CN111440326A - Nanoscale MI L-47 (V) metal organic framework compound and preparation method thereof - Google Patents
Nanoscale MI L-47 (V) metal organic framework compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nanometer MI L-47 (V) metal organic framework compound and a preparation method thereof, belonging to the technical field of nanometer materials.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nano MI L-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 molecular-level topological structure adjustability and the diversity of metals and organic ligands, various structures and different classes of metal-organic framework compounds are widely prepared in recent years, and the unique characteristics thereofMI L-47 (V) is a metal organic framework material which is firstly synthesized and reported in 2002 by Farrey project group of Lavartin research institute in France, takes vanadium as a metal center, takes 1, 4-dimethyl phthalate as a ligand and has a three-dimensional framework structure with diamond-shaped pore channels, and has high BET specific surface area (900 m) of the metal organic framework material2G), larger pore diameter
In particular high thermal stability, which makes it of interest to researchers, a great variety of applications around it have been explored successively, in particular in the field of gas adsorption storage and separation, and MI L-47 (V) has shown great application value, especially for H2、CH4、H2The excellent adsorption and storage properties of gases such as S further increase the enthusiasm of researchers for research.
Since organic ligands must coordinate to metal ions, self-assemble, etc. in solution to form metal-organic frameworks, in metal-organic frameworks centered on vanadium, traditional inorganic vanadates, such as sodium vanadate (Na)3VO4) Although there has been recent research on MI L-47 (V), most reports continue to use the most primitive method reported in the F é rey group 2002 for the preparation of MI L-47 (V). in this method, vanadium trichloride (VCl) was used to obtain vanadium ions alone in solution3) As a source of vanadium, VCl3In addition, the severe reaction conditions of the method also enable the prepared MI L-47 (V) crystal powder to show a huge rod-shaped structure (about 1um thick), and the large particle structure also limits the MI L-47 (V) to fully exert the application potential.
Disclosure of Invention
In view of the above, the present invention provides a nanoscale MI L-47 (V) metal-organic framework compound, and a preparation method of the nanoscale MI L-47 (V) metal-organic framework compound.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a nanoscale MI L-47 (V) metal-organic framework compound is rod-shaped, and has a length of 150-300nm and a width of 15-45 nm.
2. The preparation method of the nanoscale MI L-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 the nanometer MI L-47 (V) metal organic framework compound and the preparation method thereof, in the method, the cheap, safe and chemical property mild vanadium disulfide 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, and terephthalic acid and the vanadium ions are coordinated to form the nanometer MI L-47 (V) metal organic framework compound, so that the V with high toxicity, high activity, strong irritation and high price is avoided on one handCl3The use of (1) makes the whole preparation process safe and nontoxic and low in cost, and on the other hand, avoids the defect that the finally prepared metal organic framework compound has larger size due to violent reaction in the prior art, ensures that the finally prepared MI L-47 (V) metal organic framework compound has the length of 150-300nm and the width of 15-45nm, wherein the pH value is adjusted to 1-2 because the vanadium disulfide cannot be effectively dissolved when the pH value exceeds 2, so that enough free vanadium ions cannot be formed in a reaction system, the purity of the finally prepared compound cannot be ensured, the product is more complex and is doped with vanadium disulfide which is not completely reacted, and when the pH value is less than 1, the vanadium disulfide is dissolved too fast, so that the finally generated MI L-47 (V) metal organic framework compound has overlarge crystals, the crystal structure and the morphology of the compound are influenced, and a heterogeneous phase is generated.
In addition, the method uses a methanol solution as a solvent, the high polarity of the methanol solution can ensure the dissolution of terephthalic acid, and the weak acidity presented by hydroxyl in the molecular formula of the methanol is more favorable for the reaction, so that the finally prepared MI L-47 (V) metal organic framework compound can be ensured to present a more uniform and regular appearance.
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 representation of the crystal structure of the nanoscale MI L-47 (V) metal-organic framework compounds prepared in examples 1-3;
FIG. 2 is an XRD pattern of the nanoscale MI L-47 (V) metal-organic framework compound prepared in example 1;
FIG. 3 is a field emission scanning electron microscope image of the nanoscale MI L-47 (V) metal-organic framework compound prepared in example 1;
FIG. 4 is a thermogravimetric plot of the nanoscale MI L-47 (V) metal-organic framework compounds prepared in example 1;
FIG. 5 is a field emission scanning electron microscope image of the nanoscale MI L-47 (V) metal-organic framework compound prepared in example 2;
FIG. 6 is a field emission scanning electron microscope photograph of the nanoscale MI L-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 MI L-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 1 mol/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 MI L-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 MI L-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 1 mol/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 of the crystal structure of the nanoscale MI L-47 (V) metal-organic framework compounds prepared in examples 1-3, wherein each V atom is coordinated by an 8-face body formed by 6O atoms, as can be seen from FIG. 1.
FIG. 2 is an XRD pattern of the nano-sized MI L-47 (V) metal-organic framework compound prepared in example 1, and from FIG. 2, the nano-sized MI L-47 (V) metal-organic framework compound has an ordered crystal structure, which corresponds to a standard card.
FIG. 3 is a scanning electron microscope image of a field emission scanning electron microscope showing the nano-scaled MI L-47 (V) MOM prepared in example 1, and it can be seen from FIG. 3 that the primary structure of the nano-scaled MI L-47 (V) MOM is in a bulk state, but the bulk state is composed of a rod-shaped MI L-47 (V) MOM with a length of 150-300nm and a width of 15-45 nm.
FIG. 4 is a thermogravimetric analysis graph of the nanoscale MI L-47 (V) metal-organic framework compound prepared in example 1, and it can be seen from FIG. 4 that even though the nanoscale MI L-47 (V) metal-organic framework compound prepared exhibits a nanoscale crystal structure, it still exhibits high thermal stability.
FIG. 5 is a SEM image of the nanoscale MI L-47 (V) MOM prepared in example 2, and it can be seen from FIG. 5 that the primary structure of the nanoscale MI L-47 (V) MOM is in a bulk form, but the bulk form is composed of the rod-shaped MI L-47 (V) MOM with 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 showing the nanoscale MI L-47 (V) metal-organic framework compound prepared in example 3, and it can be seen from FIG. 6 that the nanoscale MI L-47 (V) metal-organic framework compound has a primary structure of a spherical structure, but the spherical structure is composed of rod-shaped MI L-47 (V) metal-organic framework compounds with a length of 150-300nm and a width of 15-45 nm.
Comparative example 1
The difference from example 1 is that 1 mol/L of hydrochloric acid is not added to adjust the pH.
FIG. 7 is an XRD pattern of the product, and from FIG. 7, it can be seen that the product is not MI L-47 (V) metal organic framework compound crystals.
FIG. 8 is a SEM image of the product, which is agglomerated and disordered, and no MI L-47 (V) metal-organic framework compound crystal can be observed under high magnification condition, and the incompletely reacted vanadium disulfide is doped in the product, as can be seen from FIG. 8.
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 1 mol/L of hydrochloric acid is added to adjust the pH to 0.
FIG. 9 is the 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 MI L-47 (V) metal organic framework, which indicates 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 nanometer MI L-47 (V) metal-organic framework compound cannot be obtained, and the finally generated MI L-47 (V) metal-organic framework compound has too large crystals, influences the crystal structure and morphology and generates a heterogeneous phase.
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 (8)
1. A nanoscale MI L-47 (V) metal-organic framework compound is characterized in that the MI L-47 (V) metal-organic framework compound is rod-shaped, the length of the rod-shaped metal-organic framework compound is 150-300nm, and the width of the rod-shaped metal-organic framework compound is 15-45 nm.
2. The method of claim 1 for the preparation of nanoscale MI L-47 (V) metal organic framework compounds, said method comprising:
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 ℃.
3. The method of claim 2, wherein the mass ratio of the vanadium disulfide, terephthalic acid, and methanol solution is from 1:1 to 10: 200.
4. The method according to claim 2, wherein the volume fraction of the methanol solution is 95% or more.
5. The method of claim 2, wherein the blending specifically comprises: performing ultrasonic treatment in an ultrasonic machine with power of more than 100W for more than 5 min.
6. The method of claim 2, wherein the acid is one of hydrochloric acid or dilute sulfuric acid.
7. The method according to claim 2, wherein the washing is in particular: washing with methanol or ethanol.
8. The method according to claim 2, characterized in that the drying is in particular: drying at 40-80 deg.C under vacuum to constant weight.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113831544A (en) * | 2021-09-22 | 2021-12-24 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
| CN114348991A (en) * | 2022-01-24 | 2022-04-15 | 河北工业大学 | Preparation method and application of two-dimensional vanadium-based metal organic framework series film-based interlayer material |
| CN115490213A (en) * | 2022-08-30 | 2022-12-20 | 华东师范大学 | Metal organic framework derived VSe 2 Material, preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113831544A (en) * | 2021-09-22 | 2021-12-24 | 同济大学 | Non-linear nano hybrid material of titanium carbide quantum dots and vanadium metal organic framework and preparation method thereof |
| CN114348991A (en) * | 2022-01-24 | 2022-04-15 | 河北工业大学 | Preparation method and application of two-dimensional vanadium-based metal organic framework series film-based interlayer material |
| CN115490213A (en) * | 2022-08-30 | 2022-12-20 | 华东师范大学 | Metal organic framework derived VSe 2 Material, preparation method and application thereof |
| CN115490213B (en) * | 2022-08-30 | 2023-08-18 | 华东师范大学 | VSe derived from metal-organic frameworks 2 Material, preparation method and application thereof |
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