CN111440326B - Nano-scale MIL-47(V) metal organic framework compound and preparation method thereof - Google Patents
Nano-scale MIL-47(V) metal organic framework compound and preparation method thereof Download PDFInfo
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- CN111440326B CN111440326B CN202010201647.6A CN202010201647A CN111440326B CN 111440326 B CN111440326 B CN 111440326B CN 202010201647 A CN202010201647 A CN 202010201647A CN 111440326 B CN111440326 B CN 111440326B
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Abstract
The invention relates to a nanoscale MIL-47(V) metal organic framework compound and a preparation method thereof, belonging to the technical field of nano materials. The compound is prepared by the following method: adding vanadium disulfide and terephthalic acid into a methanol solution, uniformly mixing, adding acid to adjust the pH value to 1-2, reacting for 12-36h at the temperature of 140-180 ℃ by a solvothermal method, washing, filtering, drying to obtain a powdery product, and finally preserving the heat of the powdery product for 12-36h at the temperature of 200-300 ℃. The compound is rod-shaped, has the length of 150-300nm and the width of 15-45nm, has the size which is lower than that of the traditional compound by two orders of magnitude, can further broaden and endow more applications of the MIL-47(V) metal organic framework compound, particularly in the fields of gas adsorption and catalysis, has the advantages of simple preparation method, easy operation, safety, no toxicity and low cost, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nano-scale MIL-47(V) metal organic framework compound and a preparation method thereof.
Background
The metal-organic framework compound is a crystal material with a regular structure formed by self-assembly of metal ions and multidentate organic ligands through coordination connection. Due to the adjustability of the topological structure at the molecular level, the diversity of metal and organic ligands, various different structures and different types of metal organic framework compounds are widely prepared in recent years, and the unique molecular structure of the metal organic framework compounds has great potential application value in the fields of gas storage and separation, catalysis, nonlinear optics, light capture, drug loading and energy storage. MIL-47(V) is a metal organic framework material which is synthesized and reported in 2002 by F é rey project group of Lavartin research institute in France, is centered on vanadium, is matched with dimethyl 1, 4-phthalate, and has a three-dimensional framework structure with rhombic pores. Its high BET specific surface area (900 m)2G), larger pore diameter
In particular, high thermal stability, which makes it of great interest to researchers, a great variety of applications around it have been explored, and in particular, in the field of gas adsorption storage and separation, MIL-47(V) has shown great utility, especially for H2、CH4、H2The excellent adsorption and storage properties of gases such as S further increase the enthusiasm of researchers for research.
Since the organic ligand must pass through in solutionMetal ion coordination, self-assembly, etc. can form metal-organic frameworks, and thus in metal-organic frameworks centered on vanadium, traditional inorganic vanadates, such as sodium vanadate (Na)3VO4) And may not be a vanadium source. Although the research on MIL-47(V) is continuous in recent years, most reports still use the most original method reported in 2002 by the F é y project group for the preparation of MIL-47 (V). In this process, vanadium trichloride (VCl) is used for Ferey in order to obtain the individual vanadium ions in solution3) As a source of vanadium, VCl3As a highly toxic, highly reactive, highly irritating, expensive chemical, it severely limits the large scale production of MIL-47 (V). In addition, the severe reaction conditions of the method also enable the MIL-47(V) crystal powder prepared to show a huge rod-like structure (about 1um thick), and the large particle structure also limits the MIL-47(V) to fully exert the application potential.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a nanoscale MIL-47(V) metal-organic framework compound; the second purpose is to provide a preparation method of the nanometer MIL-47(V) metal organic framework compound.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a nanometer MIL-47(V) metal organic framework compound, wherein the MIL-47(V) metal organic framework compound is rod-shaped, the length of the MIL-47(V) metal organic framework compound is 150-300nm, and the width of the MIL-47(V) metal organic framework compound is 15-45 nm.
2. The preparation method of the nanometer MIL-47(V) metal organic framework compound comprises the following steps:
adding vanadium disulfide and terephthalic acid into a methanol solution, uniformly mixing, adding acid to adjust the pH value to 1-2, reacting for 12-36h at the temperature of 140-180 ℃ by a solvothermal method, washing, filtering, drying to obtain a powdery product, and finally preserving the heat of the powdery product for 12-36h at the temperature of 200-300 ℃.
Preferably, the mass ratio of the vanadium disulfide to the terephthalic acid to the methanol solution is 1:1-10: 200.
Preferably, the volume fraction of the methanol solution is 95% or more.
Preferably, the blending specifically comprises: performing ultrasonic treatment in an ultrasonic machine with power of more than 100W for more than 5 min.
Preferably, the acid is one of hydrochloric acid or dilute sulfuric acid.
Preferably, the washing is specifically: washing with methanol or ethanol.
Preferably, the drying specifically comprises: drying at 40-80 deg.C under vacuum to constant weight.
The invention has the beneficial effects that: the invention provides a nanometer MIL-47(V) metal organic framework compound and a preparation method thereof, wherein vanadium disulfide with low price, safety and mild chemical property is used as a vanadium source, the vanadium disulfide is dissolved under the acidic condition by adjusting the pH value of a reaction solution, vanadium ions are slowly released, terephthalic acid and the vanadium ions are coordinated to form the nanometer MIL-47(V) metal organic framework compound, so that high toxicity, high activity, strong irritation and expensive VCl are avoided on one hand3The use of the method ensures that the whole preparation process is safe, nontoxic and low in cost, and on the other hand, the defect that the finally prepared metal organic framework compound has larger size due to violent reaction in the prior art is avoided, and the finally prepared MIL-47(V) metal organic framework compound has the length of 150-300nm and the width of 15-45 nm. The reason why the pH value is adjusted to 1-2 is that when the pH value exceeds 2, vanadium disulfide cannot be effectively dissolved, so that enough abundant free vanadium ions cannot be formed in a reaction system, the purity of a finally prepared compound cannot be ensured, a product is complex, and incompletely reacted vanadium disulfide is doped; and when the pH value is less than 1, the vanadium disulfide is dissolved too fast, so that the finally generated MIL-47(V) metal organic framework compound crystal is too large, the crystal structure and the appearance of the compound are influenced, and a mixed phase is generated.
In addition, in the method, a methanol solution is used as a solvent, the high polarity of the methanol solution can ensure the dissolution of terephthalic acid, the weak acidity presented by hydroxyl in the molecular formula of the methanol is more beneficial to the reaction, and the finally prepared MIL-47(V) metal organic framework compound can be ensured to present a more uniform and regular shape. In addition, the mass ratio of the vanadium disulfide to the terephthalic acid, the reaction temperature and the reaction time of the solvothermal method are further limited in the method, so that the finally prepared MIL-47(V) metal organic framework compound is further ensured to be nanoscale and has a uniform size, wherein the proper mass ratio of the vanadium disulfide to the terephthalic acid is limited, so that the solid vanadium disulfide can be ensured to fully react, and the defects of large and uneven particles caused by over violent local reaction can be avoided; the temperature and time of the solvothermal method reaction are limited, so that the MIL-47(V) metal organic framework compound crystal can be prevented from further growing in a relatively long-time reaction process while the reaction is fully carried out. The size of the nanometer MIL-47(V) metal organic framework compound is lower than that of the traditional compound by nearly two orders of magnitude, more applications of the MIL-47(V) metal organic framework compound can be further widened and endowed, particularly in the fields of gas adsorption and catalysis, and the preparation method is simple, easy to operate, safe, nontoxic, low in cost and suitable for industrial production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram of the crystal structure of the nano-sized MIL-47(V) metal-organic framework compound prepared in examples 1 to 3;
FIG. 2 is an XRD pattern of a nanoscale MIL-47(V) metal-organic framework compound prepared in example 1;
FIG. 3 is a field emission scanning electron microscope image of a nanoscale MIL-47(V) metal-organic framework compound prepared in example 1;
FIG. 4 is a thermogravimetric plot of the nanoscale MIL-47(V) metal-organic framework compound prepared in example 1;
FIG. 5 is a field emission scanning electron microscope photograph of a nanoscale MIL-47(V) metal-organic framework compound prepared in example 2;
FIG. 6 is a field emission scanning electron microscope photograph of a nanoscale MIL-47(V) metal-organic framework compound prepared in example 3;
FIG. 7 is an XRD pattern of the product prepared in comparative example 1;
FIG. 8 is a field emission scanning electron microscope photograph of the product prepared in comparative example 1;
FIG. 9 is an XRD pattern of the product prepared in comparative example 2;
FIG. 10 is a field emission scanning electron microscope photograph of the product prepared in comparative example 2.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparation of nanoscale MIL-47(V) Metal-organic framework Compounds
Adding vanadium disulfide and terephthalic acid into a methanol solution with the volume fraction of 99% according to the mass ratio of 1:1.5:200, carrying out ultrasonic treatment in an ultrasonic machine with the power of 150W for 5min, adding 1mol/L hydrochloric acid to adjust the pH value to 1, transferring the obtained product into an inner container of a tetrafluoroethylene reaction kettle, carrying out reaction at 160 ℃ for 24h, washing the obtained product by the methanol solution with the volume fraction of 99%, carrying out suction filtration, carrying out vacuum drying at 60 ℃ until the weight is constant to obtain a powdery product, and finally carrying out heat preservation on the powdery product at 250 ℃ for 24 h.
Example 2
Preparation of nanoscale MIL-47(V) Metal-organic framework Compounds
Adding vanadium disulfide and terephthalic acid into a methanol solution with a volume fraction of 98% according to a mass ratio of 1:6:200, carrying out ultrasonic treatment in an ultrasonic machine with a power of 100W for 10min, adding dilute sulfuric acid to adjust the pH value to 2, transferring the mixture into a liner of a tetrafluoroethylene reaction kettle, reacting at 140 ℃ for 36h, washing the mixture with the methanol solution with the volume fraction of 98%, carrying out suction filtration, carrying out vacuum drying at 40 ℃ to constant weight to obtain a powdery product, and finally, carrying out heat preservation on the powdery product at 200 ℃ for 36 h.
Example 3
Preparation of nanoscale MIL-47(V) Metal-organic framework Compounds
Adding vanadium disulfide and terephthalic acid into a methanol solution with a volume fraction of 97% according to a mass ratio of 1:10:200, carrying out ultrasonic treatment in an ultrasonic machine with a power of 120W for 8min, adding 1mol/L hydrochloric acid to adjust the pH value to 1.5, transferring the obtained product into an inner container of a tetrafluoroethylene reaction kettle, carrying out reaction at 180 ℃ for 12h, washing the obtained product with an ethanol solution with a volume fraction of 97%, carrying out suction filtration, carrying out vacuum drying at 80 ℃ until the weight is constant to obtain a powdery product, and finally carrying out heat preservation on the powdery product at 300 ℃ for 12 h.
FIG. 1 is a schematic diagram showing the crystal structure of the nano-sized MIL-47(V) metal-organic framework compound prepared in examples 1 to 3, and it can be seen from FIG. 1 that each V atom is coordinated by an 8-face body formed by 6O atoms.
FIG. 2 is an XRD pattern of the nano-sized MIL-47(V) metal-organic framework compound prepared in example 1, and it can be seen from FIG. 2 that the nano-sized MIL-47(V) metal-organic framework compound has an ordered crystal structure, corresponding to a standard card.
FIG. 3 is a SEM image of the primary structure of the nano-sized MIL-47(V) MOM prepared in example 1, and it can be seen from FIG. 3 that the primary structure of the nano-sized MIL-47(V) MOM is in a bulk state, but the bulk state is composed of the rod-shaped MIL-47(V) MOM having a length of 150-300nm and a width of 15-45 nm.
FIG. 4 is a thermogravimetric analysis graph of the nano-sized MIL-47(V) metal-organic framework compound prepared in example 1, and it can be seen from FIG. 4 that the nano-sized MIL-47(V) metal-organic framework compound prepared exhibits a nano-sized crystal structure, but still exhibits high thermal stability.
FIG. 5 is a SEM image of the nano-sized MIL-47(V) MOM prepared in example 2, and it can be seen from FIG. 5 that the primary structure of the nano-sized MIL-47(V) MOM is in a bulk state, but the bulk state is composed of the rod-shaped MIL-47(V) MOM having a length of 150-300nm and a width of 15-45 nm.
FIG. 6 is a scanning electron microscope image of a field emission scanning electron microscope of the nano-sized MIL-47(V) metal-organic framework compound prepared in example 3, and it can be seen from FIG. 6 that the primary structure of the nano-sized MIL-47(V) metal-organic framework compound is a spherical structure, but the spherical structure is composed of a rod-shaped MIL-47(V) metal-organic framework compound having a length of 150-300nm and a width of 15-45 nm.
Comparative example 1
The difference from example 1 is that 1mol/L hydrochloric acid is not added to adjust the pH.
FIG. 7 is an XRD pattern of the product, and from FIG. 7, the product is not MIL-47(V) metal organic framework compound crystals.
FIG. 8 is a SEM image of the product, and as can be seen from FIG. 8, the product is agglomerated and disordered, and no MIL-47(V) metal-organic framework compound crystal can be observed under high magnification, and the incompletely reacted vanadium disulfide is doped.
It is shown that the pH value is too high, the purity of the finally prepared compound cannot be ensured, and the product is relatively complex and is doped with vanadium disulfide which is not completely reacted.
Comparative example 2
The difference from example 1 is that 1mol/L hydrochloric acid is added to adjust the pH to 0.
FIG. 9 is an XRD pattern of the product, and it can be seen from FIG. 9 that the product has many hetero peaks besides the diffraction peak of the MIL-47(V) metal organic framework, indicating that the impurity is more.
FIG. 10 is a field emission scanning electron microscope photograph of the product, and it can be seen from FIG. 10 that the product is rod-shaped but has a length of about 5 μm and a width of about 1 μm, and contains many broken impurities therein.
The pH value is too low, so that the nano-scale MIL-47(V) metal organic framework compound cannot be obtained, and the finally generated MIL-47(V) metal organic framework compound crystal is too large, so that the crystal structure and the morphology of the compound are influenced, and a mixed phase is generated.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will 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, and all of them should be covered by the claims of the present invention.
Claims (6)
1. A method for preparing a nanoscale MIL-47(V) metal-organic framework compound, which is characterized by comprising the following steps:
adding vanadium disulfide and terephthalic acid into a methanol solution, uniformly mixing, adding acid to adjust the pH value to 1-2, reacting for 12-36h at the temperature of 140-180 ℃ by a solvothermal method, washing, filtering, drying to obtain a powdery product, and finally preserving the heat of the powdery product for 12-36h at the temperature of 200-300 ℃;
the mass ratio of the vanadium disulfide to the terephthalic acid to the methanol solution is 1:1-10: 200;
the MIL-47(V) metal organic framework compound is rod-shaped, the length is 150-300nm, and the width is 15-45 nm.
2. The method according to claim 1, wherein the volume fraction of the methanol solution is 95% or more.
3. The method of claim 1, wherein the blending specifically comprises: performing ultrasonic treatment in an ultrasonic machine with power of more than 100W for more than 5 min.
4. The method of claim 1, wherein the acid is one of hydrochloric acid or dilute sulfuric acid.
5. The method according to claim 1, wherein the washing is in particular: washing with methanol or ethanol.
6. The method according to claim 1, characterized in that the drying is in particular: drying at 40-80 deg.C under vacuum to constant weight.
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| CN109243829A (en) * | 2018-09-19 | 2019-01-18 | 东莞理工学院 | A kind of application of dye-sensitized cell electrode and preparation method thereof and MIL-47 material |
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| CN109243829A (en) * | 2018-09-19 | 2019-01-18 | 东莞理工学院 | A kind of application of dye-sensitized cell electrode and preparation method thereof and MIL-47 material |
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