Mofs derivative materials immobilized in glass, methods of making and using the same

Abstract

The application discloses a MOFs derivative material fixed in glass and a preparation method and application thereof, and belongs to the technical field of material engineering. The provided MOFs derivative material fixed in glass comprises glass powder and MOFs derivative material loaded on the glass powder, and the glass powder comprises glass powder made of waste glass. The preparation method of the MOFs derivative material fixed in glass comprises the following steps: providing glass powder made of waste glass; and mixing MOFs material with the glass powder and heating to obtain the MOFs derivative material fixed in glass. The material can be made into hollow microspheres or solid microspheres, and is convenient to be used as a filler of a fixed bed reactor and a fluidized bed reactor, so that continuous advanced oxidation degradation of organic pollutants can be realized. The application can alleviate the technical problems of unstable performance of the MOFs material, high heavy metal ion dissolution and difficult recovery.

Description

Technical Field

[0001] This application belongs to the field of materials engineering technology, specifically relating to a MOFs derivative material fixed in glass, its preparation method and application. Background Technology

[0002] Metal-organic frameworks (MOFs) are currently a popular material in the field of catalysis. By controlling the synthesis conditions and selecting the loading materials, a wide variety of MOFs can be prepared and applied to environmental pollution control. MOFs are porous crystalline materials with a periodic spatial arrangement, formed by the self-assembly of metal ions (metal clusters) with carboxylic acids and organic ligands such as nitrogen. MOFs combine the characteristics of both inorganic and organic materials in terms of composition and function, exhibiting advantages over traditional single inorganic or organic materials. They have a large specific surface area and abundant active sites, and have been proven to effectively catalyze the activation of oxides, generating reactive oxygen species for the efficient degradation of pollutants. However, their recycling stability is poor, and some heavy metal ions exhibit high leaching rates, limiting their practical application.

[0003] The coordination bonds between metal-ligands in MOF materials are prone to breakage in high-temperature, acidic / alkaline, or humid environments, leading to structural collapse and performance degradation. Derivatization treatments such as carbonization and sulfidation can transform MOFs into metal carbides, sulfides, or porous carbon materials, significantly enhancing their chemical and thermal stability, thereby mitigating the aforementioned problems. Currently, MOF derivatives are used through defect engineering and heteroatom doping strategies to expose more active sites, thereby improving the catalytic activity of MOF materials.

[0004] While MOF derivatives enhance catalytic activity, they also present a series of problems, such as metal ion dissolution. Most known MOFs are supported on materials like copper foam, resin, and perlite to reduce metal ion dissolution and improve material stability. However, the uneven interfacial forces formed during loading make it difficult to control the relationship between MOFs and the support. Some MOFs fail to adhere well to the support and are prone to detachment in complex environments, limiting the overall lifespan of the material. Currently, large-scale synthesis of various MOFs in the liquid phase is possible; however, repeated use in catalytic degradation of pollutants leads to a decrease in specific surface area or deactivation of active sites (e.g., oxidation or photocorrosion in photocatalysis). Furthermore, MOFs are mostly nano / micron-sized powders, which can cause pipe blockage or material loss in practical applications. Powdered materials are also difficult to recover in water treatment processes, easily dispersed, and unstable. Most MOFs contain heavy metal ions, potentially causing secondary pollution. Therefore, finding a macroscopically stable and easily recyclable MOF material remains a pressing technical challenge. Summary of the Invention

[0005] In view of the aforementioned problems, the present invention aims to at least partially solve one of the technical problems in the related art. Therefore, the present invention provides a MOFs derivative material immobilized in glass, its preparation method, and its application, which can alleviate the technical problems of unstable performance, high leaching of heavy metal ions, or difficulty in recycling of current MOFs materials, and overcome the shortcomings of the prior art.

[0006] To solve the above-mentioned technical problems, this application is implemented as follows: According to a first aspect of this application, embodiments of this application provide a MOFs derivative material fixed in glass, the MOFs derivative material fixed in glass comprising glass powder and MOFs material loaded on the glass powder, the glass powder comprising glass powder made from waste glass.

[0007] In some embodiments, the MOFs derivative material immobilized in the glass is obtained by heating a mixture of MOFs powder and glass powder made from waste glass.

[0008] In some embodiments, the MOFs derivative material immobilized in the glass satisfies at least one of the following characteristics: (1) The waste glass includes inorganic glass, and the components of the inorganic glass include silicon dioxide, aluminum oxide and sodium oxide; (2) The waste glass includes quartz glass; (3) The MOFs Materials include ZIF-8, ZIF-67, ZIF-9, ZIF-90, PCN-222, PCN-224, IRMOF-3, IRMOF-8, IRMOF-9, HKUST-1 / MOF-199 / CuBTC, C u-TCPP, MOF-5 / IRMOF-1, MOF-74, MOF-808, MOF-525, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MI At least one of L-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Al), UiO-66(Zr), NH2-UiO-66(Zr), UiO-66(Zr)-(OH)2, UiO-66-COOH, UiO-66-SO3H, UiO-67(Zr) and UiO-68; (4) The particle size of the glass powder is 10 mesh to 300 mesh; (5) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:200.

[0009] According to a second aspect of this application, embodiments of this application provide a method for preparing MOFs derivative materials immobilized in glass, the method comprising: We provide glass powder made from recycled glass; The MOF material is mixed with the glass powder and heated to obtain a MOF derivative material fixed in the glass.

[0010] In some embodiments, the step of obtaining MOFs derivative materials immobilized in glass includes: mixing MOFs materials with glass powder and then calcining them to obtain MOFs derivative materials immobilized in glass.

[0011] In some embodiments, the preparation method satisfies at least one of the following characteristics: (1) The mixing includes mixing by grinding with a mortar and pestle, and / or mixing by grinding with a glass tissue grinder; (2) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:40; (3) In the calcination process, the heating temperature is 600℃~1600℃ higher than the melting temperature of the glass powder; (4) In the calcination process, the heating temperature is 750℃~900℃; (5) In the calcination process, the heating time is 1h to 10h; (6) In the calcination process, the mold used includes gypsum; the preparation of the gypsum includes: mixing and stirring gypsum powder and water, and then solidifying it, wherein the ratio of gypsum powder to water is 1 g: 1 mL to 5 g: 1 mL.

[0012] In some embodiments, the step of obtaining MOFs derivative materials immobilized in glass includes: mixing MOFs materials with glass powder, and using a powder method to form glass microspheres from the MOFs derivative materials immobilized in glass.

[0013] In some embodiments, the preparation method satisfies at least one of the following characteristics: (1) The mixing includes: first sieving the glass powder to obtain glass powder of the target particle size, and then mixing the glass powder with the MOFs material evenly; (2) The particle size of the glass powder is 10 mesh to 60 mesh; (3) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:200; (4) The powder method includes: heating a mixture of MOFs material and glass powder to melt the glass powder, and forming glass microspheres with MOFs material attached to the surface under the action of surface tension; (5) In the powder method, the heating temperature is 600℃~1600℃ higher than the melting temperature of glass powder; (6) In the powder method, the heating temperature is 750℃~900℃; (7) In the powder method, the blowing device used is an air nozzle.

[0014] In some embodiments, the step of obtaining MOFs derivative materials immobilized in glass includes: mixing MOFs materials with glass powder, and using a melt method to form glass microspheres from the MOFs derivative materials immobilized in glass.

[0015] In some embodiments, the preparation method satisfies at least one of the following characteristics: (1) The melt method includes: calcining a mixture of MOFs material and glass powder to melt it into glass liquid, and then spraying the glass liquid with air to form glass microspheres; (2) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:200; (3) In the melt method, the calcination temperature is 600℃~1600℃ higher than the melting temperature of glass powder; (4) In the melt method, the calcination temperature is 750℃~900℃; (5) In the melt method, the blowing pressure is 0.5MPa to 3MPa; (6) In the melt method, the flow rate of the blow-spray is 5 kg / min to 20 kg / min.

[0016] According to a third aspect of this application, embodiments of this application provide an application of a MOFs derivative material immobilized in glass, wherein the MOFs derivative material immobilized in glass includes the MOFs derivative material immobilized in glass described above, and / or the MOFs derivative material immobilized in glass prepared by the preparation method described above; the application includes at least one of the following uses: (1) Used for the adsorption and removal of pollutants in water; (2) Used for the catalytic removal of pollutants in water; (3) Used for gas adsorption and storage.

[0017] In some embodiments, the catalytic removal of pollutants in water includes at least one of: catalytic degradation of organic pollutants in water, degradation of organic pollutants in water based on activated hydrogen peroxide, degradation of organic pollutants in water based on activated persulfate, or degradation of organic pollutants in water based on activated ozone.

[0018] Implementing the technical solution of the present invention has at least the following beneficial effects: In this embodiment, the provided MOFs derivative material immobilized in glass includes glass powder and MOFs material loaded on the glass powder. The glass powder is made from waste glass. This MOFs derivative material immobilized in glass is mainly obtained by mixing the MOFs material with the glass powder made from waste glass and calcining it at high temperature. Thus, this invention cleverly utilizes the melting properties of glass to immobilize MOFs material within the glass, with the glass acting as an effective carrier to encapsulate the MOFs, resulting in a MOFs derivative material immobilized in glass. This improves the degradation performance of the MOFs material while enhancing its stability. Furthermore, this method macroscopically scales up micron- or nano-sized MOFs materials, improving their recyclability and enabling MOFs-based environmental functional materials to perform effectively in larger-scale practical water treatment projects, accelerating their transition from theoretical research to industrial application.

[0019] The method for preparing MOF derivative materials immobilized in glass according to the present invention is simple, easy to implement, requires no complex equipment or harsh reaction conditions, and is suitable for large-scale industrial production.

[0020] The MOFs derivative materials immobilized in glass according to the present invention have wide applications in the fields of water pollutant removal, gas adsorption and storage, and especially demonstrate superior performance in the catalytic degradation of pollutants. Furthermore, experimental verification shows that the catalytic activity of the MOFs derivative materials immobilized in glass does not significantly decrease during multiple cycles of use, and efficient recovery can be achieved through simple physical separation and filtration methods, resulting in low consumable consumption and significantly reducing the cost and resource consumption of environmental pollution control. This demonstrates high feasibility and broad application prospects in practical applications. Attached Figure Description

[0021] Figure 1 A schematic diagram illustrating a method for preparing MOFs derivative materials fixed in glass, as provided in some exemplary embodiments of the present invention.

[0022] Figure 2 This is a schematic microscopic photograph of the MOFs derivative material fixed in glass obtained in Example 1 of the present invention.

[0023] Figure 3 This is a scanning electron microscope (SEM) schematic diagram of the MOFs derivative material fixed in glass obtained in Example 1 of the present invention.

[0024] Figure 4 This is a schematic diagram of the powder X-ray diffraction analysis results of the MOFs derivative material fixed in glass obtained in Example 1 of the present invention.

[0025] Figure 5 This is a schematic diagram comparing the infrared spectra of the MOFs derivative material fixed in glass obtained in Example 1 of the present invention with those of ZIF-67(Co).

[0026] Figure 6 This is a partial EDS elemental distribution diagram of the MOFs derivative material fixed in glass obtained in Example 2 of the present invention.

[0027] Figure 7 This is a schematic diagram comparing the MOFs derivative materials immobilized in glass prepared by different proportions of the materials of the present invention, such as those in Examples 3-7, with ZIF-67(Co) and PMS alone to catalyze the degradation of ciprofloxacin, as well as the dissolution of metal ions in each material.

[0028] Figure 8 This is a schematic diagram comparing MOF derivative materials immobilized in glass prepared with different proportions of materials of the present invention, such as those in Examples 9-13, with ZIF-8 (Zn) and PMS alone catalyzing the degradation of ciprofloxacin.

[0029] Figure 9A comparison of UV-Vis diffuse reflectance experimental data of a MOFs derivative material fixed in glass, i.e., a MOFs derivative material fixed in glass, glass, and ZIF-67(Co) provided for embodiments of the present invention.

[0030] Figure 10 This is a scanning electron microscope (SEM) image of a MOFs derivative material fixed in glass, provided as an embodiment of the present invention, that is, a MOFs derivative material fixed in glass after melting and quenching in a glass:MOFs ratio of 40:1.

[0031] Figure 11 This is a scanning electron microscope (SEM) image of a cross-section of a glass filament after being melted and quenched in a glass:MOFs ratio of 40:1, according to an embodiment of the present invention. Detailed Implementation

[0032] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply.

[0033] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the ranges, the endpoint values ​​of the ranges or individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges.

[0034] It should be noted that the terms "and / or" or " / " used herein are merely descriptions of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. The singular forms "a," "the," and "the" used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0035] In the description of this application, the list of items connected by the terms "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single element or multiple elements. Item B may contain a single element or multiple elements. Item C may contain a single element or multiple elements.

[0036] As mentioned in the background section, existing MOF materials and their loading methods or supports still have some defects. For example, some MOF materials cannot achieve good adhesion to the support and are prone to detachment in complex environments. In addition, MOFs are mostly nano / micron-sized powders, which can easily lead to pipe blockage or material loss in practical applications. Furthermore, powdered materials are difficult to recycle in water treatment processes, are easily dispersed, and have unstable properties. Most MOF materials contain heavy metal ions, which may cause secondary pollution. Therefore, there is still a need for improvement.

[0037] Based on this, the technical solution of this application provides a MOFs derivative material immobilized in glass, its preparation method, and its application. This material is a MOFs derivative material immobilized in glass, which can be applied in the field of environmental pollution control, such as in the field of catalysis, and further in the catalytic degradation of pollutants. It can alleviate the technical problems of unstable performance, high leaching of heavy metal ions, and difficulty in recovery of existing MOFs materials, and can effectively overcome the shortcomings of the above-mentioned related technologies. A detailed description of the technical solution is provided below.

[0038] Unless otherwise stated, percentages, proportions or parts referred to herein are by mass.

[0039] In some embodiments of this application, a MOFs derivative material fixed in glass is provided, the MOFs derivative material fixed in glass comprising glass powder and MOFs material loaded on the glass powder, the glass powder comprising glass powder made from waste glass.

[0040] Metal-organic frameworks (MOFs) are an emerging type of functional material. Their large specific surface area, abundant active sites, and tunable structure make them widely applicable in adsorption, catalysis, sensing, drug delivery, and energy. This invention loads MOF materials onto glass, specifically glass powder made from waste glass. On one hand, combining waste glass powder with MOF materials transforms waste into valuable resources, improving environmental benefits, conserving resources, and ensuring safety and sustainability. Furthermore, waste glass is widely available and inexpensive, which helps reduce the production cost of MOF derivatives fixed in glass, enhancing product market competitiveness. On the other hand, the glass powder from waste glass possesses good chemical stability and excellent mechanical properties, improving interfacial bonding and alleviating problems associated with existing loading carriers such as copper foam, resin, and perlite, including difficulty in controlling loading, uneven interfacial forces, poor adhesion, easy detachment, and reduced service life.

[0041] Therefore, the material provided by this invention is a MOFs derivative material fixed in glass. Utilizing the melting properties of glass, it cleverly fixes MOFs within the glass, making the glass an effective carrier to encapsulate the MOFs. This enhances both the degradation performance and stability of the MOFs material. Furthermore, this invention can macroscopically scale up micron- or nano-sized MOFs materials, improving their recyclability. Based on this characteristic, MOFs materials hold promise for achieving stable and continuous degradation and removal of various pollutants in wastewater, and are expected to serve as effective catalysts in small- to medium-sized wastewater pretreatment or advanced treatment equipment.

[0042] In some embodiments, the MOFs derivative material immobilized in glass is mainly obtained by mixing MOFs powder with glass powder made from waste glass and heating it. For example, the heating can be high-temperature calcination, thus, the MOFs derivative material immobilized in glass is obtained by immobilizing MOFs powder in waste glass through high-temperature calcination.

[0043] It should be understood that the high-temperature calcination temperature needs to be selected and set according to the temperature of the glass, such as the high-temperature calcination temperature needing to be higher than the melting temperature of the glass.

[0044] The method for preparing MOFs derivative materials immobilized in glass provided by this invention is simple. Utilizing the unique melting and cooling solidification capabilities of glass, it enables the immobilization of MOFs materials with poor stability and small particle size without complex high-temperature processes, thus achieving efficient material preparation. This innovative method, with its efficient preparation process, not only significantly reduces the cost of MOFs-supported catalysts in terms of manpower, reagents, and time, but also enhances the environmental friendliness of the preparation process through green and environmentally friendly methods. Simultaneously, the structure and performance of the MOFs derivative catalyst immobilized in glass are optimized, effectively improving its compatibility with fixed-bed reactors. This breaks through the technical bottleneck in practical applications, enabling MOFs-based environmental functional materials to exert their effectiveness in larger-scale practical water treatment projects, accelerating their transition from theoretical research to industrial application.

[0045] The MOF derivatives provided by this invention exhibit superior performance in catalytic degradation of pollutants. Furthermore, the preparation method of this invention is simple, requiring no complex equipment or harsh reaction conditions, making it suitable for large-scale industrial production. Testing has verified that the catalytic activity of these MOF derivative materials does not significantly decrease during multiple cycles of use, and they can be efficiently recovered using simple physical separation and filtration methods, resulting in low material consumption and significantly reducing the cost and resource consumption of environmental pollution control. This demonstrates high feasibility and broad application prospects in practical applications.

[0046] In this embodiment of the application, waste glass may include inorganic glass, the components of which include silicon dioxide, aluminum oxide and sodium oxide.

[0047] Optionally, the waste glass can be obtained in a variety of ways. For example, the waste glass can be obtained from laboratory waste glass, building lighting, partition, decorative glass, and everyday glass cups, etc. Of course, other acquisition methods can also be used, and there are no restrictions on this.

[0048] In some embodiments, the waste glass includes quartz glass. For example, the waste glass may be quartz glass discarded from a laboratory.

[0049] Quartz glass is an inorganic glass whose main component (usually >99%) is silicon dioxide. It has excellent mechanical and chemical properties, which helps to improve the stability of materials. Moreover, it is widely available and easy to obtain.

[0050] In the embodiments of this application, the MOFs material immobilized in glass can be selected from MOFs powder materials that are easy to synthesize in large quantities and have good performance, or from metal-organic framework powder materials that possess catalytic and / or adsorption properties. As an example, in some embodiments, the MOFs material includes, but is not limited to, any one or a combination of at least two of Zn-based MOFs, Cu-based MOFs, Co-based MOFs, or Ag-based MOFs.

[0051] Preferably, in some embodiments, the MOF materials include, but are not limited to, ZIF-8, ZIF-67, ZIF-9, ZIF-90, PCN-222, PCN-224, IRMOF-3, IRMOF-8, IRMOF-9, HKUST-1 / MOF-199 / CuBTC, Cu-TCPP, MOF-5 / IRMOF-1, MOF-74, MOF-808, MOF-525, MIL-53 (Cr / Al / Fe), MIL-100 (Fe / Cr), and MIL-101 (Fe / The following are any one or a combination of at least two of the following: Cr), MIL-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Al), UiO-66(Zr), NH2-UiO-66(Zr), UiO-66(Zr)-(OH)2, UiO-66-COOH, UiO-66-SO3H, UiO-67(Zr) and UiO-68.

[0052] More preferably, in some embodiments, the MOFs material includes any one or a combination of at least two of ZIF-8, ZIF-67, ZIF-9, ZIF-90, MIL-53 (Cr / Al / Fe), MIL-100 (Fe / Cr), MIL-101 (Fe / Cr), MIL-125 (Ti), MIL-88A (Fe), MIL-88B (Fe), NH2-MIL-125 (Ti), NH2-MIL-88B (Fe), and NH2-MIL-53 (Al).

[0053] As an example, the MOF material is selected from ZIF-67(Co), and ZIF-67(Co) is loaded onto glass powder, such as... Figure 9As shown, compared to ZIF-67(Co) and glass itself, the ZIF-67(Co) derivative material fixed to glass exhibits significant absorbance over a wider wavelength range. This indicates that the ZIF-67(Co) derivative material fixed to glass can absorb light of more different wavelengths, making it more widely applicable in optical utilization. Furthermore, in certain wavelength ranges, such as 500nm–700nm, the absorbance of the ZIF-67(Co) derivative material fixed to glass is higher than that of glass and ZIF-67(Co) itself, indicating its stronger absorption capacity for this portion of visible light. The absorption peak positions of the ZIF-67(Co) derivative material fixed to glass differ from those of ZIF-67(Co), indicating differences in their optical properties. The altered absorption characteristics of the ZIF-67(Co) derivative material fixed to glass may provide unique advantages in certain specific applications. For example, in the field of optical sensors, specific absorption peak positions can be used to more accurately detect light signals of specific wavelengths.

[0054] This demonstrates that combining the aforementioned MOF materials with glass powder enables the absorption of light of more different wavelengths, altering its absorption characteristics, broadening its application range, and enhancing its performance. Furthermore, this MOF derivative material immobilized in glass exhibits excellent recyclability and reuse capabilities, making it suitable for applications in water treatment.

[0055] Alternatively, MOF materials such as ZIF-8 and ZIF-67(Co) can be prepared using a room temperature stirring method. The room temperature stirring method for preparing ZIF-8, ZIF-67(Co) and other materials offers mild synthesis conditions, is environmentally friendly, and is easy to operate, requiring no high-temperature, high-pressure containers or equipment.

[0056] It should be noted that this application does not limit the source or preparation of MOFs materials such as ZIF-8 and ZIF-67(Co). They can be prepared by conventional methods known to those skilled in the art, or they can be obtained commercially.

[0057] In some embodiments, the particle size of the glass powder is 10 mesh to 300 mesh, for example, it can be 10 mesh, 20 mesh, 40 mesh, 200 mesh, 220 mesh, 240 mesh, 250 mesh, 260 mesh, 280 mesh, 300 mesh, etc.

[0058] In this embodiment, the glass particles in the MOFs derivative material immobilized in glass are selected from glass powder with a particle size of 10 to 300 mesh. Within this particle size range, the immobilization morphology of the material can be effectively controlled. For example, when preparing the material by powder method, considering the adhesion of the material, glass powder with a particle size of 10 to 40 mesh can be selected. When calcining by melt method or muffle furnace, the particle size can be controlled to a fine particle size so that the glass powder and MOFs material are mixed more uniformly. It should not be too small to avoid excessive sintering in the subsequent heat treatment process, thereby maintaining the porous structure of the material and the effective exposure of active sites, ensuring that it has good mass transfer efficiency and reactivity in practical applications.

[0059] In some embodiments, the mass ratio of MOFs material to glass powder is 4:1 to 1:200. Controlling the ratio of MOFs material to glass powder within an appropriate range helps ensure its catalytic performance and allows the MOFs material to be better immobilized in the glass. For example, a higher MOFs ratio can be used for the catalytic degradation of pollutants in actual wastewater; the higher the MOFs ratio, the better the catalytic effect. However, it should not be too high, as a too low glass ratio will prevent the MOFs material from being properly immobilized. When the MOFs ratio decreases, the MOFs tend to exhibit their original color, such as... Figure 2 , Figure 8 As shown, it can be observed that when the glass mixing ratio increases, the material exhibits a glossy appearance. MOF materials can be made into handicrafts, which not only have aesthetic value but also demonstrate the ability to adsorb gases.

[0060] Accordingly, such as Figure 1 As shown, in some embodiments, this application also provides a method for preparing MOFs derivative materials immobilized in glass as described above, the method comprising: We provide glass powder made from recycled glass; MOF materials are mixed with glass powder and heated to obtain MOF derivative materials fixed in glass.

[0061] The method for preparing this MOF derivative material involves doping MOF powder into glass powder prepared from waste glass, and then fixing the MOF material onto the glass in a high-temperature environment, such as during calcination. The process is simple, easy to operate, and suitable for industrial-scale production.

[0062] It should be understood that the “method for preparing MOFs derivative materials fixed in glass” and the aforementioned “MOFs derivative materials fixed in glass” are based on the same inventive concept, and therefore have at least all the features and advantages of the aforementioned “MOFs derivative materials fixed in glass”, which will not be repeated here.

[0063] The MOFs derivative material immobilized in glass of the present invention is prepared by mixing MOFs materials of different mass ratios with glass powder made from waste glass, and then calcining at high temperature to form MOFs derivatives immobilized in glass. Alternatively, it can be fabricated into glass microspheres using powder or melt methods. That is, the MOFs derivative material immobilized in glass of the present invention can be in a conventional powder state or in the form of glass microspheres.

[0064] To achieve the preparation of MOFs derivative materials with different shapes fixed in glass, the preparation methods of the MOFs derivative materials fixed in glass of the present invention can be various. As an example, the preparation of the MOFs derivative materials fixed in glass can mainly include the following three methods: muffle furnace calcination method, powder method and melt method.

[0065] As an example, MOF derivative materials immobilized in glass are prepared using a muffle furnace calcination method, including the following steps: We provide glass powder made from recycled glass; MOF materials are mixed with glass powder and then calcined to obtain MOF derivative materials fixed in glass.

[0066] In this example, the MOFs derivative material immobilized in the glass is prepared by a muffle furnace calcination method. For example, the MOFs powder and glass powder are thoroughly ground and homogenized, then calcined, and cooled to room temperature before further processing. That is, the MOFs powder and glass powder are mixed in a specific ratio and then calcined to immobilize the MOFs powder on the glass, forming a MOFs derivative material immobilized in the glass.

[0067] In this muffle furnace calcination method, glass powder made from waste glass can be directly mixed with MOF materials and placed into a muffle furnace for calcination. After removal, the mixture is crushed into particles and sieved. This method is simple, easy to operate, and low in cost, but it does not involve morphology control.

[0068] Optionally, in this muffle furnace calcination method, the MOF materials and glass powder can be mixed using a mortar and pestle, and / or a glass microstructure grinder. The mortar and pestle can be made using one or both of a quartz mortar and agate mortar.

[0069] Therefore, the mixing process can be carried out using one or more of the following: a quartz mortar and pestle, an agate mortar and pestle, or a glass tissue grinder. Preferably, a glass tissue grinder is used for mixing.

[0070] Optionally, in this muffle furnace calcination method, the mass ratio of MOFs material to glass powder is 4:1 to 1:40, preferably 1:1 to 1:10, and more preferably 1:1 to 1:3; for example, it can be 4:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:8, 1:10, 1:20, 1:30, 1:40, etc. Within this mass ratio range, the synergistic effect of the two materials can be fully utilized, which is beneficial to forming a stable MOFs derivative material fixed in glass.

[0071] Optionally, in this muffle furnace calcination method, the heating temperature during the calcination process is 600℃~1600℃ higher than the melting temperature of the glass powder, preferably 600℃~1000℃ higher than the melting temperature of the glass powder, for example, it can be 600℃, 700℃, 800℃, 900℃, 1000℃, 1200℃, 1500℃, 1600℃, etc.

[0072] Optionally, in this muffle furnace calcination method, the heating temperature during the calcination process is 750℃~900℃, preferably 800℃~860℃, and more preferably 850℃; for example, it can be 750℃, 780℃, 800℃, 850℃, 900℃, etc.

[0073] Optionally, in this muffle furnace calcination method, the heating time during the calcination process is 1h to 10h, preferably 2h to 4h, and more preferably 2.5h to 3h; for example, it can be 1h, 2h, 2.5h, 3h, 3.5h, 4h, 5h, 6h, 8h, 10h, etc.

[0074] Therefore, by controlling the calcination temperature and time within the above range, the glass powder can be fully melted, allowing MOFs to be more effectively and fully fixed onto the glass, resulting in stable and high-performance MOF derivative materials fixed in the glass.

[0075] Optionally, in this muffle furnace calcination method, the mold used in the calcination process includes gypsum. Under high-temperature conditions, the glass is in a molten state. After cooling, the glass adheres to the vessel. Refractory gypsum has the advantages of being easy to clean and having good stability under high-temperature conditions. After cooling, the material can be easily separated from the vessel without affecting the calcination process. Optionally, the preparation of gypsum includes: mixing and stirring gypsum powder and water, and then solidifying it, wherein the ratio of gypsum powder to water is 1 g:1 mL to 5 g:1 mL.

[0076] In this embodiment, the gypsum is preferably refractory gypsum. The refractory gypsum is prepared by stirring gypsum powder with water, preferably deionized water. The ratio of gypsum powder to deionized water is 1 g:1 mL to 5 g:1 mL, more preferably 2 g:1 mL. After stirring, the water has a viscous texture, which is used to make molds, and the mixture is allowed to solidify before use.

[0077] As an example two, MOF derivative materials immobilized in glass are prepared using a powder method, including the following steps: We provide glass powder made from recycled glass; MOF materials are mixed with glass powder, and the MOF derivative materials fixed in the glass are made into glass microspheres using the powder method.

[0078] In this second example, the MOFs derivative material immobilized in the glass, also known as the MOFs derivative material immobilized in glass, is prepared by a powder method, that is, the material is made into glass microspheres using a powder method. For example, MOFs powder and glass powder are thoroughly ground and homogenized, sieved, and then uniformly heated at a certain temperature to make them molten, forming glass microspheres under the action of surface tension.

[0079] When preparing glass using the powder method, waste glass is washed, crushed into particles of the desired diameter, and then sieved. MOF materials are then mixed uniformly with the glass particles, followed by uniform heating to melt the glass particles. Under surface tension, this melts the MOF materials onto the glass microspheres. This powder method can produce hard glass microspheres with easily controllable sizes, such as spherical diameters. However, the production cycle is longer and the cost is higher than that of the muffle furnace calcination method.

[0080] Optionally, in this powder method, during the mixing process, the glass powder can be sieved first to obtain glass powder of the target particle size, and then the glass powder and MOFs material can be mixed uniformly. The method of uniformly mixing the glass powder and MOFs material can be similar to the aforementioned muffle furnace calcination method, such as using a mortar and pestle and / or a glass tissue grinder for mixing. The mortar and pestle can be one or both of quartz mortar and agate mortar. That is, mixing can be performed using one or more of quartz mortar, agate mortar, or a glass tissue grinder, preferably using a glass tissue grinder.

[0081] Optionally, in this powder method, the particle size of the glass powder is 10 mesh to 60 mesh, preferably 20 mesh to 40 mesh; for example, it can be 10 mesh, 20 mesh, 40 mesh, 50 mesh, 60 mesh, etc. Within this particle size range, it is beneficial to obtain glass microspheres of the required size, which is easier to operate and also helps to improve its compatibility with some reactors, making it more adaptable.

[0082] Optionally, in this powder method, the mass ratio of MOF materials to glass powder is 4:1 to 1:200, preferably 1:5 to 1:10; for example, it can be 4:1, 1:1, 1:2, 1:5, 1:6, 1:8, 1:10, 1:20, 1:50, 1:100, 1:150, 1:200, etc. Within this mass ratio range, the synergistic effect of the two materials can be fully utilized, which is beneficial to forming MOF derivative materials with stable performance fixed in glass.

[0083] In this embodiment, the powder method includes: heating a mixture of MOFs material and glass powder to melt the glass powder, and forming glass microspheres with MOFs material attached to the surface under the action of surface tension.

[0084] Optionally, in this powder method, the heating temperature is 600℃~1600℃ higher than the melting temperature of the glass powder, preferably 600℃~1000℃ higher than the melting temperature of the glass powder, for example, it can be 600℃, 700℃, 800℃, 900℃, 1000℃, 1200℃, 1500℃, 1600℃, etc.

[0085] Optionally, in this powder method, the heating temperature is 750℃~900℃, preferably 800℃~860℃, more preferably 850℃; for example, it can be 750℃, 780℃, 800℃, 850℃, 900℃, etc.

[0086] Therefore, by controlling the heating temperature within the above range, the glass powder can be fully melted, which is more conducive to the formation of glass microspheres with MOFs material attached to the surface under the action of surface tension.

[0087] Optionally, in this powder method, the blowing device used is an air nozzle.

[0088] As an example three, MOF derivative materials immobilized in glass are prepared using a melt method, including the following steps: We provide glass powder made from recycled glass; MOF materials are mixed with glass powder, and the MOF derivative materials fixed in the glass are made into glass microspheres using the melt method.

[0089] In this melt method, glass powder and MOFs are mixed and calcined in a muffle furnace to melt into molten glass. Then, a high-temperature gas stream is used to blow the molten glass, causing it to form glass microspheres due to surface tension. This melt method has lower production costs and higher output, but the sphere size is more difficult to control compared to the powder method.

[0090] Alternatively, in this melt method, the way MOFs materials are mixed with glass powder can be the same as the mixing method of the aforementioned muffle furnace calcination method or powder method, which will not be repeated here.

[0091] In this embodiment, the MOFs derivative material fixed to glass is formed into glass microspheres using a melt method, which includes: calcining a mixture of MOFs material and glass powder to melt it into molten glass, and then spraying the molten glass with a high-speed airflow to form glass microspheres. Alternatively, the provided glass powder is melted into molten glass, thoroughly mixed with MOFs material, and then sprayed with a high-speed airflow, causing the molten glass to form microspheres due to surface tension.

[0092] Optionally, in this melt method, the mass ratio of MOF materials to glass powder is 4:1 to 1:200.

[0093] Optionally, in this molten metal method, the calcination temperature is 600℃~1600℃ higher than the melting temperature of the glass powder.

[0094] Optionally, in this melt method, the calcination temperature is 750℃~900℃.

[0095] Optionally, in this melt method, the blowing pressure is 0.5 MPa to 3 MPa, preferably 0.5 MPa to 2 MPa, and more preferably 0.8 MPa; for example, it can be 0.5 MPa, 0.8 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 3.0 MPa, etc.

[0096] In this embodiment, the blowing pressure is selected from 0.5 MPa to 3 MPa. The higher the pressure, the smaller the droplet size. The blowing pressure is preferably 0.5 MPa to 2 MPa, and more preferably 0.8 MPa.

[0097] Optionally, in this molten glass method, the flow rate of the blown glass melt should be controlled between 5 kg / min and 20 kg / min, preferably between 10 kg / min and 20 kg / min, and more preferably 18 kg / min; for example, it can be 5 kg / min, 10 kg / min, 15 kg / min, 18 kg / min, 20 kg / min, etc.

[0098] Therefore, based on the above, according to the technical solution provided in the embodiments of the present invention, the preparation method of MOFs derivative materials immobilized in glass is simple. Utilizing the unique melting and cooling solidification ability of glass, MOFs materials with poor stability and small particle size can be immobilized without complex high-temperature processes, thus achieving efficient material preparation. This method, with its efficient preparation process, not only significantly reduces the cost of MOFs-supported catalysts in terms of manpower, reagents, and time, but also enhances the environmental friendliness of the preparation process through green and environmentally friendly preparation methods. Simultaneously, the structure and performance of the MOFs derivative catalyst immobilized in glass are optimized, effectively improving its compatibility with fixed-bed reactors, thereby breaking through the technical bottleneck in practical applications. This enables MOFs-based environmental functional materials to exert their effectiveness in larger-scale practical water treatment projects, accelerating their transition from theoretical research to industrial application.

[0099] Accordingly, the present invention also provides an application of MOFs derivative materials immobilized in glass, wherein the MOFs derivative materials immobilized in glass include the aforementioned MOFs derivative materials immobilized in glass, and / or MOFs derivative materials immobilized in glass prepared by the aforementioned preparation method.

[0100] The application includes at least one of the following uses: (1) for adsorption removal of pollutants in water; (2) for catalytic removal of pollutants in water; and (3) for gas adsorption and storage.

[0101] The MOFs derivative material immobilized in glass provided in this embodiment can be applied in the field of environmental pollution control or catalysis, especially in the field of water pollutant treatment. For example, the application of this MOFs derivative material immobilized in glass includes at least one of the following: adsorption and removal of pollutants in water, catalytic removal of pollutants in water, and gas adsorption and storage.

[0102] Optionally, the catalytic removal of pollutants in water includes: degradation of organic pollutants in water based on catalytic degradation of organic pollutants in water based on activated hydrogen peroxide, degradation of organic pollutants in water based on activated persulfate, degradation of organic pollutants in water based on activated ozone, or a combination of two or more of the aforementioned technologies.

[0103] In the catalytic removal of pollutants in water, through experimental comparison, appropriate amounts of catalysts and oxidants are added to degrade the pollutants.

[0104] To fully illustrate the properties of the MOFs derivative materials immobilized in glass provided in this application and to facilitate understanding of the invention, multiple sets of experiments were conducted. The invention will be further described below with reference to specific embodiments and application examples.

[0105] Example 1 A method for preparing MOF derivative materials immobilized in glass includes: (1) Provide glass powder: Take a piece of waste glass, filter out 10-mesh glass using a sieve, put the filtered glass powder into a ceramic ball mill jar for ball milling, place 30 to 40 white corundum balls of different sizes in the ball mill jar, ball mill for 60 minutes, filter out 200-mesh glass powder using a sieve, and take it out for later use.

[0106] (2) Provide MOFs material: The MOFs material is ZIF-67(Co), which is synthesized by room temperature stirring method. For example, 7 mmol of cobalt nitrate hexahydrate and 70 mmol of 2-methylimidazole are added to 150 ml of methanol solution to dissolve. After dissolution, the solutions are mixed and stirred at room temperature for 24 h to obtain ZIF-67(Co).

[0107] (3) Provide molds: Mix refractory gypsum powder and deionized water at a ratio of 2.75 g: 1 ml. Spread the refractory gypsum with a viscous texture evenly on the surface of the ceramic boat for easy demolding. Place it in an oven to dry for later use.

[0108] (4) Mixing: The ZIF-67(Co) material and glass powder are mixed in a mass ratio of 1:40 and ground in a mortar until they are evenly mixed to obtain a mixture.

[0109] (5) Calcination in a muffle furnace: The above-ground material, i.e. the mixture, is placed in a porcelain boat, spread out, and sent into a muffle furnace. The temperature is raised to 850℃ and maintained for 2.5 h. After calcination, it is cooled to room temperature and then taken out.

[0110] (6) Sieving: The material taken out after calcination is in block form and is sieved. The sieve used for sieving is 16 mesh to obtain ZIF-67(Co) derivative material fixed in glass, that is, MOFs derivative material fixed in glass.

[0111] like Figure 2 As shown, this embodiment uses ZIF-67(Co) as an example. A microscopic illustration of the MOFs derivative material immobilized in glass, prepared by firing glass powder at a mass ratio of 1:40 to ZIF-67(Co), is shown below. Figure 2 As can be seen, the material is bright blue and has a crystal-clear surface. To conduct catalytic experiments, the MOF ratio was progressively increased in the following examples.

[0112] Figure 3 The electron microscope image of the MOFs derivative material immobilized in glass prepared in this embodiment is shown, as follows: Figure 3As shown, its surface is relatively smooth, and some blocky ZIF-67(Co) can be observed in the internal cross-section.

[0113] Figure 4 The X-ray diffraction (XRD) pattern of the MOFs derivative material immobilized in glass prepared in this embodiment is shown, as follows: Figure 4 As shown, the material exhibits an amorphous, disordered morphology.

[0114] Figure 5 The image shows the powder infrared spectrum characterization of the MOFs derivative material immobilized in glass obtained in this embodiment. The obtained material was ground into powder and then subjected to infrared spectral characterization. Figure 5 As shown, and compared with ZIF-67(Co), the infrared spectral peaks corresponded well with those of ZIF-67(Co), indicating that the material retains the characteristics of ZIF-67(Co) after calcination.

[0115] Example 2 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 1, except that: In the mixing step, ZIF-67(Co) material and glass powder are mixed at a mass ratio of 2:1.

[0116] like Figure 6 As shown, the partial elemental distribution of EDS in MOFs derivative materials immobilized in glass, obtained by firing ZIF-67(Co) at a mass ratio of 2:1 to glass powder, is as follows. Figure 6 EDS is a technique that uses characteristic X-rays generated after a sample is excited to quickly analyze the elemental composition and relative content of micro-regions on the surface of a material. The elemental distribution scan clearly shows the distribution of each element in the material. C is an element present in the conductive adhesive at the bottom of the material, and Co, Si, and O are all uniformly distributed on the surface of the material.

[0117] Example 3 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 1, except that: In the mixing step, ZIF-67(Co) material and glass powder were mixed at a mass ratio of 1:2. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as M1G2.

[0118] Example 4 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 1, except that: In the mixing step, ZIF-67(Co) material and glass powder were mixed at a mass ratio of 1:1. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as M1G1.

[0119] Example 5 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 1, except that: In the mixing step, ZIF-67(Co) material and glass powder were mixed at a mass ratio of 1.5:1. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as M1.5G1.

[0120] Example 6 The preparation method of the MOFs derivative material immobilized in glass in this embodiment (i.e., Embodiment 2) is the same as that in Embodiment 1, except that: In the mixing step, ZIF-67(Co) material and glass powder were mixed at a mass ratio of 2:1. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as M2G1.

[0121] Example 7 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 1, except that: In the mixing step, ZIF-67(Co) material and glass powder were mixed at a mass ratio of 2:1.5. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as M2G1.5.

[0122] Application Example 1 The MOFs derivative materials immobilized in glass prepared in the above embodiments were subjected to catalytic experiments. For example, the MOFs derivative materials immobilized in glass prepared in Examples 3-7 were tested for the degradation of ciprofloxacin under catalytic conditions with persulfate. The specific methods are as follows: A 50.0 mL aqueous solution of ciprofloxacin with an initial concentration of 10.0 mg L⁻¹ was used. The catalytic performance of a 20 mg material was investigated in a photocatalytic reactor (PCX-50A, Beijing Pofilai Technology Co., Ltd.) under dark conditions. Degradation was completed within 4 min in the dark. During the experiment, 1.5 mL of solution was extracted from each sampling point for subsequent analysis. The residual ciprofloxacin content in the solution was determined by liquid chromatography.

[0123] Figure 7This diagram shows a comparison of the dissolution of metal ions in MOF derivatives immobilized in glass prepared with different proportions of MOF materials and glass powder, compared with the degradation of ciprofloxacin by ZIF-67(Co) and PMS alone catalyzed by persulfate (PMS), and the dissolution of metal ions in each material; where, according to the mass ratio of ZIF-67(Co) to glass powder, they are named MxGy (x=1,2; y=1,1.5,2). Figure 7 As shown, with the increase of MOF ratio, the degradation effect gradually becomes more significant, and the performance is enhanced compared with ZIF-67(Co) alone. Moreover, the dissolution of metal ions is lower than that of ZIF-67(Co) alone, indicating that the modified material enhances the stability of ZIF-67(Co).

[0124] Example 8 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 1, except that: In the MOFs material provision step, ZIF-67(Co) material is replaced with ZIF-8(Zn) material.

[0125] Example 9 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 8, except that: In the mixing step, ZIF-8 (Zn) material and glass powder were mixed at a mass ratio of 1:2. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as Z1G2.

[0126] Example 10 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 8, except that: In the mixing step, ZIF-8 (Zn) material and glass powder are mixed at a mass ratio of 1:1. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as Z1G1.

[0127] Example 11 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 8, except that: In the mixing step, ZIF-8 (Zn) material and glass powder were mixed at a mass ratio of 1.5:1. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as Z1.5G1.

[0128] Example 12 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 8, except that: In the mixing step, ZIF-8 (Zn) material and glass powder were mixed at a mass ratio of 2:1. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as Z2G1.

[0129] Example 13 The preparation method of the MOFs derivative material immobilized in glass in this embodiment is the same as that in Example 8, except that: In the mixing step, ZIF-8 (Zn) material and glass powder were mixed at a mass ratio of 2:1.5. The MOF derivative material immobilized in glass obtained in this embodiment is denoted as Z2G1.5.

[0130] Application Example 2 The MOFs derivative materials immobilized in glass obtained in the above embodiments were subjected to catalytic experiments. For example, the MOFs derivative materials immobilized in glass obtained in Examples 9-13 were tested for the degradation of ciprofloxacin under catalytic conditions with persulfate. The specific method is as follows: A 50.0 mL aqueous solution of ciprofloxacin with an initial concentration of 10.0 mg L⁻¹ was used. The catalytic performance of a 20 mg material was investigated in a photocatalytic reactor (PCX-50A, Beijing Pofilai Technology Co., Ltd.) under dark conditions. Degradation was completed within 4 min in the dark. During the experiment, 1.5 mL of solution was extracted from each sampling point for subsequent analysis. The residual ciprofloxacin content in the solution was determined by liquid chromatography.

[0131] Figure 8 This diagram shows MOFs (Metal-Oxide-Factory) materials prepared with different proportions of MOFs and glass powder. It compares MOF derivatives immobilized in glass with ZIF-8 (Zn) and PMS (persulfate monophosphate) alone in their catalytic degradation of ciprofloxacin. The materials are named ZxGy (x=1, 2; y=1, 1.5, 2) according to the mass ratio of ZIF-8 (Zn) to glass powder. Figure 8 As shown, the degradation effect becomes increasingly significant with increasing MOF ratio. Catalytic tests reveal that MOFs exhibit excellent catalytic properties. MOFs can be well immobilized in the glass, and by adding PMS oxidant, they are adsorbed onto the Zn active sites of the catalyst and activated, promoting electron transfer and thus achieving rapid oxidative degradation of pollutants. Figure 8 As shown, the degradation efficiency of ZIF-8 (Zn) added alone is significantly lower than that of the MOFs material involved in this patent, thus improving the material's practical application capability.

[0132] The embodiments of this application have been described above with reference to the accompanying drawings. However, this application is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of this application without departing from the spirit and scope of the claims, and all of these forms are within the protection scope of this application.

Claims

1. A MOFs derivative material immobilized in glass, characterized in that, The MOFs derivative material immobilized in the glass includes glass powder and MOFs material loaded on the glass powder, wherein the glass powder includes glass powder made from waste glass.

2. The MOFs derivative material immobilized in glass according to claim 1, characterized in that, The MOFs derivative material fixed in the glass is obtained by mixing MOFs powder with glass powder made from waste glass and heating it.

3. The MOFs derivative material immobilized in glass according to claim 1 or 2, characterized in that, The MOFs derivative material immobilized in the glass satisfies at least one of the following characteristics: (1) The waste glass includes inorganic glass, and the components of the inorganic glass include silicon dioxide, aluminum oxide and sodium oxide; (2) The waste glass includes quartz glass; (3) The MOFs Materials include ZIF-8, ZIF-67, ZIF-9, ZIF-90, PCN-222, PCN-224, IRMOF-3, IRMOF-8, IRMOF-9, HKUST-1 / MOF-199 / CuBTC, C u-TCPP, MOF-5 / IRMOF-1, MOF-74, MOF-808, MOF-525, MIL-53(Cr / Al / Fe), MIL-100(Fe / Cr), MIL-101(Fe / Cr), MI At least one of L-125(Ti), MIL-88A(Fe), MIL-88B(Fe), MIL-68(Al / Fe), NH2-MIL-125(Ti), NH2-MIL-88B(Fe), NH2-MIL-53(Al), UiO-66(Zr), NH2-UiO-66(Zr), UiO-66(Zr)-(OH)2, UiO-66-COOH, UiO-66-SO3H, UiO-67(Zr) and UiO-68; (4) The particle size of the glass powder is 10 mesh to 300 mesh; (5) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:

200.

4. A method for preparing MOFs derivative materials immobilized in glass, characterized in that, The method includes: We provide glass powder made from recycled glass; The MOF material is mixed with the glass powder and heated to obtain a MOF derivative material fixed in the glass.

5. The method for preparing MOFs derivative materials immobilized in glass according to claim 4, characterized in that, The steps for obtaining MOF derivative materials immobilized in glass include: MOF materials are mixed with glass powder and then calcined to obtain MOF derivative materials fixed in glass.

6. The method for preparing MOFs derivative materials immobilized in glass according to claim 5, characterized in that, The preparation method satisfies at least one of the following characteristics: (1) The mixing includes mixing by grinding with a mortar and pestle, and / or mixing by grinding with a glass tissue grinder; (2) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:40; (3) In the calcination process, the heating temperature is 600℃~1600℃ higher than the melting temperature of the glass powder; (4) In the calcination process, the heating temperature is 750℃~900℃; (5) In the calcination process, the heating time is 1h to 10h; (6) The mold used in the calcination process includes gypsum; The preparation of the gypsum includes: mixing and stirring gypsum powder and water, and then solidifying it, wherein the ratio of gypsum powder to water is 1 g: 1 mL to 5 g: 1 mL.

7. The method for preparing MOFs derivative materials immobilized in glass according to claim 4, characterized in that, The steps for obtaining MOF derivative materials immobilized in glass include: MOF materials are mixed with glass powder, and the MOF derivative materials fixed in the glass are made into glass microspheres using the powder method.

8. The method for preparing MOFs derivative materials immobilized in glass according to claim 7, characterized in that, The preparation method satisfies at least one of the following characteristics: (1) The mixing includes: first sieving the glass powder to obtain glass powder of the target particle size, and then mixing the glass powder with the MOFs material evenly; (2) The particle size of the glass powder is 10 mesh to 60 mesh; (3) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:200; (4) The powder method includes: heating a mixture of MOFs material and glass powder to melt the glass powder and forming glass microspheres with MOFs material attached to the surface under the action of surface tension; (5) In the powder method, the heating temperature is 600℃~1600℃ higher than the melting temperature of glass powder; (6) In the powder method, the heating temperature is 750℃~900℃; (7) In the powder method, the blowing device used is an air nozzle.

9. The method for preparing MOFs derivative materials immobilized in glass according to claim 4, characterized in that, The steps for obtaining MOF derivative materials immobilized in glass include: MOF materials are mixed with glass powder, and the MOF derivative materials fixed in the glass are made into glass microspheres by the melt method. The preparation method satisfies at least one of the following characteristics: (1) The melt method includes: calcining a mixture of MOFs material and glass powder to melt it into glass liquid, and spraying the glass liquid with high-speed airflow to form glass microspheres; (2) The mass ratio of the MOFs material to the glass powder is 4:1 to 1:200; (3) In the melt method, the calcination temperature is 600℃~1600℃ higher than the melting temperature of glass powder; (4) In the melt method, the calcination temperature is 600℃~1600℃; (5) In the melt method, the blowing pressure is 0.5MPa to 3MPa; (6) In the melt method, the flow rate of the blow-spray is 5 kg / min to 20 kg / min.

10. An application of a MOFs derivative material immobilized in glass, characterized in that, The MOFs derivative material immobilized in glass includes the MOFs derivative material immobilized in glass according to any one of claims 1 to 3, and / or the MOFs derivative material immobilized in glass prepared by the preparation method according to any one of claims 4 to 9; The application includes at least one of the following uses: (1) Used for the adsorption and removal of pollutants in water; (2) Used for the catalytic removal of pollutants in water; (3) Used for gas adsorption and storage; The catalytic removal of pollutants in water includes at least one of the following: catalytic degradation of organic pollutants in water, degradation of organic pollutants in water based on activated hydrogen peroxide, degradation of organic pollutants in water based on activated persulfate, or degradation of organic pollutants in water based on activated ozone.

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