 100°C for 12 h to obtain purified MOF-801 material. This preparation method is highly efficient, environmentally friendly, and low-cost, contributing to improved environmental friendliness and economic efficiency in production.

Description

Technical Field

[0001] This invention relates to the field of materials technology, and in particular to a method for preparing MOF-801 material and its application, as well as a method for testing the water absorption rate of MOF-801 material. Background Technology

[0002] Faced with water scarcity, adsorbent-based atmospheric water harvesting (AWH) technology is considered a promising solution, capable of directly capturing moisture from the air to provide safe drinking water for water-scarce regions. Metal-organic frameworks (MOFs) are important candidates for water adsorption materials due to their highly ordered pore structure, abundant adsorption sites, and excellent water stability. Among them, MOF-801, with its outstanding hydrolytic stability—maintaining structural and performance stability even after 150 water adsorption-desorption cycles without significant material degradation—is considered a highly efficient and stable water adsorbent with broad application prospects in water management and gas storage. However, the operation of AWH equipment requires large quantities of adsorbent, and the challenges of large-scale production of MOF-801 limit its practical application.

[0003] The synthesis of MOF-801 typically employs solvothermal or hydrothermal methods. These traditional methods require high-temperature and high-pressure conditions and rely on expensive and large quantities of organic solvents, resulting in complex synthesis processes, long reaction times, and low yields, making them unsuitable for industrial production. Furthermore, the use of solvents not only increases production costs but also generates substantial amounts of hazardous waste, causing environmental pollution. Therefore, existing synthesis methods have limitations in terms of economy, environmental friendliness, and production efficiency, necessitating the development of a more efficient, green, and large-scale production strategy to meet the practical application needs of MOF-801 in the AWH (Autoclaved Acid) field.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The primary objective of this invention is to provide a method for preparing MOF-801 material to solve the aforementioned technical problems.

[0006] The second objective of this invention is to provide the application of the MOF-801 material prepared by the above-described method in atmospheric water collection.

[0007] A third objective of this invention is to provide a method for testing the water absorption rate of MOF-801 material.

[0008] To achieve the above objectives, the following technical solution is adopted:

[0009] In a first aspect, the present invention provides a method for preparing MOF-801 material, comprising the following steps:

[0010] a. A zirconium source and an organic acid are mixed and reacted, and then dried to obtain a pre-nucleation precursor product;

[0011] b. The prenucleation precursor product obtained in step a is mixed with fumaric acid and water to obtain a mixture, and then the mixture is ball-milled to obtain the crude MOF-801 product after reaction; the ball milling speed is 1500 rpm and the time is 1.5 h;

[0012] c. Wash the crude MOF-801 product obtained in step b with water, then soak it in methanol for 48 h, and replace the methanol with fresh methanol twice a day during the soaking period. After soaking, dry the product at 100℃ for 12 h to prepare the purified MOF-801 material.

[0013] The zirconium source is selected from zirconium propoxide, ZrCl4, or ZrOCl2·8H2O;

[0014] The organic acid is selected from acetic acid or formic acid.

[0015] As a further technical solution, the molar ratio of zirconium to organic acid in the zirconium source is 1:20 to 1:50.

[0016] As a further technical solution, the organic acid is acetic acid, and the molar ratio of zirconium to organic acid in the zirconium source is 1:20.

[0017] As a further technical solution, the organic acid is formic acid, and the molar ratio of zirconium to organic acid in the zirconium source is 1:50.

[0018] As a further technical solution, the molar ratio of the prenucleation precursor product, fumaric acid and water is 1:10:100 to 1:12:110.

[0019] As a further technical solution, when the organic acid is formic acid, the molar ratio of the prenucleation precursor product, fumaric acid and water is 1:10:100.

[0020] As a further technical solution, when the organic acid is acetic acid, the molar ratio of the prenucleation precursor product, fumaric acid and water is 1:12:106.

[0021] As a further technical solution, ball milling is performed using the classic PULVERISETTE 6 planetary single mill.

[0022] Secondly, the present invention provides the application of the MOF-801 material prepared by the above preparation method in atmospheric water collection.

[0023] Thirdly, the present invention provides a method for testing the water absorption rate of MOF-801 material, the method comprising:

[0024] MOF-801 material was prepared using the above-described preparation method;

[0025] The prepared MOF-801 material was vacuum dried at 150℃ for 7 h in an oven to obtain the dried MOF-801 material, and a mass of m was weighed. 干燥后 ;

[0026] Select a dryer, the dryer includes a hollow drying chamber with an open top and a sealing cover at the top opening of the drying chamber. A partition with through holes is provided in the drying chamber, the partition divides the drying chamber into upper and lower spaces, and a digital temperature and humidity meter is provided in the space above the partition.

[0027] A sulfuric acid solution is placed in the space below the partition inside the dryer to maintain the relative humidity inside the dryer between 45% and 55%, and the temperature inside the dryer is adjusted to a preset temperature based on a digital thermometer and hygrometer, the preset temperature including 15°C, 25°C and 35°C.

[0028] After drying for 7 hours, the MOF-801 material was placed in a petri dish, which was then placed on the desiccator shelf, sealed, and placed at the preset temperature for 24 hours. The water-absorbed MOF-801 material was then collected and weighed to a mass of m. 吸附后 ;

[0029] The water absorption rate of MOF-801 material was calculated using the following formula:

[0030] Water absorption rate = (m 吸附后 -m 干燥后 ) / m 吸附后 .

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The method for preparing MOF-801 material provided by this invention is highly efficient, capable of completing the preparation of MOF-801 material within hours, significantly shortening the preparation time and improving production efficiency; it is environmentally friendly, as it eliminates the need for additional heating or high pressure on the reaction mixture to achieve efficient synthesis of MOF-801, making the entire process more efficient and controllable; it is low-cost, reducing the need for prolonged heating or high-pressure conditions, and lowering reliance on expensive high-pressure equipment; it avoids the use of large amounts of organic solvents, significantly reducing solvent consumption compared to the typical solvothermal synthesis process of MOF-801, conforming to the basic principles of green chemistry, and helping to reduce environmental pollution and waste liquid treatment costs, thereby improving the environmental friendliness and economy of production. Attached Figure Description

[0033] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0034] Figure 1 Here is a flowchart of the mechanochemical synthesis of MOF-801;

[0035] Figure 2 XRD patterns of MOF-801 samples obtained under different ball milling times (a) and rotation speeds (b);

[0036] Figure 3 The nitrogen adsorption isotherm of MOF-801 sample at 77 K was measured under different ball milling times (a) and rotation speeds (b).

[0037] Figure 4 SEM image of MOF-801 prepared by grinding at 1500 rpm for 1.5 hours;

[0038] Figure 5 The water absorption properties of MOF-801 prepared by grinding at 1500 rpm for 1.5 hours at different temperatures were investigated. Detailed Implementation

[0039] Below in conjunction with embodiment and example, embodiment of the present invention is described in detail, but those skilled in the art will appreciate that the following embodiment and example are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiment in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise all fall within the scope of protection of the present invention. Unspecified conditions are carried out according to the conditions of normal conditions or manufacturer's recommendations. Reagents used or instruments not specified by the manufacturer are conventional products that can be purchased commercially.

[0040] In a first aspect, the present invention provides a method for preparing MOF-801 material, comprising the following steps:

[0041] a. A zirconium source and an organic acid are mixed and reacted, and then dried to obtain a pre-nucleation precursor product (i.e., an organic acid zirconium cluster with a stable [Zr6] core structure).

[0042] b. The prenucleation precursor product obtained in step a is mixed with fumaric acid and water to obtain a mixture, and then the mixture is ball-milled to obtain the crude MOF-801 product after reaction; the ball milling speed is 1500 rpm and the time is 1.5 h;

[0043] c. Wash the crude MOF-801 product obtained in step b with water, then soak it in methanol for 48 h, and replace the methanol with fresh methanol twice a day during the soaking period. After soaking, dry the product at 100℃ for 12 h to prepare the purified MOF-801 material.

[0044] The zirconium source is selected from zirconium propoxide, ZrCl4, or ZrOCl2·8H2O;

[0045] The organic acid is selected from acetic acid or formic acid.

[0046] The method for preparing MOF-801 material provided by this invention is highly efficient, capable of completing the preparation of MOF-801 material within hours, significantly shortening the preparation time and improving production efficiency; it is environmentally friendly, as it eliminates the need for additional heating or high pressure on the reaction mixture to achieve efficient synthesis of MOF-801, making the entire process more efficient and controllable; it is low-cost, reducing the need for prolonged heating or high-pressure conditions, and lowering reliance on expensive high-pressure equipment; it avoids the use of large amounts of organic solvents, significantly reducing solvent consumption compared to the typical solvothermal synthesis process of MOF-801, conforming to the basic principles of green chemistry, and helping to reduce environmental pollution and waste liquid treatment costs, thereby improving the environmental friendliness and economy of production.

[0047] In some alternative embodiments, the molar ratio of zirconium to organic acid in the zirconium source can be, for example, but not limited to, 1:20, 1:30 or 1:50.

[0048] In some preferred embodiments, the organic acid is acetic acid, and the molar ratio of zirconium to organic acid in the zirconium source is 1:20.

[0049] In some preferred embodiments, the organic acid is formic acid, and the molar ratio of zirconium to organic acid in the zirconium source is 1:50.

[0050] In some alternative embodiments, the molar ratio of the prenucleation precursor product, fumaric acid and water may be, for example, but not limited to, 1:10:100, 1:11:105 or 1:12:110.

[0051] In some preferred embodiments, when the organic acid is formic acid, the molar ratio of the prenucleation precursor product, fumaric acid, and water is 1:10:100.

[0052] In some preferred embodiments, when the organic acid is acetic acid, the molar ratio of the prenucleation precursor product, fumaric acid, and water is 1:12:106.

[0053] In some alternative implementations, ball milling is performed using a classic planetary single mill, the PULVERISETTE 6.

[0054] Secondly, the present invention provides the application of the MOF-801 material prepared by the above preparation method in atmospheric water collection.

[0055] The MOF-801 material prepared by this invention has good water absorption properties and can be used for atmospheric water collection.

[0056] Thirdly, the present invention provides a method for testing the water absorption rate of MOF-801 material, the method comprising:

[0057] MOF-801 material was prepared using the above-described preparation method;

[0058] The prepared MOF-801 material was vacuum dried at 150℃ for 7 h in an oven to obtain the dried MOF-801 material, and a mass of m was weighed. 干燥后 ;

[0059] Select a dryer, the dryer includes a hollow drying chamber with an open top and a sealing cover at the top opening of the drying chamber. A partition with through holes is provided in the drying chamber, the partition divides the drying chamber into upper and lower spaces, and a digital temperature and humidity meter is provided in the space above the partition.

[0060] A sulfuric acid solution is placed in the space below the partition inside the dryer to maintain the relative humidity inside the dryer between 45% and 55%, and the temperature inside the dryer is adjusted to a preset temperature based on a digital thermometer and hygrometer, the preset temperature including 15°C, 25°C and 35°C.

[0061] After drying for 7 hours, the MOF-801 material was placed in a petri dish, which was then placed on the desiccator shelf, sealed, and placed at the preset temperature for 24 hours. The water-absorbed MOF-801 material was then collected and weighed to a mass of m. 吸附后 ;

[0062] The water absorption rate of MOF-801 material was calculated using the following formula:

[0063] Water absorption rate = (m 吸附后 -m 干燥后 ) / m 吸附后 .

[0064] This testing method is simple, convenient, and accurate.

[0065] The present invention will be further illustrated below with specific embodiments. However, it should be understood that these embodiments are merely for the purpose of more detailed illustration and should not be construed as limiting the present invention in any way.

[0066] Comparative Example 1

[0067] A method for preparing a material includes the following steps:

[0068] Zirconium propoxide (IV) (70 wt% 1-propanol solution), acetic acid, fumaric acid, and deionized water (the amounts of each raw material were the same as in Example 1) were sequentially added to a 45 mL ceramic grinding jar, and eight ceramic grinding balls with a diameter of 1 cm were placed inside. Mechanical ball milling synthesis experiments were conducted using a PULVERISETTE 6 classic planetary single-mill mill. To systematically investigate the influence of grinding parameters on product formation, a single-factor variable method was used: under a fixed grinding time (1.5 h), the effects of different rotation speeds (1000 rpm, 1300 rpm, 1500 rpm) on the crystallization behavior of the product were investigated sequentially; conversely, under a fixed rotation speed (1500 rpm), the effects of different grinding times (1 h, 1.5 h, 2 h, 2.5 h) on product formation were investigated.

[0069] Experimental results showed that no MOF-801 structure products were obtained under the above conditions. Further analysis suggests that directly mixing zirconium source with fumaric acid under ball milling conditions is easily interfered with by competition from ligands such as acetate / ion, making it difficult for the [Zr6] cluster structure to form stably, thereby inhibiting the self-assembly process of the MOF framework and causing crystallization failure.

[0070] To overcome this problem, the inventors proposed the following embodiment, which introduces a pre-synthesis strategy. A stable zirconium acetate cluster precursor is first prepared in the solution phase to ensure the formation of a stable [Zr6] core structure in the reaction system. Subsequently, this zirconium cluster precursor is ball-milled with fumaric acid, which helps promote the ordered construction of MOF-801 and improves the crystallinity and phase purity of the target product.

[0071] Example 1

[0072] A method for preparing MOF-801 material, the preparation process is as follows: Figure 1 As shown, it includes the following steps:

[0073] 1. Zirconium propoxide (IV) (70 wt% 1-propanol solution) and acetic acid were mixed in a sealed beaker at a molar ratio of 1:20 and allowed to stand overnight at room temperature. The microcrystalline colorless powder was collected by vacuum filtration, gently washed with acetic acid, and dried at room temperature to finally obtain the prenucleation precursor product (zirconium acetate cluster precursor).

[0074] 2. The prenucleation precursor product, fumaric acid, and water were weighed and added sequentially to a 45 mL ceramic grinding bowl in a molar ratio of 1:12:106. Eight ceramic balls with a diameter of 1 cm were then placed inside. Ball milling was performed using a classic PULVERISETTE 6 planetary single-roll mill at speeds of 1000 rpm, 1300 rpm, and 1500 rpm for 1 h, 1.5 h, 2 h, and 2.5 h, respectively. After ball milling, white powder samples were obtained under different milling conditions.

[0075] 3. The white powder synthesized under different ball milling conditions was first washed with water, and then the washed product was soaked in methanol for 48 hours. During this period, the methanol was exchanged with fresh methanol twice a day. After that, it was dried in an oven at 100°C for 12 hours to finally obtain the MOF-801 product synthesized under different ball milling conditions.

[0076] Different grinding times and speeds significantly affect the crystallization behavior and pore structure of MOF-801. To systematically evaluate the influence of these two key process parameters on product formation, an experimental design using the controlled variable method was employed. Grinding speed or grinding time was fixed, while the other parameter was changed sequentially, obtaining XRD patterns under different conditions, such as... Figure 2 As shown in the figure. By comparing the intensity and distribution of the characteristic diffraction peaks of each sample in the spectrum, the optimal synthesis conditions for preparing MOF-801 with high crystallinity and high porosity were finally determined to be ball milling at 1500 rpm for 1.5 hours.

[0077] Figure 2 Figure 'a' shows the effect of different grinding times on the formation of the product crystal structure under a fixed grinding speed of 1500 rpm. As can be seen from the figure, grinding for 1 hour is insufficient to promote the nucleation and crystallization of MOF-801, resulting only in weak diffraction signals related to organic ligands. Extending the ball milling time to 1.5 hours significantly enhances the characteristic diffraction peaks of MOF-801, indicating successful crystal structure formation. However, further extending the time to 2 hours and 2.5 hours results in a decrease in the intensity of the main peak, presumably due to crystal defects introduced by excessive grinding, thus affecting structural integrity.

[0078] Figure 2 Figure b further investigated the effect of different grinding speeds on crystal formation under a fixed grinding time of 1.5 hours. When the rotation speed was 1000 rpm, no characteristic diffraction peaks of MOF-801 were observed in the spectrum, indicating that a crystal structure had not yet formed under this condition. When the rotation speed was increased to 1300 rpm, although a low-intensity diffraction signal appeared, crystallization was still insufficient. Only when the rotation speed was increased to 1500 rpm did clear and high-intensity characteristic peaks appear in the spectrum, indicating that this condition was most conducive to promoting the ordered growth of crystals and the development of porous structures.

[0079] Combination Figure 2 a in Figure 2 The analysis results of b in the figure show that ball milling at 1500 rpm for 1.5 hours was identified as the optimal ball milling synthesis condition for achieving high crystallinity and high porosity MOF-801.

[0080] The nitrogen adsorption isotherm of the synthesized MOF-801 sample at 77 K was determined. Figure 3 The left side (Figure a) shows MOF-801 samples prepared at a grinding speed of 1500 rpm for ball milling times of 1.5 h, 2.5 h, and 3.5 h; the right side (Figure b) shows MOF-801 samples prepared at a grinding speed of 1300 rpm and 1500 rpm for a ball milling time of 1.5 h. The results indicate that the nitrogen isotherm conforms to Type I characteristics in the IUPAC classification, typically indicating that the material has a microporous structure. It is worth noting that the isotherm curves of different samples may exhibit slight curvature in the low-pressure region, which may be related to structural defects within the material. These defects may originate from local lattice distortion or incompletely crystallized regions during ball milling, thus forming additional adsorption sites within the channels or framework structure. In particular, these defects may affect the material's affinity for water molecules, thereby affecting its stability and adsorption behavior under humid conditions.

[0081] The adsorption isotherms of different samples may exhibit slight bending or deviation from linear behavior in the low-pressure region. This is usually related to a certain number of structural defects within the material, such as local lattice distortion or incomplete crystallization in some areas. These defects are a microscopic feature formed during the rapid, solvent-free synthesis process of ball milling, and may introduce additional adsorption sites within the framework, thereby enhancing its affinity for small molecules (such as water and CO2). It should be noted that such structural defects do not necessarily lead to a decrease in material performance. On the contrary, multiple studies have confirmed that moderate defects can improve the adsorption capacity, catalytic activity, and functional tunability of MOF materials. Therefore, these microstructural differences induced by the ball milling process not only do not weaken the overall performance of MOF-801, but may also expand its potential application space in moisture stability regulation and functionalized adsorption.

[0082] The MOF-801 sample prepared under optimal synthesis conditions (milling at 1500 rpm for 1.5 hours) was morphologically analyzed by scanning electron microscopy (SEM), and the results are as follows: Figure 4As shown, the MOF-801 particles synthesized by ball milling are uniformly dispersed with a relatively consistent particle size distribution and exhibit a tendency towards spherical morphology, rather than the cubic structure obtained by traditional solution synthesis methods. The particle surface is slightly rough, and a certain degree of crystal agglomeration can be observed in local areas, which may be related to the microstructural changes caused by the interaction between particles and mechanical forces during ball milling.

[0083] MOF-801 samples prepared under optimal synthesis conditions (milling at 1500 rpm for 1.5 hours) were subjected to isothermal adsorption experiments at different temperatures using a water adsorption apparatus to systematically study the effect of temperature on the material's adsorption performance. By evaluating the water adsorption capacity of ball-milled MOF-801 under different temperature conditions, its applicability in practical applications such as water adsorption is provided as a reference.

[0084] To investigate the effect of temperature on the adsorption performance of MOF-801, the MOF-801 sample prepared under optimal synthesis conditions was first vacuum dried at 150℃ for 7 h to remove adsorbed water vapor, thereby performing activation treatment.

[0085] Subsequently, under controlled relative humidity (50% ± 5%), water vapor adsorption tests were conducted on the samples at 15℃, 25℃, and 35℃ (± 1℃). To achieve a constant temperature and humidity environment, sulfuric acid solutions of different concentrations were placed in the desiccator to maintain a specific relative humidity, and deionized water was used to dilute the sulfuric acid to regulate the humidity level. In addition, a digital thermometer was placed in the desiccator to monitor temperature and humidity changes in real time.

[0086] The adsorption experiment procedure is as follows: First, the sample is dried in an oven to remove adsorbed water vapor. Then, the dried sample is weighed and placed in a petri dish within a desiccator to adsorb water vapor under controlled humidity. The adsorption performance is determined using the weight gain method, expressed as the amount of water absorbed per unit mass of adsorbent (g / 100 g), calculated using the following formula:

[0087] Water absorption rate = (m 吸附后 -m 干燥后 ) / m 吸附后 ;

[0088] Where, m 吸附后 m represents the mass of MOF-801 after water vapor adsorption. 干燥后 The mass of MOF-801 after heating and desorption.

[0089] All adsorption tests were completed within 24 hours, and the maximum adsorption capacity of each sample (i.e., the amount adsorbed after 24 hours) was compared. The results are as follows: Figure 5As shown, MOF-801 has a maximum adsorption capacity of 30.2 g / 100 g at 25 °C, which decreases to 28.5 g / 100 g when the temperature drops to 15 °C. At 35 °C, the maximum adsorption capacity of MOF-801 further decreases to 27.5 g / 100 g. Furthermore, as... Figure 5 As shown, the adsorption curve of MOF-801 showed signs of instability after 6 h at 35℃. The results indicate that MOF-801 exhibits the best adsorption performance at 25℃ under constant relative humidity (50%), while higher temperatures (35℃) lead to a slight decrease in its water vapor adsorption capacity.

[0090] Example 2

[0091] A method for preparing MOF-801 material, the preparation method is as follows:

[0092] 1. Acetic acid was slowly added at a molar ratio of ZrOCl2·8H2O to acetic acid of 1:20. After gentle stirring for several minutes, the mixture was placed in a sealed container and allowed to stand at room temperature for 24 hours to promote coordination and self-assembly of the cluster structure. The reaction solution was filtered to collect the white microcrystalline product, which was then quickly washed with a small amount of acetic acid to remove unreacted components. The resulting product was dried overnight in a vacuum drying oven at room temperature to obtain the zirconium acetate cluster precursor.

[0093] 2. The prenucleation precursor product, fumaric acid, and water were weighed and added sequentially to a 45 mL ceramic grinding bowl in a molar ratio of 1:12:106. Eight ceramic balls with a diameter of 1 cm were then placed inside. Ball milling was performed using a classic PULVERISETTE 6 planetary single-roll mill at 1500 rpm for 1.5 h. After ball milling, a white powder sample was obtained.

[0094] 3. The white powder synthesized by ball milling was first washed with water, and then the washed product was soaked in methanol for 48 hours. During this period, the methanol was exchanged with fresh methanol twice a day. After that, it was dried in an oven at 100°C for 12 hours. After testing, the MOF-801 product was successfully synthesized.

[0095] Example 3

[0096] A method for preparing MOF-801 material, the preparation method is as follows:

[0097] 1. Weigh an appropriate amount of ZrCl4 as the zirconium source. Add formic acid slowly dropwise to the stirred system at a zirconium to formic acid molar ratio of 1:50. Then, stir at medium speed at 40°C for 6 hours to ensure complete reaction and zirconium cluster formation. Immediately after the reaction, filter and collect the white microcrystalline product. Wash with a small amount of formic acid to remove residues. Dry the product overnight at room temperature in a desiccator to obtain the high-purity zirconium formate cluster precursor.

[0098] 2. Weigh the prenucleation precursor product, fumaric acid, and water into a 45 mL ceramic grinding bowl at a molar ratio of 1:10:100, and place eight ceramic balls with a diameter of 1 cm inside. Ball milling synthesis was performed using a PULVERISETTE 6 classic planetary single-roll mill at 1500 rpm for 1.5 h. After ball milling, a white powder sample was obtained.

[0099] 3. The white powder synthesized by ball milling was first washed with water, and then the washed product was soaked in methanol for 48 hours. During this period, the methanol was exchanged with fresh methanol twice a day. After that, it was dried in an oven at 100°C for 12 hours. After testing, the MOF-801 product was successfully synthesized.

[0100] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing MOF-801 material, characterized in that, Includes the following steps: a. A zirconium source and an organic acid are mixed and reacted, and then dried to obtain a prenucleation precursor product, an organic acid zirconium cluster, wherein the molar ratio of zirconium to organic acid in the zirconium source is 1:20 to 1:50; b. The prenucleation precursor product obtained in step a is mixed with fumaric acid and water to obtain a mixture, which is then added to a 45 mL ceramic grinding bowl. Eight ceramic balls with a diameter of 1 cm are placed in the bowl, and the mixture is then ball-milled to obtain a crude MOF-801 product after the reaction. The ball milling speed is 1500 rpm and the time is 1.5 h. The molar ratio of the prenucleation precursor product, fumaric acid and water is 1:10:100 to 1:12:

110. c. Wash the crude MOF-801 product obtained in step b with water, then soak it in methanol for 48 h, and replace the methanol with fresh methanol twice a day during the soaking period. After soaking, dry the product at 100℃ for 12 h to prepare the purified MOF-801 material. The zirconium source is selected from zirconium propoxide, ZrCl4, or ZrOCl2·8H2O; The organic acid is selected from acetic acid or formic acid.

2. The method for preparing MOF-801 material according to claim 1, characterized in that, The organic acid is acetic acid, and the molar ratio of zirconium to organic acid in the zirconium source is 1:

20.

3. The method for preparing MOF-801 material according to claim 1, characterized in that, The organic acid is formic acid, and the molar ratio of zirconium to organic acid in the zirconium source is 1:

50.

4. The method for preparing MOF-801 material according to claim 1, characterized in that, When the organic acid is formic acid, the molar ratio of the prenucleation precursor product, fumaric acid, and water is 1:10:

100.

5. The method for preparing MOF-801 material according to claim 1, characterized in that, When the organic acid is acetic acid, the molar ratio of the prenucleation precursor product, fumaric acid, and water is 1:12:

106.

6. The method for preparing MOF-801 material according to claim 1, characterized in that, Ball milling was performed using a classic planetary single mill, PULVERISETTE 6.

7. The application of the MOF-801 material prepared by the preparation method according to any one of claims 1-6 in atmospheric water collection.

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