CN115181281A - Bismuth-based metal organic framework material and preparation method thereof - Google Patents
Bismuth-based metal organic framework material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 77
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 77
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- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
- -1 halogenated alkyl quaternary ammonium salts Chemical class 0.000 claims description 21
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 8
- FIHWSKZZMQZEGE-UHFFFAOYSA-N 2-[2,4-bis(2-carboxyphenyl)-1h-triazin-6-yl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1N1N=C(C=2C(=CC=CC=2)C(O)=O)C=C(C=2C(=CC=CC=2)C(O)=O)N1 FIHWSKZZMQZEGE-UHFFFAOYSA-N 0.000 claims description 5
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HWSISDHAHRVNMT-UHFFFAOYSA-N Bismuth subnitrate Chemical compound O[NH+]([O-])O[Bi](O[N+]([O-])=O)O[N+]([O-])=O HWSISDHAHRVNMT-UHFFFAOYSA-N 0.000 claims description 3
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- PFKRTWCFCOUBHS-UHFFFAOYSA-N dimethyl(octadecyl)azanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCCCCCC[NH+](C)C PFKRTWCFCOUBHS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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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Abstract
The invention relates to a bismuth-based metal organic framework material and a preparation method thereof. The preparation method of the bismuth-based metal organic framework material comprises the following steps: mixing bismuth salt, a polybasic acid organic ligand and a cationic surfactant to obtain a mixture; and mixing the mixture with water, and carrying out ultrasonic treatment to obtain the bismuth-based metal organic framework material. The preparation method utilizes the cationic surfactant to prepare the bismuth-based metal organic framework material with good crystallinity, smaller size and more uniform mass distribution in a water system, has the advantages of low energy consumption, short period and the like, and is beneficial to large-scale production and application of the bismuth-based metal organic framework material.
Description
Technical Field
The invention relates to the technical field of organic-inorganic hybrid materials, in particular to a bismuth-based metal organic framework material and a preparation method thereof.
Background
The main approach for preparing the bismuth-based metal organic framework material in the traditional technology is a solvothermal method, an organic solvent is required to be used as a reaction system, and the solvothermal method is simple and convenient to operate, but has the problems of long period, high energy consumption and the like in the preparation process.
Although the bismuth-based metal organic framework material can be prepared in a water system through multi-step reaction, the bismuth-based metal organic framework material prepared in the water system traditionally still has space structure defects, and the yield of the bismuth-based metal organic framework material is reduced.
Disclosure of Invention
In view of the above, it is necessary to provide a bismuth-based metal-organic framework material and a method for preparing the same; the preparation method utilizes the cationic surfactant to prepare the bismuth-based metal organic framework material with good crystallinity, smaller size and more uniform mass distribution in a water system, has the advantages of low energy consumption, short period and the like, and is beneficial to large-scale production and application of the bismuth-based metal organic framework material.
A preparation method of a bismuth-based metal organic framework material comprises the following steps:
mixing bismuth salt, a polybasic acid organic ligand and a cationic surfactant to obtain a mixture; and
and mixing the mixture with water, and carrying out ultrasonic treatment to obtain the bismuth-based metal organic framework material.
In one embodiment, the mass ratio of the bismuth salt to the cationic surfactant is 30.
In one embodiment, the cationic surfactant is selected from at least one of halogenated alkyl quaternary ammonium salt and higher amine salt.
In one embodiment, the quaternary ammonium haloalkyl salt is selected from at least one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide.
In one embodiment, the higher amine salt is selected from at least one of primary, secondary, and tertiary alkyl amine salts.
In one embodiment, the mass ratio of the bismuth salt to the polybasic acid organic ligand is 1 to 1.
In one embodiment, the bismuth salt is selected from at least one of bismuth nitrate pentahydrate, bismuth acetate, and bismuth subnitrate.
In one embodiment, the polyacid organic ligand is selected from at least one of 1,3, 5-trimesic acid, triazine-2, 4, 6-triyl-tribenzoic acid, biphenyl-3, 3', 5' -tetracarboxylic acid.
In one embodiment, the ultrasonic treatment time is 1min-90min, and the ultrasonic treatment working frequency is 30KHz-90KHz.
The bismuth-based metal organic framework material is prepared by the preparation method of the bismuth-based metal organic framework material.
According to the preparation method of the bismuth-based metal organic framework material, the lone pair electrons contained in the cationic surfactant are utilized, so that the cationic surfactant can preferentially replace hydrogen ions on carboxyl on the surface of the polybasic acid organic ligand in a water system, and the problem of incomplete deprotonation of the polybasic acid organic ligand is solved, so that the polybasic acid organic ligand can be effectively combined with bismuth ions, and the bismuth-based metal organic framework material with good crystallinity, smaller size and more uniform mass distribution can be prepared. In addition, the preparation method has the advantages of low energy consumption, short period and the like, and is beneficial to large-scale production and application of the bismuth-based metal organic framework material.
Drawings
FIG. 1 is a scanning electron microscope image of the bismuth-based metal organic framework material prepared in example 1;
FIG. 2 is an X-ray diffraction pattern of the bismuth-based metal-organic framework material prepared in example 1;
FIG. 3 is a scanning electron micrograph of the products prepared in comparative example 1, comparative example 2 and comparative example 3;
fig. 4 is an X-ray diffraction pattern of the products prepared in comparative example 1, comparative example 2, and comparative example 3.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described in more detail. It is understood, however, that the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments or examples set forth herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention.
The applicant has found, through long-term and intensive research, that during the synthesis of metal organic framework Materials (MOFs), deprotonation is required when organic ligands are dissolved in a solvent system, so that the organic ligands are more easily bonded with metal ions, thereby forming a complete metal organic framework. However, in aqueous systems, deprotonation of the polyacid organic ligand is incomplete, resulting in the reaction of bismuth ions with only partially deprotonated carboxyl groups, yielding intermediates. In aqueous systems, these intermediates are difficult to grow to fully build the complete metal organic framework.
Based on the above, the invention provides a preparation method of a bismuth-based metal organic framework material, which comprises the following steps:
s1, mixing bismuth salt, a polybasic acid organic ligand and a cationic surfactant to obtain a mixture; and
and S2, mixing the mixture with water, and carrying out ultrasonic treatment to obtain the bismuth-based metal organic framework material.
In step S1, the cationic surfactant can effectively bind to the polyacid organic ligand, thereby facilitating improvement of complete deprotonation of the polyacid organic ligand.
In order to completely deprotonate the polyacid organic ligand, the mass ratio of the bismuth salt to the cationic surfactant is 30.
Specifically, the halogenated alkyl quaternary ammonium salt is selected from at least one of hexadecyl trimethyl ammonium bromide and dodecyl trimethyl ammonium bromide; the higher amine salt is selected from at least one of alkyl primary amine salt, alkyl secondary amine salt and alkyl tertiary amine salt, wherein the alkyl primary amine salt is selected from dodecyl amine hydrochloride, the alkyl secondary amine salt is selected from dioctadecyl amine hydrochloride, and the alkyl tertiary amine salt is selected from N, N-dimethyl octadecyl amine hydrochloride.
The cationic surfactant can form micelles in the solution, so that the effect of enriching bismuth ions and polybasic acid organic ligands is realized, and the synthesis of the bismuth-based metal organic framework material is promoted.
In order to ensure the generation of the bismuth-based metal organic framework material, the mass ratio of the bismuth salt to the polyacid organic ligand is regulated to be 1-1.
Specifically, the bismuth salt is selected from at least one of bismuth nitrate pentahydrate, bismuth acetate and bismuth subnitrate, and is preferably bismuth nitrate pentahydrate; the polyacid organic ligand is at least one selected from 1,3, 5-trimesic acid, triazine-2, 4, 6-triyl-tribenzoic acid and biphenyl-3, 3', 5' -tetracarboxylic acid, and is preferably 1,3, 5-trimesic acid.
Further, the 1,3, 5-trimesic acid and the bismuth salt can react to form CAU-7 and CAU-17, the triazine-2, 4, 6-triyl-tribenzoic acid and the bismuth salt can react to form CAU-35, the biphenyl-3, 3', 5' -tetracarboxylic acid and the bismuth salt can react to form NOTT-220, and the CAU-7, CAU-17, CAU-35 and NOTT-220 are bismuth-based metal organic framework materials with different topological structures.
In the step S2, in the aqueous solution at normal temperature and normal pressure, the lone pair electrons contained in the cationic surfactant are utilized, so that the cationic surfactant can preferentially replace hydrogen ions on carboxyl groups on the surface of the polybasic acid organic ligand in a water system, the problem of incomplete deprotonation of the polybasic acid organic ligand is solved, and the efficient bonding of the deprotonated polybasic acid organic ligand and bismuth ions is promoted.
In order to improve the product conversion rate, the mass ratio of the bismuth salt to the water is 10-10.
In order to further reduce the influence of the micro-ions in the water on the reaction process, the water is preferably deionized water.
Because the water system is mixed with the bismuth salt, the polyacid organic ligand and the cationic surfactant in a certain proportion, when ultrasonic treatment is carried out under a certain ultrasonic frequency condition, the cationic surfactant preferentially replaces hydrogen ions on carboxyl groups on the surface of the polyacid organic ligand, so that the polyacid organic ligand is completely deprotonated, and the bismuth ions and the deprotonated polyacid organic ligand are favorably bonded.
Meanwhile, due to the action of ultrasonic treatment, severe intermolecular vibration is generated between bismuth ions and the deprotonated polyacid organic ligand, so that tiny gaps are generated inside molecules, the tiny gaps are rapidly expanded and closed along with ultrasonic frequency, severe collision action is generated between the molecules, the bonding between the bismuth ions and the deprotonated polyacid organic ligand is further improved, the crystal growth of a bismuth-based organic metal framework is efficiently promoted, and therefore the bismuth-based metal organic framework material is good in crystallinity, smaller in size and more uniform in mass distribution.
In some embodiments, the time of the ultrasonic treatment is 1min to 90min, and the working frequency of the ultrasonic treatment is 30KHz to 90KHz; further, in order to reduce energy loss, improve preparation efficiency and shorten preparation period, the time of ultrasonic treatment is preferably 30min to 60min; the working frequency of the ultrasonic treatment is preferably 35KHz-50KHz.
Therefore, the bismuth-based metal organic framework material with good crystallinity, smaller size and more uniform mass distribution is prepared in a water system by using the cationic surfactant, and the preparation method has the advantages of low energy consumption, short period, mild and safe preparation process, no pollution and the like, and is beneficial to large-scale production and application of the bismuth-based metal organic framework material.
In addition, the bismuth-based metal organic framework material prepared by the invention has the characteristics of unique three-dimensional porous structure unit, high specific surface area, high structural stability and the like, has adjustable pore size, and can be widely used for carbon dioxide adsorption reduction,Adsorption of pollutants in water body and preparation of BiVO with photocatalytic activity by using pollutants as precursor 4 Materials, and the like.
The invention also provides a bismuth-based metal organic framework material obtained by the preparation method.
Compared with the traditional hydrothermal method and the bismuth-based metal organic framework material prepared by a multi-step method in a water system, the bismuth-based metal organic framework material prepared by the preparation method provided by the invention has smaller size and is more uniform.
Specifically, the bismuth-based metal organic framework material is in a short rod shape, and the length of the bismuth-based metal organic framework material is 200nm-2 μm, preferably 800nm-1.5 μm.
Hereinafter, the method for producing the bismuth-based metal-organic framework material will be further described with reference to the following specific examples.
In the examples, the acceleration voltage was 0.5kV to 30kV and the magnification was 10 ten thousand to 50 ten thousand in a scanning electron microscope (Zeiss v ultra 55) test.
In the examples, an X-ray powder diffractometer (Bruker D8) having a light source of Cu-Kal and a test angle of 5 to 50 ℃ was tested under conditions of a 40mA scanning current and a 40kV scanning voltage.
Example 1
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
FIG. 1 shows a scanning electron microscope image of the prepared bismuth-based metal organic framework material, and it can be seen from FIG. 1 that the bismuth-based metal organic framework material is in a short rod shape, has a length of 800nm-1.5 μm, and has a uniform size distribution.
FIG. 2 contains the X-ray diffraction pattern of the prepared bismuth-based metal-organic framework material, and it can be seen from FIG. 2 that the bismuth-based metal-organic framework material is excellent in crystallization property, shows layered diffraction peaks peculiar to the bismuth-based metal-organic framework material in diffraction angles of 5 to 50 degrees, and the positions of all diffraction peaks of the bismuth-based metal-organic framework material correspond one-to-one to the positions of diffraction peaks of the known CAU-17 crystal structure, indicating that the bismuth-based metal-organic framework material and CAU-17 have the same crystal structure, i.e., the bismuth-based metal-organic framework material is CAU-17.
Example 2
Mixing 100mg of bismuth nitrate pentahydrate, 100mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, then adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 3
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 50mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, then adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 4
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 100mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, then adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 5
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 50KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 6
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, then adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 90KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 7
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 20min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 8
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 90min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 9
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 30mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 10
Mixing 100mg of bismuth acetate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 11
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of triazine-2, 4, 6-triyl-tribenzoic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 12
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of dodecyl trimethyl ammonium bromide, and stirring uniformly to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Example 13
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of dioctadecyl amine hydrochloride, and stirring uniformly to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, then adding 15mL of deionized water, carrying out ultrasonic oscillation treatment for 40min under the condition of 37KHz ultrasonic working frequency, transferring the final product into a large beaker, adding deionized water, and carrying out centrifugal washing for three times to obtain the bismuth-based metal organic framework material.
Comparative example 1
Uniformly mixing and stirring 100mg of bismuth nitrate pentahydrate and 500mg of 1,3, 5-trimesic acid to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 20mL of deionized water, and carrying out ultrasonic oscillation treatment for 40min under the condition of an ultrasonic working frequency of 37 KHz. After ultrasonic oscillation, a product is generated in the mixed solution, and the product is centrifugally washed with deionized water for three times.
Fig. 3 contains a scanning electron micrograph of the resulting product, and from fig. 3 (a), the product is in the form of a micron-sized plate and has a non-uniform size distribution.
FIG. 4 contains the X-ray diffraction pattern of the resulting product, and from FIG. 4 (a), the position of the diffraction peak of the product is different from the position of the diffraction peak of the known CAU-17 crystal structure, indicating that the product is not CAU-17.
Comparative example 2
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; then 20mL of deionized water was added and the vessel was left to stand at room temperature for 40min, the product was formed in the mixed solution and the product was washed three times by centrifugation with deionized water.
Fig. 3 contains a scanning electron micrograph of the product obtained, and from fig. 3 (b), the product is in the form of agglomerated fragments in which a portion of the fragments are doped.
FIG. 4 contains the X-ray diffraction pattern of the resulting product, and from FIG. 4 (b), the position of the diffraction peak of the product is different from the position of the diffraction peak of the known CAU-17 crystal structure, indicating that the product is not CAU-17.
Comparative example 3
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of hexadecyl trimethyl ammonium bromide, and uniformly stirring to obtain a mixture; then 20mL of deionized water was added and the vessel was placed on a stirring table and stirred at room temperature for 40min, the product was formed in the mixed solution and the product was washed three times by centrifugation with deionized water.
Fig. 3 contains a scanning electron micrograph of the resulting product, and as can be seen from fig. 3 (c), the product is in the form of large blocks of micron-sized particles with fragments distributed on the surface.
FIG. 4 contains the X-ray diffraction pattern of the resulting product, and from FIG. 4 (c), the position of the diffraction peak of the product is different from the position of the diffraction peak of the known CAU-17 crystal structure, indicating that the product is not CAU-17.
Comparative example 4
Mixing 100mg of bismuth nitrate pentahydrate, 500mg of 1,3, 5-trimesic acid and 5mg of sodium dodecyl sulfate, and stirring uniformly to obtain a mixture; and (3) placing the container containing the mixture sample in an ultrasonic oscillator, adding 20mL of deionized water, and carrying out ultrasonic oscillation treatment for 40min under the condition of an ultrasonic working frequency of 37 KHz. After ultrasonic oscillation, no product is generated in the mixed solution.
As can be seen from examples 1 to 13 and comparative example 1, the bismuth-based metal organic framework material could not be prepared by placing the bismuth salt and the polybasic acid organic ligand into a dehydration reaction system and carrying out the ultrasonic oscillation reaction without adding the cationic surfactant.
As can be seen from examples 1 to 13 and comparative examples 2 and 3, the bismuth-based metal organic framework material could not be prepared by putting the bismuth salt, the polyacid organic ligand and the cationic surfactant into the water reaction system without ultrasonic oscillation reaction.
According to examples 1-13 and comparative example 4, no product is generated by using sodium dodecyl sulfate, bismuth salt and polybasic acid organic ligand to carry out ultrasonic oscillation reaction in a water reaction system.
In summary, in the preparation method of the bismuth-based metal organic framework material provided by the invention, the cationic surfactant and the ultrasonic treatment are necessary technical conditions for preparing the bismuth-based metal organic framework material, and the bismuth-based metal organic framework material with good crystallinity, smaller size and more uniform mass distribution can be prepared only under the action of the cationic surfactant and the ultrasonic action.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The preparation method of the bismuth-based metal organic framework material is characterized by comprising the following steps of:
mixing bismuth salt, a polybasic acid organic ligand and a cationic surfactant to obtain a mixture; and
and mixing the mixture with water, and carrying out ultrasonic treatment to obtain the bismuth-based metal organic framework material.
2. The method for producing a bismuth-based metal-organic framework material according to claim 1, wherein the mass ratio of the bismuth salt to the cationic surfactant is 30.
3. The method for preparing a bismuth-based metal organic framework material according to claim 1, wherein the cationic surfactant is at least one selected from the group consisting of halogenated alkyl quaternary ammonium salts and higher amine salts.
4. The method of claim 3, wherein the quaternary ammonium haloalkyl salt is at least one selected from the group consisting of cetyltrimethylammonium bromide and dodecyltrimethylammonium bromide.
5. The method for producing a bismuth-based metal organic framework material according to claim 3, wherein the higher amine salt is at least one selected from the group consisting of primary alkyl amine salts, secondary alkyl amine salts, and tertiary alkyl amine salts.
6. The method for producing a bismuth-based metal-organic framework material according to any one of claims 1 to 5, wherein the mass ratio of the bismuth salt to the polybasic acid organic ligand is 1 to 1.
7. A method for preparing a bismuth-based metal organic framework material as claimed in any one of claims 1 to 5, wherein the bismuth salt is selected from at least one of bismuth nitrate pentahydrate, bismuth acetate, and bismuth subnitrate.
8. The method for preparing a bismuth-based metal-organic framework material according to any one of claims 1 to 5, wherein the polyacid organic ligand is selected from at least one of 1,3, 5-trimesic acid, triazine-2, 4, 6-triyl-tribenzoic acid, biphenyl-3, 3', 5' -tetracarboxylic acid.
9. The method for preparing a bismuth-based metal organic framework material according to any one of claims 1 to 5, wherein the time of the ultrasonic treatment is 1min to 90min, and the working frequency of the ultrasonic treatment is 30KHz to 90KHz.
10. A bismuth-based metal organic framework material prepared by the method for preparing the bismuth-based metal organic framework material as claimed in any one of claims 1 to 9.
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