Aluminum-based metal-organic frameworks grown in situ on metal and metal oxide substrates and methods of making the same
By growing aluminum-based MOF materials in situ on aluminum mesh or activated alumina spheres, the problems of low purity and difficulty in control in traditional methods have been solved, realizing efficient and environmentally friendly MOF material preparation and obtaining excellent structure and properties.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- HOHAI UNIV
- Filing Date
- 2023-03-21
- Publication Date
- 2026-05-29
AI Technical Summary
In existing MOF material preparation methods, the violent reaction between dissolved metal ions and organic ligands leads to low material purity, high disorder, complex solvent recovery, and difficulty in controlling crystal growth, resulting in problems such as metal ion leaching and anion release.
An in-situ growth method using metal and metal oxide substrates is employed, in which aluminum-based MOF materials are directly grown on aluminum mesh or activated alumina spheres using insoluble metal precursors. Uniform in-situ growth of organic ligands is achieved through hydrothermal synthesis and surface treatment, avoiding the violent reactions and dissolution problems of traditional methods.
A rapid and simple preparation of aluminum-based MOF materials has been achieved, which has the advantages of being environmentally friendly, low-cost, and easy to control. 2D and 3D macroscopic and microscopic structures have been obtained, and the purity and performance of the materials have been improved.
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Figure CN116731331B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of MOFs material preparation technology, and relates to an aluminum-based metal-organic framework grown in situ on metal and metal oxide substrates and its preparation method. Background Technology
[0002] Metal-organic frameworks (MOFs) are crystalline organic-inorganic hybrid porous materials composed of metal nodes and organic linkers, exhibiting diverse pore structures and physicochemical properties. Various types of MOFs, such as MILs, ZIFs, and HKUST-1, have been known, and studies have revealed their different compositions, frameworks, and pore structures, as well as their wide range of applications in catalysis, gas storage, molecular separation, and sensors.
[0003] Generally, most MOF materials are prepared using a one-pot reaction of soluble metal salts and organic ligands. Ionic metal salts are the most common source of metals and can efficiently produce MOFs. However, this method has many drawbacks: the violent reaction between dissolved metal ions and organic ligands produces a large number of side reactions, resulting in low purity and high disorder of the material, thus reducing its performance; secondly, the dissolution of ionic metal salts complicates solvent recovery, and there are problems with metal ion leaching and potential anion release during use; finally, traditional soluble metal precursors are difficult to manipulate and control in time and space, making it difficult to reasonably control MOF crystals during synthesis. Summary of the Invention
[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide an aluminum-based metal-organic framework grown in situ on a metal and metal oxide substrate and its preparation method, which can rapidly and simply synthesize aluminum-based MOF materials.
[0005] To achieve the above objectives, the present invention is implemented using the following technical solution:
[0006] A method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate includes the following steps:
[0007] Aluminum mesh is surface treated to obtain a pretreated aluminum mesh carrier;
[0008] The activated alumina balls were soaked in deionized water until the water became clear; the soaked activated alumina balls were then dried to obtain the pretreated activated alumina ball carrier.
[0009] The organic ligands are uniformly dispersed in a solvent to obtain an organic ligand solution;
[0010] A pretreated aluminum mesh carrier or pretreated activated alumina ball carrier is mixed with an organic ligand solution and placed in a reaction vessel for hydrothermal synthesis of aluminum-based MOF materials. The aluminum-based MOF materials are then removed after cooling to room temperature.
[0011] The removed aluminum-based MOF material was then soaked, cleaned, and dried in sequence.
[0012] Optionally, the aluminum mesh can be surface-treated in a static alkaline solvent.
[0013] Optionally, the surface-treated aluminum mesh can be cleaned with ethanol.
[0014] Optionally, organic ligands include isophthalic acid, 1,3,5-benzenetricarboxylic acid, or terephthalic acid.
[0015] Optionally, the solvent may include one or a mixture of two of N,N-dimethylformamide and deionized water.
[0016] Optionally, after isophthalic acid disperses the organic ligands uniformly in the solvent, acetic acid is added for adjustment, and the solution is obtained by stirring and dissolving.
[0017] Optionally, after the 1,3,5-benzenetricarboxylic acid organic ligand is uniformly dispersed in the solvent, nitric acid is added for adjustment, and the solution is obtained by stirring and dissolving.
[0018] Optionally, the removed aluminum-based MOF material can be immersed in N,N-dimethylformamide.
[0019] Optionally, the aluminum-based MOF material can be cleaned in deionized water.
[0020] An aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate is prepared by the above-described preparation method.
[0021] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:
[0022] The present invention provides an aluminum-based metal-organic framework and its preparation method grown in situ on a metal and metal oxide substrate. It does not require an additional aluminum source. Zero-valent metals or metal oxides are used as substrates to act as reaction sources to participate in the formation of MOFs. It has the advantages of being environmentally friendly, low-cost and readily available.
[0023] Insoluble metal precursors themselves provide metal ions as active sites for the uniform nucleation and continuous growth of MOFs, and coordinate with organic ligands in solution. Therefore, by controlling the growth position of MOFs, the uniform in-situ growth of organic ligands on aluminum mesh or activated alumina spheres can be achieved.
[0024] The preparation process of this invention is simple and controllable, the raw materials are simple and readily available, and it can be prepared on a large scale.
[0025] The MOFs materials synthesized using solvents and insoluble solid matrices as templates in this invention possess 2D and 3D macroscopic and microscopic structures that are difficult to obtain using traditional solution-based synthesis methods. Attached Figure Description
[0026] Figure 1 The XRD pattern of the sample CAU-10-H@Al prepared in Example 1 of this invention;
[0027] Figure 2 This is a photograph of the sample CAU-10-H@Al prepared in Example 1 of the present invention.
[0028] Figure 3 The XRD pattern of sample MIL-96@Al prepared in Example 2 of this invention;
[0029] Figure 4 This is a photograph of the sample MIL-96@Al prepared in Example 2 of the present invention.
[0030] Figure 5 The XRD pattern of sample MIL-53@Al prepared in Example 3 of this invention;
[0031] Figure 6 This is a photograph of the sample MIL-53@Al prepared in Example 3 of the present invention.
[0032] Figure 7 The XRD pattern of sample MIL-96@Al2O3 prepared in Example 4 of this invention;
[0033] Figure 8 This is a photograph of the sample MIL-96@Al2O3 prepared in Example 4 of the present invention.
[0034] Figure 9 This is a photograph of the aluminum mesh of the present invention.
[0035] Figure 10 This is a photograph of the actual activated alumina balls of the present invention;
[0036] Figure 11 This is a comparison chart of the adsorption performance of the sample MIL-96@Al prepared in Example 2 of the present invention and the MIL-96 synthesized from aluminum nitrate nonahydrate.
[0037] Figure 12 The image shows a comparison of SEM images of the sample MIL-96@Al prepared in Example 2 of this invention and the MIL-96 synthesized from aluminum nitrate nonahydrate (the sample on the left is from Example 2, and the sample synthesized from aluminum nitrate nonahydrate is on the right). Detailed Implementation
[0038] The present invention will be further described below with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and should not be used to limit the scope of protection of the present invention.
[0039] 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 various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0040] For the purposes of this specification and the appended claims, unless otherwise stated, all expressions, percentages, or proportions, and other numerical values used in this specification and the appended claims, are to be understood to be modified by the term "about" in all cases. Furthermore, all scopes disclosed herein include their endpoints and can be combined independently. Example 1
[0041] like Figure 1 , Figure 2 and Figure 9 As shown, a method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate includes the following steps:
[0042] S1. A circular aluminum mesh with a diameter of 25 mm, 100 mesh, purity of 99%, and weight of 0.115 g was cut. The cut aluminum mesh was placed in a sodium hydroxide solution with a molar concentration of 0.1 M and reacted for 1 min. Then it was washed three times with ethanol to obtain a pretreated aluminum mesh carrier.
[0043] S2, 1.07 mmol of isophthalic acid was dispersed in a mixed solution of 0.86 ml N,N-dimethylformamide, 3.44 ml deionized water and 0.39 ml acetic acid, and stirred at 500 rpm for 2 h to obtain an organic ligand solution;
[0044] S3, the pretreated aluminum mesh carrier and organic ligand solution were transferred to a 100ml Teflon reaction vessel inner liner, reacted at 135℃ for 24h, and then removed after cooling to room temperature;
[0045] The MOF materials obtained in S4 and S3 were soaked and washed several times with N,N-dimethylformamide and deionized water, and then dried in an oven at 100°C.
[0046] The CAU-10-H@Al material was prepared using the method described above.
[0047] from Figure 1As can be seen, the MOF obtained by directly participating in the reaction with aluminum mesh as the substrate material is consistent with the results obtained from the standard spectrum. Example 2
[0048] like Figure 3 , Figure 4 and Figure 9 As shown, a method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate includes the following steps:
[0049] S1. A circular aluminum mesh with a diameter of 25 mm, 100 mesh, purity of 99%, and weight of 0.115 g was cut. The cut aluminum mesh was placed in a sodium hydroxide solution with a molar concentration of 0.1 M and reacted for 1 min. Then it was washed three times with ethanol to obtain a pretreated aluminum mesh carrier.
[0050] S2, 0.77 mmol of 1,3,5-benzenetricarboxylic acid was dispersed in a mixed solution of 10 ml of deionized water and 9 μl of nitric acid, and stirred at 500 rpm for 2 h to obtain an organic ligand solution;
[0051] S3, the pretreated aluminum mesh carrier and organic ligand solution were transferred to a 100ml Teflon reaction vessel inner liner, reacted at 200℃ for 24h, and then removed after cooling to room temperature;
[0052] The MOF materials obtained in S4 and S3 were soaked and washed several times with N,N-dimethylformamide and deionized water, and then dried in an oven at 80°C.
[0053] The MIL-96@Al material was prepared using the method described above.
[0054] from Figure 3 As can be seen, the MOF obtained by directly participating in the reaction with aluminum mesh as the substrate material is consistent with the results obtained from the standard spectrum.
[0055] from Figure 11 It can be seen that MIL-96 synthesized from aluminum mesh precursor has better fluoride ion adsorption efficiency.
[0056] from Figure 12 It can be seen that MIL-96 synthesized from aluminum mesh precursor has different crystal morphology from MIL-96 synthesized from soluble metal salt precursor. MIL-96 synthesized from aluminum mesh precursor has larger (100) and (101) exposed crystal planes, and the (100) and (101) crystal planes have more active sites for adsorbing fluoride ions. Example 3
[0057] like Figure 5 , Figure 6 and Figure 9As shown, a method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate includes the following steps:
[0058] S1. A circular aluminum mesh with a diameter of 25 mm, 100 mesh, purity of 99%, and weight of 0.115 g was cut. The cut aluminum mesh was placed in a sodium hydroxide solution with a molar concentration of 0.1 M and reacted for 1 min. Then it was washed three times with ethanol to obtain a pretreated aluminum mesh carrier.
[0059] S2, 6.42 mmol of terephthalic acid was dispersed in 9.2 ml of deionized water and stirred at 500 rpm for 2 h to obtain an organic ligand solution;
[0060] S3, the pretreated aluminum mesh carrier and organic ligand solution were transferred to a 100ml Teflon reaction vessel inner liner, reacted at 150℃ for 72h, and then removed after cooling to room temperature;
[0061] The MOF materials obtained in S4 and S3 were soaked and washed several times with N,N-dimethylformamide and deionized water, and then dried in an oven at 120°C.
[0062] The MIL-53@Al material was prepared using the method described above.
[0063] from Figure 5 As can be seen, the MOF obtained by directly participating in the reaction with aluminum mesh as the substrate material is consistent with the results obtained from the standard spectrum. Example 4
[0064] like Figure 7 , Figure 8 and Figure 10 As shown, a method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate includes the following steps:
[0065] S1. Take 1 mmol of activated alumina sphere with a diameter of 1.5 mm and soak it in deionized water until the water quality is clear; dry the soaked activated alumina sphere to obtain the pretreated activated alumina sphere carrier.
[0066] S2, 0.09 mmol of 1,3,5-benzenetricarboxylic acid was dispersed in a mixed solution of deionized water and nitric acid, the pH was adjusted to 0.69 with nitric acid, and the mixture was stirred at 500 rpm for 2 h to obtain an organic ligand solution;
[0067] S3, the pretreated activated alumina ball carrier and organic ligand solution were transferred to a 100ml Teflon reaction vessel inner liner, reacted at 200℃ for 24h, and then removed after cooling to room temperature;
[0068] The MOF materials obtained in S4 and S3 were soaked and washed several times with N,N-dimethylformamide and deionized water, and then dried in an oven at 80°C.
[0069] The MIL-96@Al2O3 material was prepared using the method described above.
[0070] from Figure 7 As can be seen, the MOF obtained by directly participating in the reaction with activated alumina spheres as the substrate material is consistent with the results obtained from the standard spectrum.
[0071] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate, characterized in that, Includes the following steps: The aluminum mesh is surface treated to obtain a pretreated aluminum mesh carrier; the surface treatment involves placing the aluminum mesh in a 0.1M sodium hydroxide solution and reacting for 1 minute, followed by ethanol cleaning. The activated alumina balls were soaked in deionized water until the water became clear; the soaked activated alumina balls were then dried to obtain the pretreated activated alumina ball carrier. An organic ligand is uniformly dispersed in a solvent to obtain an organic ligand solution; the organic ligand is isophthalic acid, 1,3,5-benzenetricarboxylic acid, or terephthalic acid; the solvent is a mixture of N,N-dimethylformamide and deionized water; when the organic ligand is isophthalic acid, acetic acid is added for adjustment; when the organic ligand is 1,3,5-benzenetricarboxylic acid, nitric acid is added for adjustment; the organic ligand solution is obtained after stirring and dissolving. A pretreated aluminum mesh carrier or pretreated activated alumina sphere carrier was mixed with an organic ligand solution and placed in a reaction vessel for hydrothermal synthesis of aluminum-based MOF materials. The aluminum-based MOF materials were then cooled to room temperature and removed. When the organic ligand was isophthalic acid, the hydrothermal synthesis conditions were 135℃ for 24 hours; when the organic ligand was 1,3,5-benzenetricarboxylic acid solution, the hydrothermal synthesis conditions were 200℃ for 24 hours; and when the organic ligand was terephthalic acid, the hydrothermal synthesis conditions were 150℃ for 72 hours. The removed aluminum-based MOF material was then soaked, cleaned, and dried in sequence.
2. The method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate according to claim 1, characterized in that: The removed aluminum-based MOF material was immersed in N,N-dimethylformamide.
3. The method for preparing an aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate according to claim 1, characterized in that: The aluminum-based MOF material was cleaned in deionized water.
4. An aluminum-based metal-organic framework grown in situ on a metal or metal oxide substrate, characterized in that: Prepared by the preparation method according to any one of claims 1-3.