CN111647119B - Method for preparing covalent organic framework material by using mechanical ball milling method - Google Patents
Method for preparing covalent organic framework material by using mechanical ball milling method Download PDFInfo
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a method for preparing covalent organic framework materials by utilizing a mechanical ball milling method, which comprises the steps of putting 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde raw materials into a stainless steel ball milling tank under the protection of nitrogen or argon atmosphere, uniformly mixing, and adding ball milling liquid; at room temperature, adding stainless steel medium small balls according to a ball-to-material ratio of 10:1, and adding a ball milling tank into a planetary ball mill; and washing the product powder after the ball milling reaction by using a washing solution, drying for 12h at 90 ℃, and heating to 120 ℃ for drying for 3h to obtain the covalent organic framework material. Compared with other preparation methods of covalent organic framework materials, the mechanical ball milling method has the advantages of environmental protection, energy conservation, short reaction time, simple operation and low reaction condition cost, and the prepared material has obvious effect of removing organic matters and suspended matters in water.
Description
Technical Field
The invention belongs to the technical field of high-molecular organic porous materials, and particularly relates to a method for preparing a covalent organic framework material by using a mechanical ball milling method.
Background
Covalent organic framework materials (COFs) are constructed by linking light elements C, O, N, B and the like through Covalent bonds, are ingeniously constructed by strong Covalent bonds and organic construction units, are organic porous materials with ordered crystal structures, have uniform pore sizes, and are also called as 'organic zeolites'. Compared with inorganic porous materials, the building units are organic micromolecules which are wide in source and various in variety, so that the building units are diversified, and the structure and the function of the target material can be conveniently regulated and controlled through the building units; the structure is connected by covalent bonds to form a space network structure, and has better thermal stability and chemical stability; it is composed of light elements (C, H, O, N and B, etc.) and has the characteristic of low density; as a crystalline material, COFs has large specific surface area and regular structure, so that the material is widely applied to the fields of gas adsorption and storage, gas separation, catalysis and the like.
The covalent organic framework material is an ordered porous crystalline material formed by reversible polymerization under thermodynamic control, is generally prepared by a thermodynamic reversible reaction, and is beneficial to forming a long-range ordered structure. The main preparation methods at present are solvothermal methods, exemplified thermal methods, microwave irradiation methods and surface-controlled synthesis methods, of which solvothermal synthesis methods are the most common.
The covalent organic framework material prepared by the solvothermal synthesis method has good universality on COFs materials, but has long synthesis time, needs a large amount of organic solvent in the synthesis and post-treatment processes, has harsh synthesis experimental conditions, and usually needs higher temperature conditions and Pyrex tube container support.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a covalent organic framework material by using a mechanical ball milling method, so as to solve the problems of long synthesis time and large use amount of organic solvent in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
a method of preparing a covalent organic framework material comprising the steps of:
under the condition of inert gas, 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde are used as raw materials, are uniformly mixed, added with ball milling liquid, and are subjected to ball milling reaction to obtain the covalent organic framework material.
Further, the molar ratio of the 2,3,5, 6-tetramethyl-p-phenylenediamine to the trimesic aldehyde is 1:1 to 2.
Further, the temperature of the ball-milling reaction is 0-40 ℃, the ball-milling rotation speed is 100-500 rpm/min, and the ball-milling time is 100-300 min.
Further, the ball milling liquid is p-toluenesulfonic acid, and the amount of the p-toluenesulfonic acid is 1-5 mL.
Further, the grinding balls for the grinding ball reaction are stainless steel balls; the ratio of the total mass of the mixture of the 2,3,5, 6-tetramethyl-p-phenylenediamine and the trimesic aldehyde to the total mass of the grinding balls is 1: 10.
Further, the inert gas is nitrogen or argon.
Further, the method further comprises:
and after the ball milling reaction is finished, taking out the product in an inert atmosphere, washing the product with different washing solutions, drying the product at 90 ℃ for 12h, and heating to 120 ℃ for drying for 3h to obtain the covalent organic framework material.
Further, the washing liquid is trimethylbenzene, ultrapure water and acetone.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with a solvent thermal synthesis method, the method has the advantages of environmental protection, energy conservation, short reaction time, simple operation and low reaction condition cost.
(2) The organic framework material COF-m prepared by the method has a good effect of removing pollutants such as particulate matters and Natural Organic Matters (NOM) in water, and the effect is obviously reduced after 5 times of repeated utilization, so that the method has an important significance on control of related pollution indexes.
Drawings
FIG. 1 is a schematic synthesis of the covalent organic framework material COF-m of example 1;
FIG. 2 is a PXRD pattern of the covalent organic framework material COF-m of example 1;
FIG. 3 is an IR spectrum of the covalent organic framework material COF-m of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
S1, under the protection of nitrogen gas, uniformly mixing 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde according to the molar ratio of 1:1, adding into a stainless steel ball milling tank, and adding 1mL of p-toluenesulfonic acid ball milling solution;
s2, putting the ball milling pot into a planetary ball mill at room temperature of 0 ℃. Adding stainless steel medium small balls into a ball mill according to a ball-to-material ratio of 10:1, and performing ball milling reaction at a rotating speed of 100r/min for 100 min;
and S3, removing the product in a nitrogen atmosphere after the reaction is finished, washing the product with trimethylbenzene, ultrapure water and acetone in sequence, drying the product at 90 ℃ for 12 hours, and heating to 120 ℃ for 3 hours to obtain the covalent organic framework material COF-m. The specific synthetic steps are shown in figure 1.
Application of covalent organic framework material COF-m in adsorption of pollutants in water: in a 250mL Erlenmeyer flask, 100mg COF-m material was added to 100mL of raw tap water with 1% H2SO4After the pH value is adjusted to 7.0, the water sample is automatically vibrated for 1 hour at 150r/min, and the processing result is as follows:
table 1 use of covalent organic framework materials COF-m in water treatment results 1
| Soluble organic carbon mg/L | UV254 cm-1 | Soluble organic nitrogen mg/L | |
| Raw water sample | 2.7 | 0.062 | 0.49 |
| Treatment for 1h | 0.7 | 0.009 | 0.16 |
| Recycling for 5 times | 0.8 | 0.011 | 0.18 |
| Removal rate | 74.07%（70.37%） | 85.48%（82.26%） | 67.35%（63.27%） |
Fig. 2 is a PXRD pattern corresponding to this example, from which it can be seen that two major characteristic peaks are observed at 2 θ =9.3 and 31.8, indicating that the covalent organic framework material has an ordered crystal structure.
FIG. 3 is a Fourier infrared spectrum corresponding to this example, which is shown at 1625cm-1A distinct-C = N-bond vibrational peak was formed, indicating successful formation of the covalent organic framework material.
Example 2
S1, under the protection of nitrogen atmosphere, uniformly mixing 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde raw materials according to the molar ratio of 1:1, adding the mixture into a stainless steel ball milling tank, and adding 1mL of p-toluenesulfonic acid ball milling solution;
s2, putting the ball milling pot into a planetary ball mill at room temperature of 20 ℃. Adding stainless steel medium small balls into a ball mill according to a ball-to-material ratio of 10:1, and performing ball milling reaction at a rotating speed of 100r/min for 200 min;
and S3, removing the product in a nitrogen atmosphere after the reaction is finished, washing the product with trimethylbenzene, ultrapure water and acetone in sequence, drying the product at 90 ℃ for 12 hours, and heating to 120 ℃ for 3 hours to obtain the covalent organic framework material COF-m.
Application of covalent organic framework material COF-m in adsorption of pollutants in water: in a 250mL Erlenmeyer flask, 100mg COF-m material was added to 100mL of raw tap water with 1% H2SO4After the pH value is adjusted to 7.0, the water sample is automatically vibrated for 1 hour at 150r/min, and the processing result is as follows:
TABLE 2 application of covalent organic framework materials COF-m in Water treatment results 2
| Soluble organic carbon mg/L | UV254 cm-1 | Soluble organic nitrogen mg/L | |
| Raw water sample | 2.8 | 0.065 | 0.52 |
| Treatment for 1h | 0.8 | 0.010 | 0.18 |
| Recycling for 5 times | 0.9 | 0.013 | 0.19 |
| Removal rate | 71.43%（67.86%） | 84.62%（80.00%） | 65.38%（63.46%） |
Example 3
S1, under the protection of nitrogen atmosphere, uniformly mixing 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde raw materials according to the molar ratio of 2:3, adding the mixture into a stainless steel ball milling tank, and adding 3mL of p-toluenesulfonic acid ball milling solution;
s2, putting the ball milling pot into a planetary ball mill at room temperature of 20 ℃. Adding stainless steel medium balls into a ball mill according to a ball-to-material ratio of 10:1, and performing ball milling reaction at a rotating speed of 300r/min for 200 min;
and S3, removing the product in a nitrogen atmosphere after the reaction is finished, washing the product with trimethylbenzene, ultrapure water and acetone in sequence, drying the product at 90 ℃ for 12 hours, and heating to 120 ℃ for 3 hours to obtain the covalent organic framework material COF-m.
Application of covalent organic framework material COF-m in adsorption of pollutants in water: in a 250mL Erlenmeyer flask, 100mg COF-m material was added to 100mL of raw tap water with 1% H2SO4After the pH value is adjusted to 7.0, the water sample is automatically vibrated for 1 hour at 150r/min, and the processing result is as follows:
TABLE 3 application of covalent organic framework materials COF-m in Water treatment results 3
| Soluble organic carbon mg/L | UV254 cm-1 | Soluble organic nitrogen mg/L | |
| Raw water sample | 2.7 | 0.061 | 0.53 |
| Treatment for 1h | 0.6 | 0.006 | 0.17 |
| Recycling for 5 times | 0.7 | 0.007 | 0.19 |
| Removal rate | 77.78%（74.07%） | 90.16%（88.52%） | 67.92%（64.15%） |
Example 4
S1, under the protection of nitrogen atmosphere, uniformly mixing 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde raw materials according to the molar ratio of 2:3, adding the mixture into a stainless steel ball milling tank, and adding 3mL of p-toluenesulfonic acid ball milling solution;
s2, putting the ball milling pot into a planetary ball mill at room temperature of 20 ℃. Adding stainless steel medium balls into a ball mill according to a ball-to-material ratio of 10:1, and performing ball milling reaction at a rotating speed of 300r/min for 200 min;
and S3, removing the product in a nitrogen atmosphere after the reaction is finished, washing the product with trimethylbenzene, ultrapure water and acetone in sequence, drying the product at 90 ℃ for 12 hours, and heating to 120 ℃ for 3 hours to obtain the covalent organic framework material COF-m.
Application of covalent organic framework material COF-m in adsorption of pollutants in water: in a 250mL Erlenmeyer flask, 100mg COF-m material was added to 100mL of raw tap water with 1% H2SO4After the pH value is adjusted to 7.0, the water sample is automatically vibrated for 1 hour at 150r/min, and the processing result is as follows:
table 4 use of covalent organic framework materials COF-m in aqueous treatment results 4
| Soluble organic carbon mg/L | UV254 cm-1 | Soluble organic nitrogen mg/L | |
| Raw water sample | 3.0 | 0.068 | 0.50 |
| Treatment for 1h | 0.8 | 0.009 | 0.16 |
| Recycling for 5 times | 1.0 | 0.010 | 0.17 |
| Removal rate | 73.33%（66.67%） | 86.76%（85.29%） | 68.00%（66.00%） |
Example 5
S1, under the protection of nitrogen atmosphere, uniformly mixing 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde raw materials according to the molar ratio of 2:3, adding the mixture into a stainless steel ball milling tank, and adding 5mL of p-toluenesulfonic acid ball milling solution;
s2, putting the ball milling pot into a planetary ball mill at room temperature of 20 ℃. Adding stainless steel medium balls into a ball mill according to a ball-to-material ratio of 10:1, and performing ball milling reaction at a rotating speed of 500r/min for 100 min;
and S3, removing the product in a nitrogen atmosphere after the reaction is finished, washing the product with trimethylbenzene, ultrapure water and acetone in sequence, drying the product at 90 ℃ for 12 hours, and heating to 120 ℃ for 3 hours to obtain the covalent organic framework material COF-m.
Application of covalent organic framework material COF-m in adsorption of pollutants in water: in a 250mL Erlenmeyer flask, 100mg COF-m material was added to 100mL of raw tap water with 1% H2SO4After the pH value is adjusted to 7.0, the water sample is automatically vibrated for 1 hour at 150r/min, and the processing result is as follows:
TABLE 5 application of covalent organic framework materials COF-m in Water treatment results 5
| Soluble organic carbon mg/L | UV254 cm-1 | Soluble organic nitrogen mg/L | |
| Raw water sample | 2.9 | 0.063 | 0.49 |
| Treatment for 1h | 0.8 | 0.008 | 0.15 |
| Recycling for 5 times | 0.8 | 0.009 | 0.15 |
| Removal rate | 72.41%（72.41%） | 87.30%（85.71%） | 69.39%（69.39%） |
Example 6
S1, under the protection of argon atmosphere, uniformly mixing 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde raw materials according to the molar ratio of 2:4, adding the mixture into a stainless steel ball milling tank, and adding 3mL of p-toluenesulfonic acid ball milling solution;
s2, putting the ball milling pot into a planetary ball mill at room temperature of 40 ℃. Adding stainless steel medium balls into a ball mill according to a ball-to-material ratio of 10:1, and performing ball milling reaction at a rotating speed of 300r/min for 300 min;
and S3, removing the product in an argon atmosphere after the reaction is finished, washing the product with trimethylbenzene, ultrapure water and acetone in sequence, drying the product at 90 ℃ for 12 hours, and heating to 120 ℃ for 3 hours to obtain the covalent organic framework material COF-m.
Application of covalent organic framework material COF-m in adsorption of pollutants in water: in a 250mL Erlenmeyer flask, 100mg COF-m material was added to 100mL of raw tap water with 1% H2SO4After the pH value is adjusted to 7.0, the water sample is automatically vibrated for 1 hour at 150r/min, and the processing result is as follows:
TABLE 6 application of covalent organic framework materials COF-m in Water treatment results 6
| Soluble organic carbon mg/L | UV254 cm-1 | Soluble organic nitrogen mg/L | |
| Raw water sample | 2.7 | 0.064 | 0.48 |
| Treatment for 1h | 0.5 | 0.010 | 0.13 |
| Recycling for 5 times | 0.6 | 0.010 | 0.14 |
| Removal rate | 81.48%（77.78%） | 84.38%（84.38%） | 72.92%（70.83%） |
The treatment of the raw water of tap water with the organic framework material COF-m in examples 1 to 6 gave: the organic framework material prepared by the method has good removal effect on particulate matters, Natural Organic Matters (NOM) and the like in water, and the effect is obviously reduced after 5 times of repeated utilization, so that the organic framework material has important significance on control of related pollution indexes.
The invention improves the ball milling parameters, improves the stability of the covalent organic framework material synthesized by the mechanical ball milling method, and thus improves the preparation quality and efficiency of the COFs to the maximum extent. The method is simple to operate and rapid to synthesize. Compared with a solvent thermal synthesis method, the mechanical ball milling method has the advantages of green and environment-friendly preparation process, simple synthesis operation and low cost, and provides possibility for the wide production of COFs.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (5)
1. A method of preparing a covalent organic framework material, comprising the steps of:
under the condition of inert gas, 2,3,5, 6-tetramethyl-p-phenylenediamine and trimesic aldehyde are used as raw materials, are uniformly mixed, are added with ball milling liquid, and are subjected to ball milling reaction to obtain a covalent organic framework material;
the temperature of the grinding ball reaction is 0-40 ℃, the grinding rotation speed is 100-;
the ball milling liquid is p-toluenesulfonic acid, and the amount of the p-toluenesulfonic acid is 1-5 mL;
the grinding balls for the grinding ball reaction are stainless steel balls; the ratio of the total mass of the mixture of the 2,3,5, 6-tetramethyl-p-phenylenediamine and the trimesic aldehyde to the total mass of the grinding balls is 1: 10.
2. The method of claim 1, wherein the molar ratio of 2,3,5, 6-tetramethylp-phenylenediamine to trimesic aldehyde is 1:1 to 2.
3. The method of claim 1, wherein the inert gas is nitrogen or argon.
4. The method of claim 1, further comprising:
and after the ball milling reaction is finished, taking out the product in an inert atmosphere, washing the product with different washing solutions, drying the product at 90 ℃ for 12h, and heating to 120 ℃ for drying for 3h to obtain the covalent organic framework material.
5. The method of claim 4, wherein the washing solution is trimethylbenzene, ultrapure water, and acetone.
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