CN114672034A - Method for preparing MOFs material by thermally-assisted mechanical ball milling method - Google Patents
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- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Health & Medical Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing MOFs material by a heat-assisted mechanical ball milling method, which comprises the steps of mixing metal salt, metal oxide or metal hydroxide and an organic ligand according to the molar ratio of 1:1-1:10 to obtain a mixture; the mixture is put into a ball milling tank of a ball mill according to the ball-to-material ratio of 5:1-40:1, and is subjected to ball milling reaction for 0.5-36h at the temperature of 50-600 ℃ according to the heating rate of 5 ℃/min; and cooling to room temperature, taking out the reacted substances, and washing and drying the reacted substances to obtain the MOFs material. The method for preparing the MOFs material by the heat-assisted mechanical ball milling method is simple, efficient, green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a method for preparing MOFs material by a heat-assisted mechanical ball milling method.
Background
Metal organic framework Materials (MOFs) have attracted special attention because of their excellent properties such as high porosity, high specific surface area, diversity, good designability, and the ability to modify metal centers or organic ligands on the MOFs as needed to adjust their chemical versatility. To date, a great deal of research shows that the MOFs material has high potential in the aspects of catalysis, gas adsorption, drug delivery, water treatment, energy storage, sensing, electrochemistry and the like.
For the research and application of MOFs, the ideal synthesis method should have at least one of the following elements, namely, the ability to produce single crystal, phase-pure single crystal or microcrystal (powder) products of appropriate size; the operation is simple, the repetition is easy, the yield is high, and the large-scale synthesis can be realized; good atomic economy and environmental protection. The main synthesis methods of the MOFs material include common solution reaction, a water (solvent) thermal method (including microwave-assisted heating), a diffusion method, a mechanochemical method and the like.
The water (solvent) thermal method is the most common method for preparing the MOFs at present, but has the defects of large organic reagent dosage, large pollution, low efficiency, complexity, poor economy and the like. Mechanochemistry is an efficient and environment-friendly alternative method for preparing various MOFs materials, and comprises the preparation of MOFs materials with the most popular structures such as MOF-5, ZIF-8, HKUST-1, MIL-101, UiO-66 and the like. The MOFs material prepared by the mechanochemical method has higher specific surface area and can be synthesized into multi-metal MOFs materials.
However, the MOFs material prepared by the current mechanochemical method mostly adopts metal salts, the metal salts are expensive and are easy to introduce impurities, the requirement of a product with higher purity cannot be met, and particularly, Cl element can form coordination in the process of forming a coordination compound by metal chloride, so that the product purity is influenced. In addition, the method adopts metal oxides, hydroxides, certain stable metal salts (carbonates) and the like as metal ions to introduce precursors, and has the defects of long synthesis time or difficult synthesis and the like in the synthesis of the MOFs material, thereby limiting the large-scale production of the MOFs material. Therefore, a simple, efficient, green and environment-friendly method for synthesizing various MOFs materials is needed.
Disclosure of Invention
The invention aims to provide a simple, efficient, green and environment-friendly method for preparing MOFs materials by a heat-assisted mechanical ball milling method.
In order to solve the technical problem, the invention provides a method for preparing MOFs material by a heat-assisted mechanical ball milling method, which comprises the following steps:
mixing metal salts, metal oxides or metal hydroxides with an organic ligand according to a molar ratio of 1:1-1:10 to obtain a mixture;
the mixture is put into a ball milling tank of a ball mill according to the ball-to-material ratio of 5:1-40:1, and is subjected to ball milling reaction for 0.5-36h at the temperature of 50-600 ℃ according to the heating rate of 5 ℃/min;
and cooling to room temperature, taking out the reacted substances, and washing and drying the reacted substances to obtain the MOFs material.
Further, for metal salts with good solubility, the metal salts are dissolved in deionized water or absolute ethyl alcohol to form a solution, then organic ligands are added into the solution, and the mixture is uniformly mixed and evaporated to dryness at the temperature of 80-100 ℃ to obtain a mixture.
Further, the metal in the metal salts, metal oxides and metal hydroxides is one or more of Mn, Fe, Co, Ni, Cu, Zn, Ag, Al, Cr, Zr, Ti, V, Mo, Sr, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Sc.
Further, the organic ligand is a carboxylic acid or pyridine ligand which is solid at normal temperature.
Further, the washing of the reacted substance is carried out by washing with N, N-dimethylformamide or methanol and the like according to the solubility of the unreacted organic ligand contained in the reacted substance, and then washing with ethanol or deionized water, wherein the washing times are respectively 1-4 times.
Further, the drying of the reacted substance is to carry out drying at the temperature of 50-150 ℃ under the air or vacuum condition according to the stability of the prepared MOFs material.
Further, the ball milling tank of the ball mill is a stainless steel tank, a zirconia tank or a corundum tank, and the milling balls of the ball mill are stainless steel balls or zirconia balls.
Furthermore, the diameters of the grinding balls of the ball mill are respectively 16mm, 12mm and 8mm, and the mass ratio of the grinding balls with the diameters of 16mm, 12mm and 8mm is 2:1: 1.
Further, the rotation speed of the ball mill is set to 50-100 rpm.
Furthermore, the MOFs material comprises ZIFs, IRMOFs, MILs, UiOs, single metal or/and multi-metal organic framework materials of Ni, Cu and rare earth and doped compounds thereof.
The invention provides a method for preparing MOFs material by a heat-assisted mechanical ball milling method, which comprises the steps of mixing one or more metal salts, metal oxides or/and metal hydroxides of metals such as Mn, Fe, Co, Ni, Cu, Zn, Ag, Al, Cr, Zr, Ti, V, Mo, Sr, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and the like with organic ligands such as carboxylic acids or pyridines and the like which are solid at normal temperature according to a set molar ratio, promoting the proceeding of coordination reaction by adopting a heating-assisted and mechanical ball milling method, enabling the metal oxides, metal hydroxides or/and metal salts with low solubility to be used as precursors for preparing the MOFs material, and finally preparing the MOFs material by controlling the ball-to-material ratio, the ball milling temperature, the ball milling time and the rotating speed of a ball mill, wherein the materials comprise ZIFs, IRMOFs, MILs and Sc, UiOs, single metal or multi-metal organic framework materials such as Ni, Cu, rare earth metals and the like, and MOFs materials such as doped composites thereof. The method has the advantages of high yield of MOFs materials, no need of adding an organic solvent in the preparation process, environmental friendliness, rapidness, high efficiency, low cost, large-scale preparation and the like, and is suitable for industrial production.
Drawings
FIG. 1 is a flowchart of a method for preparing MOFs material by a thermally assisted mechanical ball milling method according to an embodiment of the present invention;
FIG. 2 is a comparison diagram of XRD patterns of a target product and a simulated product, which are prepared by the method for preparing MOFs material by using the heat-assisted mechanical ball milling method provided by embodiment 1 of the present invention;
FIG. 3 is a comparison diagram of XRD patterns of a target product and a simulated product, which are prepared by the method for preparing MOFs material by using the heat-assisted mechanical ball milling method provided in embodiment 2 of the present invention;
FIG. 4 is a comparison diagram of XRD spectra of a target product and a simulated product prepared by the method for preparing MOFs material by using a thermally assisted mechanical ball milling method provided in embodiment 3 of the present invention;
FIG. 5 is a comparison diagram of XRD spectra of a target product and a simulated product obtained by the method for preparing MOFs material by using a thermally assisted mechanical ball milling method provided in embodiment 4 of the present invention;
FIG. 6 is a comparison diagram of XRD spectra of a target product and a simulated product obtained by the method for preparing MOFs material by using a thermally assisted mechanical ball milling method provided in embodiment 5 of the present invention;
fig. 7 is a comparison diagram of XRD spectra of the target product and the simulated product prepared by the method for preparing the MOFs material by the heat-assisted mechanical ball milling method provided in embodiment 6 of the present invention.
Detailed Description
Referring to fig. 1, a method for preparing MOFs materials by using a thermally assisted mechanical ball milling method according to an embodiment of the present invention includes the following steps:
Step 1) mixing metal salts, metal oxides or metal hydroxides with organic ligands according to a molar ratio of 1:1-1:10 to obtain a mixture. Wherein, the metal in the metal salt, metal oxide and metal hydroxide is one or more of Mn, Fe, Co, Ni, Cu, Zn, Ag, Al, Cr, Zr, Ti, V, Mo, Sr, Cd and lanthanide rare earth elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Sc). The organic ligand is solid organic ligand such as carboxylic acid or pyridine at normal temperature.
And 2) putting the mixture into a ball milling tank of a ball mill according to a ball-to-material ratio of 5:1-40:1, in order to prevent the organic ligand in the mixture from being decomposed at high temperature, in the reaction process, firstly heating the temperature of the ball milling tank to 50-600 ℃ according to a heating rate of 5 ℃/min, and then carrying out ball milling reaction on the mixture at the temperature for 0.5-36 h. The ball milling tank of the ball mill can be made of stainless steel, zirconia or corundum, and the grinding balls in the ball mill can be made of stainless steel balls or zirconia balls. And the grinding balls are three grinding balls with the diameters of 16mm, 12mm and 8mm respectively, and the mass ratio of the grinding balls with the three diameters added into the ball milling tank is 2:1: 1. Meanwhile, the rotating speed of a ball milling tank in the ball mill is set to be 50-100rpm in the ball milling reaction process.
And 3) stopping the ball mill after the reaction is finished, naturally cooling to room temperature, taking out the reacted substances in the ball mill tank, and washing and drying the reacted substances to obtain the MOFs material. In order to improve the purity of the MOFs material finally prepared, when the reacted material is washed, the unreacted organic ligand can be washed by N, N-dimethylformamide or methanol according to the solubility of the unreacted organic ligand in a washing solvent, so as to remove the organic ligand in the reacted material, and then the reacted material is washed by ethanol or deionized water, so as to remove other impurities in the reacted material. In order to effectively wash away impurities in reacted substances, according to different raw materials for preparing the MOFs material, the reacted substances can be washed for 1-4 times respectively by washing twice. And drying the MOFs material after washing is finished, wherein drying is carried out under the air or vacuum condition according to different stability of the prepared MOFs material in order to fully activate the obtained MOFs material, and the drying temperature is 50-150 ℃.
Some metal salts in the metal salts, such as metal carbonate, have weak solubility, and the metal oxides and metal hydroxides have weak solubility, and the carbonates, metal oxides and metal hydroxides with poor solubility are directly mixed with organic ligands according to a set molar ratio to obtain a mixture, and then subsequent processes are carried out according to the step 2) and the step 3), so as to finally obtain the single-metal or/and multi-metal organic framework materials containing ZIFs, IRMOFs, MILs, UiOs, Ni, Cu and rare earth and the MOFs material of the doped compound thereof.
As a specific implementation process of the invention, for metal salts with good solubility, in order to enable the metal salts and the organic ligands to be mixed more uniformly, the metal salts can be firstly dissolved in deionized water or absolute ethyl alcohol to form a solution, then the organic ligands are added into the solution, and the mixture is uniformly mixed and evaporated to dryness at the temperature of 80-100 ℃ to obtain a mixture. And then carrying out subsequent process according to the step 2) and the step 3), and finally obtaining the MOFs material comprising the ZIFs, the IRMOFs, the MILs and the UiOs as well as the single metal or/and multi-metal organic framework materials of Ni, Cu and rare earth and doped compounds thereof.
The method for preparing MOFs material by the heat-assisted mechanical ball milling method provided by the invention is specifically described by the following embodiments.
Example 1
Preparation of Metal organic framework Material MIL-53(Fe)
56.76g of FeCl are taken3·6H2And O, stirring and dissolving in 200mL of absolute ethanol, dissolving in hot ethanol in an accelerating manner, then adding 34.64g of terephthalic acid, stirring uniformly, and evaporating ethanol to dryness at 90 ℃ to obtain a mixed material. Putting the mixed material into a stainless steel tank with the volume of 2L, respectively adding 1000g, 500g and 500g of steel balls with the diameters of 16mm, 12mm and 8mm, and sealing at the ball-material ratio of 25: 1.
Setting the heating rate to be 5 ℃/min, the heat preservation temperature to be 300 ℃, the heat preservation time to be 6h, the rotating speed to be 60rpm and starting the program. After the reaction is finished and the temperature is cooled to room temperature, taking out the reaction product, respectively washing the reaction product once by using N, N-Dimethylformamide (DMF), washing the reaction product twice by using anhydrous hot ethanol and washing the reaction product twice by using deionized water. And finally, drying for 8 hours at 120 ℃ in vacuum to finally obtain the target product metal organic framework material MIL-53 (Fe). FIG. 2 is a comparison of XRD patterns of ball-milled as-synthesized MIL-53(Fe) and simulated MIL-53 (Fe). As can be seen from FIG. 2, the MIL-53(Fe) produced in this example substantially completely matched the simulated MIL-53(Fe), indicating that the crystals produced in the examples of the present invention were pure MIL-53 (Fe).
Example 2
Preparation of Metal organic framework Material MIL-88A (Fe)
Taking 43.41g FeOOH, then adding 56.59g fumaric acid, mixing uniformly, loading the mixture into a stainless steel tank with the volume of 2L, respectively adding 1000g, 500g and 500g of steel balls with the diameters of 16mm, 12mm and 8mm, and sealing at the ball-to-material ratio of 20: 1.
Setting the heating rate at 5 ℃/min, the heat preservation temperature at 250 ℃, the heat preservation time at 5h, the rotating speed at 60rpm and starting the program. After the reaction is finished and the temperature is cooled to room temperature, taking out the reaction product, and drying the reaction product in vacuum at 80 ℃ for 8h to obtain the product MIL-88A (Fe). FIG. 3 is a comparison of XRD patterns of ball-milled synthesized MIL-88A (Fe) and simulated MIL-88A (Fe). As can be seen from FIG. 3, the MIL-88A (Fe) produced in this example is substantially a perfect match with the simulated MIL-88A (Fe), indicating that the crystals produced in this example are pure MIL-88A (Fe).
Example 3
Preparation of Metal organic framework Material UiO-66(Zr)
58.40g of ZrCl were taken4Stirring and dissolving in 200mL of absolute ethyl alcohol, dissolving in hot ethyl alcohol in an accelerating manner, then adding 41.60g of terephthalic acid, stirring uniformly, and evaporating the ethyl alcohol to dryness at 90 ℃ to obtain a mixed material. Putting the mixed material into a stainless steel tank with the volume of 2L, respectively adding 1000g, 500g and 500g of steel balls with the diameters of 16mm, 12mm and 8mm, and sealing at the ball-material ratio of 20: 1.
Setting the heating rate at 5 ℃/min, the heat preservation temperature at 300 ℃, the heat preservation time at 5h, the rotating speed at 60rpm and starting the program. After the reaction is finished and the temperature is cooled to room temperature, taking out reaction products, respectively washing the reaction products once by DMF, twice by anhydrous hot ethanol and twice by deionized water, and finally drying the reaction products for 8 hours in vacuum at 120 ℃ to obtain the product UiO-66 (Zr). FIG. 4 is a comparison of XRD patterns of ball-milled synthesized UiO-66(Zr) and simulated UiO-66 (Zr). As can be seen from FIG. 4, the UiO-66(Zr) produced in this example is substantially matched with the simulated UiO-66(Zr), indicating that the crystal produced in this example is pure UiO-66 (Zr).
Example 4
Preparation of metal organic framework material ZIF-8
14.84g of ZnO and 35.16g of dimethyl imidazole are taken, uniformly ground, the mixture is put into a stainless steel tank, the volume of the tank is 2L, 1000g, 500g and 500g of steel balls with the diameters of 16mm, 12mm and 8mm are respectively added, the ball-to-material ratio is 40:1, and finally the stainless steel tank is sealed.
Setting the heating rate to be 5 ℃/min, the heat preservation temperature to be 180 ℃, the heat preservation time to be 3h, the rotating speed to be 60rpm and starting the program. After the reaction is finished and the temperature is cooled to room temperature, taking out a reaction product, respectively washing the reaction product twice by using methanol and twice by using deionized water, and finally drying the reaction product for 10 hours in vacuum at the temperature of 80 ℃ to obtain the ZIF-8. FIG. 5 is a comparison of XRD patterns of ball milled synthetic ZIF-8 and simulated ZIF-8. As can be seen from FIG. 5, the ZIF-8 produced in this example is a substantially perfect match to the simulated ZIF-8, indicating that the crystals produced in this example are pure ZIF-8.
Example 5
Preparation of metal organic framework material HKUST-1Cu3(btc)2
Taking the dried CuCO3·Cu(OH)266.34g of trimesic acid and 65.68g of trimesic acid were ground and mixed. The mixed materials are put into a stainless steel tank, the solvent in the tank is 2L, 1000g, 500g and 500g of steel balls with the diameters of 16mm, 12mm and 8mm are respectively added, and the ball-material ratio is 15: 1. And finally sealing.
Setting the heating rate to be 5 ℃/min, the heat preservation temperature to be 200 ℃, the heat preservation time to be 3h, the rotating speed to be 60rpm and starting the program. After the reaction is finished and the temperature is cooled to the room temperature, taking out the reaction product, respectively washing the reaction product twice by absolute ethyl alcohol and deionized water, and finally drying the reaction product in vacuum at 120 ℃ for 10 hours to obtain the HKUST-1Cu product3(btc)2. FIG. 6 is a HKUST-1Cu synthesized by ball milling 3(btc)2And simulation HKUST-1Cu3(btc)2Comparing XRD patterns of the two parts. As can be seen from FIG. 6, HKUST-1Cu was obtained in this example3(btc)2And simulation HKUST-1Cu3(btc)2The crystal prepared by the embodiment of the invention is pure HKUST-1Cu3(btc)2。
Example 6
Preparation of bimetallic organic framework material ZnCu-MOF-74
Taking ZnO 22.6g, Cu (OH)227.1g and 55g of 2, 5-dihydroxyterephthalic acid were mixed by grinding. The mixed materials are put into a stainless steel tank, the volume of the tank is 2L, 1000g, 500g and 500g of steel balls with the diameters of 16mm, 12mm and 8mm are respectively added, and the ball-material ratio is 20: 1. And finally sealing.
Setting the heating rate at 5 ℃/min, the heat preservation temperature at 200 ℃, the heat preservation time at 5h, the rotating speed at 60rpm and starting the program. And after the reaction is finished and the temperature is cooled to room temperature, taking out reaction products, respectively washing the reaction products twice by DMF (dimethyl formamide), twice by anhydrous hot ethanol and twice by deionized water, and finally, drying the reaction products for 10 hours in vacuum at 100 ℃ to obtain the ZnCu-MOF-74. FIG. 7 is a comparison of XRD patterns of ball-milled synthesized ZnCu-MOF-74 and simulated ZnCu-MOF-74. As can be seen from FIG. 7, the ZnCu-MOF-74 produced in this example is substantially a perfect match with the simulated ZnCu-MOF-74, indicating that the crystals produced in this example are pure ZnCu-MOF-74.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A method for preparing MOFs materials by a heat-assisted mechanical ball milling method is characterized by comprising the following steps:
mixing metal salts, metal oxides or metal hydroxides with an organic ligand according to a molar ratio of 1:1-1:10 to obtain a mixture;
the mixture is put into a ball milling tank of a ball mill according to the ball-to-material ratio of 5:1-40:1, and ball milling reaction is carried out for 0.5-36h at the temperature of 50-600 ℃ according to the heating rate of 5 ℃/min;
and cooling to room temperature, taking out the reacted substances, and washing and drying the reacted substances to obtain the MOFs material.
2. The method for preparing MOFs materials by the heat-assisted mechanical ball milling method according to claim 1, wherein for metal salts with good solubility, the metal salts are firstly dissolved in deionized water or absolute ethyl alcohol to form a solution, then an organic ligand is added into the solution, and after uniform mixing, the mixture is evaporated to dryness at a temperature of 80-100 ℃ to obtain a mixture.
3. The method for preparing MOFs materials according to claim 2, wherein the metal in said metal salts, metal oxides and metal hydroxides is one or more selected from Mn, Fe, Co, Ni, Cu, Zn, Ag, Al, Cr, Zr, Ti, V, Mo, Sr, Cd, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Sc.
4. The method for preparing MOFs materials according to claim 3, wherein said organic ligand is a solid carboxylic acid or pyridine ligand at room temperature.
5. The method for preparing MOFs materials according to claim 1, wherein the washing of the reacted substances is carried out by washing with N, N-dimethylformamide or methanol and then with ethanol or deionized water according to the solubility of the unreacted organic ligands contained in the reacted substances, and the washing times are respectively 1-4 times.
6. The method for preparing MOFs materials according to claim 1, wherein said drying of the reacted substances is performed at a temperature of 50-150 ℃ in air or vacuum condition according to the stability of the prepared MOFs materials.
7. The method for preparing MOFs materials by using the heat-assisted mechanical ball milling method according to claim 1, wherein the ball milling tank of the ball mill is a stainless steel tank, a zirconia tank or a corundum tank, and the milling balls of the ball mill are stainless steel balls or zirconia balls.
8. The method for preparing MOFs materials by using the heat-assisted mechanical ball milling method according to claim 7, wherein the diameters of the grinding balls of said ball mill are respectively 16mm, 12mm and 8mm, and the mass ratio of the grinding balls with the diameters of 16mm, 12mm and 8mm is 2:1: 1.
9. The method for preparing MOFs material by using the heat assisted mechanical ball milling method according to claim 8, wherein the rotation speed of said ball mill is set to 50-100 rpm.
10. The method for preparing MOFs material according to any one of claims 1 to 9, wherein said MOFs material comprises ZIFs, IRMOFs, MILs, UiOs, and single metal or/and multi-metal organic framework material of Ni, Cu, rare earth and doped compound thereof.
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| CN114570334A (en) * | 2022-03-17 | 2022-06-03 | 中国科学院兰州化学物理研究所 | Preparation and application of water system stability MOFs/graphite phase carbon nitride composite material |
| CN115784665A (en) * | 2022-11-28 | 2023-03-14 | 陕西科技大学 | Preparation method of foaming wave-absorbing material derived based on MOFs (metal-organic frameworks) |
| CN115975209A (en) * | 2022-12-29 | 2023-04-18 | 武汉理工大学 | Method for synthesizing MOFs material in all solid phases |
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| CN114570334A (en) * | 2022-03-17 | 2022-06-03 | 中国科学院兰州化学物理研究所 | Preparation and application of water system stability MOFs/graphite phase carbon nitride composite material |
| CN115784665A (en) * | 2022-11-28 | 2023-03-14 | 陕西科技大学 | Preparation method of foaming wave-absorbing material derived based on MOFs (metal-organic frameworks) |
| CN115784665B (en) * | 2022-11-28 | 2023-10-24 | 陕西科技大学 | Preparation method of foaming wave-absorbing material based on MOFs (metal-organic frameworks) derivative |
| CN115975209A (en) * | 2022-12-29 | 2023-04-18 | 武汉理工大学 | Method for synthesizing MOFs material in all solid phases |
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