CN112851938A - One-dimensional organic nano material and preparation method thereof - Google Patents

One-dimensional organic nano material and preparation method thereof Download PDF

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CN112851938A
CN112851938A CN202110032279.1A CN202110032279A CN112851938A CN 112851938 A CN112851938 A CN 112851938A CN 202110032279 A CN202110032279 A CN 202110032279A CN 112851938 A CN112851938 A CN 112851938A
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dimensional organic
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CN112851938B (en
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林海波
刘富
陈佳萍
李贵亮
韩秋
王建强
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
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Abstract

The invention relates to a one-dimensional organic nano material which is a covalent triazine organic framework material. The invention also provides a preparation method of the one-dimensional organic nano material, which comprises the following steps: mixing polycyanobenzene, a catalyst and a solvent, and carrying out polymerization reaction at a first temperature to obtain an intermediate product containing a covalent triazine organic framework material, wherein the triazine organic framework material is an organic nanosheet; and cooling the intermediate product to a second temperature and mixing the intermediate product with an inducer to obtain the one-dimensional organic nano material. The preparation method of the one-dimensional organic nano material can realize low-temperature preparation and low energy consumption, and meanwhile, the one-dimensional organic nano material has excellent adsorption, catalysis, reinforcement and other properties, and has good interface compatibility and dispersion performance with polymer materials.

Description

One-dimensional organic nano material and preparation method thereof
Technical Field
The invention relates to the field of nano materials, in particular to a one-dimensional organic nano material and a preparation method thereof.
Background
The nano material is a special material with at least one dimension in a three-dimensional space in a nano size, and the material often shows physicochemical properties different from those of a macroscopic material due to small constituent unit size and large interface proportion. Among them, the nanotube is a one-dimensional tubular nanomaterial with a radial dimension of nanometer level (less than 100 nm) and an axial dimension of micrometer level, has many special properties of mechanics, electricity, chemistry, etc., and has received extensive attention and research. However, the conventional nanotubes are generally inorganic nanotubes, such as carbon nanotubes, boron nitride nanotubes, silicon nanotubes, etc., and the preparation of these inorganic nanotubes usually requires a high temperature environment as high as several hundred degrees celsius or even over 1000 ℃, which results in very high energy consumption for production.
Disclosure of Invention
In view of the above, it is necessary to provide a one-dimensional organic nanomaterial with low synthesis temperature and low energy consumption and a preparation method thereof.
A one-dimensional organic nano material is a covalent triazine organic framework material.
In one embodiment, the one-dimensional organic nanomaterial includes at least one of organic nanotubes and organic nanofibers.
In one embodiment, the axial dimension of the one-dimensional organic nanomaterial is 10-1000 times the radial dimension; the axial size of the one-dimensional organic nano material is 0.5-5 mu m, and the radial size of the one-dimensional organic nano material is 5-100 nm.
The one-dimensional organic nano material has excellent performances of adsorption, catalysis, reinforcement and the like, and meanwhile, the one-dimensional organic nano material is an organic material and has good interface compatibility with a polymer material. Therefore, compared with inorganic nanotubes, the one-dimensional organic nanomaterial disclosed by the invention has more excellent dispersing performance in a polymer material and has wider application prospects in the fields of polymer functional materials, coatings, functional film materials and the like.
A preparation method of the one-dimensional organic nano material comprises the following steps:
mixing polycyanobenzene, a catalyst and a solvent, and carrying out polymerization reaction at a first temperature to obtain an intermediate product containing a covalent triazine organic framework material, wherein the covalent triazine organic framework material is a two-dimensional organic nanosheet;
and cooling the intermediate product to a second temperature, and mixing the intermediate product with an inducer to obtain the one-dimensional organic nano material.
In one embodiment, the inducer is selected from an alcohol or an aqueous alcohol solution, wherein the alcohol comprises at least one of methanol, ethanol, isopropanol, and n-propanol.
In one embodiment, the first temperature is 80 ℃ to 120 ℃ and the second temperature is less than or equal to 60 ℃.
In one embodiment, the polycyanobenzene comprises at least one of dicyanobenzene, tricyanobenzene; wherein the dicyanobenzene comprises at least one of 4, 4' -biphenylcarbonitrile, tetrafluoroterephthalonitrile and 2, 5-dichloroterephthalonitrile, and the tricyanobenzene comprises at least one of 1,3, 4-benzenetricyano group and 1,3, 5-benzenetricyano group.
In one embodiment, the solvent comprises at least one of dimethylformamide, dimethylsulfoxide, acetone, dichloromethane, and tetrahydrofuran.
In one embodiment, the catalyst comprises at least one of trifluoromethanesulfonic acid, fluorine-free ethanesulfonic acid, trifluoroacetic acid, pentafluoroacetic acid, heptafluoropropionic acid.
In one embodiment, the solvent, the catalyst, the polycyanobenzene and the inducer are mixed in the following ratio: 3mL-10mL of the catalyst, 0.5g-2g of the polycyanobenzene and 10mL-100mL of the inducer are prepared in each 100mL of the solvent.
According to the preparation method of the one-dimensional organic nanomaterial, firstly, the covalent triazine organic framework material is obtained by catalyzing poly-cyanobenzene to perform polymerization reaction, wherein the covalent triazine organic framework material is an organic nanosheet, then, an inducer is used for promoting the organic nanosheet to release interface stress and break interface charge balance at the same time, the organic nanosheet is induced to curl, and finally, the one-dimensional organic nanomaterial is formed, so that the preparation of the one-dimensional organic nanomaterial is realized.
In addition, compared with the high-temperature synthesis condition that the one-dimensional inorganic nano material such as a carbon nano tube, a boron nitride nano tube, a silicon nano tube and the like is up to hundreds of degrees centigrade and even more than 1000 degrees centigrade, in the preparation method of the one-dimensional organic nano material, the organic nano sheet can be prepared at the temperature of below 120 degrees centigrade, and when the inducer is used for inducing the organic nano sheet to be curled into the one-dimensional organic nano material, the temperature is further lower than the synthesis temperature of the organic nano sheet. Therefore, the preparation method of the one-dimensional organic nano material has the advantages of low energy consumption, high efficiency, energy conservation and environmental protection.
Drawings
FIG. 1 is a transmission electron micrograph of a one-dimensional organic nanomaterial obtained in example 1;
FIG. 2 is an enlarged photograph of a TEM image of the one-dimensional organic nanomaterial obtained in example 1;
FIG. 3 is an infrared spectrum of the one-dimensional organic nanomaterial obtained in example 1;
FIG. 4 is a transmission electron micrograph of an organic powder material obtained in comparative example 1;
FIG. 5 is a transmission electron micrograph of the one-dimensional organic nanomaterial obtained in example 2;
FIG. 6 is a TEM image of the one-dimensional organic nanomaterial obtained in example 3;
FIG. 7 is an enlarged photograph of a TEM image of the one-dimensional organic nanomaterial obtained in example 3;
FIG. 8 is a TEM image of the one-dimensional organic nanomaterial obtained in example 4.
Detailed Description
The one-dimensional organic nano-material and the preparation method thereof provided by the present invention will be further explained below.
The invention provides a one-dimensional organic nano material which is a covalent triazine organic framework material.
In one or more embodiments, the one-dimensional organic nanomaterial includes at least one of organic nanotubes and organic nanofibers, preferably organic nanotubes.
In one or more embodiments, the one-dimensional organic nanomaterials have an axial dimension that is 10 to 1000 times the radial dimension. The axial size of the one-dimensional organic nano material is 0.5-5 μm, preferably 0.5-3 μm; the radial size of the one-dimensional organic nano material is 5nm-100nm, preferably 5nm-50 nm.
The one-dimensional organic nano material has excellent performances of adsorption, catalysis, reinforcement and the like, and meanwhile, the one-dimensional organic nano material is an organic material and has good interface compatibility with a polymer material.
Therefore, compared with the one-dimensional inorganic nano material, the one-dimensional organic nano material has more excellent dispersing performance in a polymer material and has wider application prospect in the fields of polymer functional materials, coatings, functional film materials and the like.
The invention also provides a preparation method of the one-dimensional organic nano material, which comprises the following steps:
s1, mixing polycyanobenzene, a catalyst and a solvent, and carrying out a polymerization reaction at a first temperature to obtain an intermediate product containing a covalent triazine organic framework material, wherein the covalent triazine organic framework material is an organic nanosheet;
and S2, cooling the intermediate product to a second temperature, mixing the intermediate product with an inducer, and obtaining the one-dimensional organic nano material at the second temperature.
In step S1, the polycyanobenzene includes at least one of dicyanobenzene and tricyanobenzene; wherein the dicyanobenzene comprises at least one of 4, 4' -biphenylcarbonitrile, tetrafluoroterephthalonitrile, 2, 5-dichloroterephthalonitrile; the tricyanobenzene includes at least one of 1,3, 4-benzene tricyano group and 1,3, 5-benzene tricyano group.
In one or more embodiments, the solvent comprises at least one of dimethylformamide, dimethylsulfoxide, acetone, dichloromethane, tetrahydrofuran, preferably dichloromethane.
In one or more embodiments, the catalyst comprises at least one of triflic acid, non-fluorinated ethanesulfonic acid, trifluoroacetic acid, pentafluoroacetic acid, heptafluoropropionic acid, preferably triflic acid. In order to better improve the synthesis yield of the covalent triazine organic framework material, the purity of the catalyst is preferably greater than or equal to 90%.
In one or more embodiments, the solvent, the catalyst, and the polycyanobenzene are in the following proportions: 3mL to 10mL of the catalyst and 0.5g to 2g of the polycyanobenzene per 100mL of the solvent.
In the actual reaction process, firstly adding a catalyst into a reaction kettle, then heating to a first temperature, and stirring to enable the catalyst to form a plurality of fine catalyst droplets; and then, adding the mixed solution of the polycyanobenzene and the solvent into the catalyst, and continuously stirring to react for 3-10 h.
Specifically, during agitation, the solvent and catalyst droplets may form interfacial contacts, such as: dichloromethane and trifluoromethanesulfonic acid are two immiscible substances and form interfacial contact during stirring. At the contact interface of the fine liquid drops, the catalyst can catalyze the polyreaction of the polycyanobenzene to generate the nano-flaky covalent triazine organic framework material. The multi-site reaction of numerous fine interfaces can be regulated and controlled by regulating the reaction conditions such as the purity and the proportion of raw materials, the reaction time and the like, so that the control on the synthesis rate and the transverse dimension of the organic nano-sheets is synchronously realized, and the regulation and control on the axial dimension of the one-dimensional organic nano-material are further realized.
In addition, in the stirring process, the stirring speed has important influence on the size of the organic nanosheets, and when the stirring speed is low, the shearing acting force applied to a solution system in the reaction process can be weakened, so that the organic nanosheets can grow towards the large-size direction, and the organic nanosheets with large transverse size can be obtained; on the contrary, the organic nano-sheet with smaller transverse dimension is obtained, but the yield of the organic nano-sheet can be improved. Therefore, in practical application, in order to better control the transverse dimension and the yield of the organic nanosheets and further realize the regulation and control of the axial dimension and the yield of the one-dimensional organic nanomaterial, the stirring speed is preferably 100rpm to 500rpm, and more preferably 100rpm to 300 rpm.
In order to better increase the yield of organic nanoplatelets, in one or more embodiments, the first temperature is between 80 ℃ and 120 ℃, preferably between 90 ℃ and 110 ℃. Meanwhile, the low-temperature preparation of the organic nanosheet is realized, and the energy consumption in the preparation process is low.
In step S2, the inducer is selected from alcohol or an aqueous solution of alcohol, wherein the alcohol includes at least one of methanol, ethanol, isopropanol and n-propanol; wherein the volume concentration of the alcohol in the alcohol aqueous solution is more than or equal to 50% and less than 100%, preferably 75%. The dosage of the inducer is 10mL-100mL per 100mL of the solvent.
In order to better introduce the inducer into the intermediate product, reduce the risk of volatilization of the inducer during the feeding process, and simultaneously maintain the interfacial activity of the organic framework material of the triazine in the intermediate product, the temperature of the intermediate product needs to be reduced to a second temperature which is less than or equal to 60 ℃, and preferably 30-60 ℃.
After the inducer is added, the second temperature and the stirring speed are continuously kept for 10min to 40min, during which, alcohol in the inducer promotes the nano-flaky triazine organic framework material in the intermediate product to release the interface stress, and simultaneously breaks the interface charge balance, induces the nano-flaky triazine organic framework material to curl, and finally forms the suspension containing the one-dimensional organic nano-material.
Further, the control of the curling rate of the organic nanosheets can be realized by controlling the addition amount of alcohol in the inducer: when the addition amount of alcohol is less, the charge balance of the organic nanosheets is slowly broken, the interface stress is slowly released, and then slow and ordered curling motion occurs, so that one-dimensional organic nanomaterials which tend to be solid, namely organic nanofibers, are favorably formed; when the addition amount of alcohol is large, the charge balance of the organic nano-sheet is quickly broken, the interface stress is quickly released, and then quick curling motion is generated, which is beneficial to forming a one-dimensional organic nano-material which tends to be hollow, namely an organic nano-tube.
And filtering, cleaning and drying the suspension to obtain the one-dimensional organic nano material. Because the catalyst in the suspension has strong corrosivity to conventional polymer materials, a separation membrane with stable chemical properties and moderate pore size is preferably selected during filtration, and a polytetrafluoroethylene separation membrane is preferably selected. And after the filtration is finished, obtaining solid powder containing the one-dimensional organic nano material, and then cleaning. The solvent used in the cleaning operation includes at least one of ethanol, deionized water, and Dimethylformamide (DMF), and preferably deionized water. Finally, drying the cleaned solid powder at 80-150 ℃.
Hereinafter, the one-dimensional organic nanomaterial and the method for preparing the same will be further described with reference to the following specific examples.
Example 1
5mL of trifluoromethanesulfonic acid having a purity of 98% was added to a three-necked flask, the temperature was raised to 100 ℃ and the stirring speed was adjusted to 150 rpm. Dissolving 1g of 4, 4' -biphenylcarbonitrile in 100mL of dichloromethane to obtain a mixed solution, then slowly adding the mixed solution into a three-neck flask, mixing with trifluoromethanesulfonic acid, and reacting at a stirring speed of 150rpm for 5 hours to obtain a mixed solution containing organic nanosheets.
And (3) closing the heating switch, cooling the three-neck flask to 60 ℃, measuring 100mL of absolute ethyl alcohol, slowly adding the absolute ethyl alcohol into the three-neck flask, and continuously stirring for 20min to obtain a suspension.
And filtering the obtained suspension through a tetrafluoroethylene filter membrane, washing solid powder on the filter membrane with deionized water, and finally drying the solid powder together with the filter membrane in a 120-DEG C drying oven to obtain the one-dimensional organic nano material.
Fig. 1 is a transmission electron micrograph of the one-dimensional organic nanomaterial in this embodiment, and it can be seen from fig. 1 that the radial size distribution of the obtained one-dimensional organic nanomaterial is about 5nm to 20nm, the axial size distribution is 0.5 μm to 1.5 μm, and the size distribution uniformity is good.
Fig. 2 is an enlarged photograph of a transmission electron microscope photograph of the one-dimensional organic nano material in the present embodiment, and it can be seen from fig. 2 that the obtained organic nano material is an organic nano tube.
FIG. 3 is an infrared spectrum of the one-dimensional organic nano-material in this example, which is 1517.1cm in FIG. 1-1The position is a C ═ N stretching vibration peak, and C ═ N is a main chemical bond of a triazine ring formed by polymerizing 4, 4' -biphenyl formonitrile monomers; 1407.2cm-1And 1358.2cm-1The peak is the vibration peak of the skeleton caused by the conjugation of the triazine skeleton and the benzene ring. Therefore, the material of the organic nanomaterial obtained in this example is a covalent triazine organic framework material.
Comparative example 1
5mL of trifluoromethanesulfonic acid having a purity of 98% was added to a three-necked flask, the temperature was raised to 100 ℃ and the stirring speed was adjusted to 150 rpm. Dissolving 1g of 4, 4' -biphenylcarbonitrile in 100mL of dichloromethane to obtain a mixed solution, then slowly adding the mixed solution into a three-neck flask, mixing with trifluoromethanesulfonic acid, and reacting at a stirring speed of 150rpm for 5 hours to obtain a mixed solution containing organic nanosheets.
And (3) closing the heating switch, cooling the three-neck flask to 60 ℃, measuring 3mL of absolute ethyl alcohol, slowly adding the absolute ethyl alcohol into the three-neck flask, and continuously stirring for 20min to obtain a suspension.
And filtering the obtained suspension through a tetrafluoroethylene filter membrane, washing solid powder on the filter membrane with deionized water, and finally drying the solid powder together with the filter membrane in a 120-DEG C drying oven to obtain dried solid powder.
FIG. 4 is a transmission electron micrograph of the organic powder material of this comparative example, and it can be seen from FIG. 4 that the organic powder material obtained was agglomerated and piled up, and no significant one-dimensional orientation was formed. The reason is that the amount of the added ethanol is too small, the charge balance among the nano sheets cannot be effectively broken, and the release of the interface stress of the nano sheets is incomplete.
Example 2
3mL of 90% pure trifluoromethanesulfonic acid was added to a three-necked flask, the temperature was raised to 120 ℃ and the stirring speed was adjusted to 100 rpm. Dissolving 0.5g of 2, 5-dichloro-terephthalonitrile into 100mL of dichloromethane to obtain a mixed solution, then slowly adding the mixed solution into a three-neck flask to mix with trifluoromethanesulfonic acid, and reacting at a stirring speed of 100rpm for 10 hours to obtain a mixed solution containing organic nanosheets.
And (3) closing the heating switch, cooling the three-neck flask to 30 ℃, measuring 25mL of methanol, slowly adding the methanol into the three-neck flask, and continuously stirring for 40min to obtain a suspension.
And filtering the obtained suspension through a tetrafluoroethylene filter membrane, washing solid powder on the filter membrane with deionized water, and finally drying the solid powder together with the filter membrane in an oven at 80 ℃ to obtain the one-dimensional organic nano material.
Fig. 5 is a transmission electron micrograph of the one-dimensional organic nanomaterial in this embodiment, and it can be seen from fig. 5 that the radial size distribution of the one-dimensional organic nanomaterial obtained in this embodiment is about 25nm to 50nm, the axial size distribution is 1.0 μm to 3.0 μm, and the size distribution uniformity is good.
Example 3
10mL of trifluoromethanesulfonic acid having a purity of 95% was added to a three-necked flask, the temperature was raised to 80 ℃ and the stirring speed was adjusted to 200 rpm. 1g of 4, 4' -biphenylcarbonitrile and 1g of 1,3, 4-benzenetricarboxylic acid are dissolved in 100mL of dichloromethane to obtain a mixed solution, and then the mixed solution is slowly added into a three-neck flask to be mixed with trifluoromethanesulfonic acid, and the mixture is reacted for 3 hours at a stirring speed of 200rpm to obtain a mixed solution containing organic nanosheets.
And (3) closing the heating switch, cooling the three-neck flask to 40 ℃, measuring 10mL of isopropanol, slowly adding the isopropanol into the three-neck flask, and continuously stirring for 25min to obtain a suspension.
And filtering the obtained suspension through a tetrafluoroethylene filter membrane, washing solid powder on the filter membrane with deionized water, and finally drying the solid powder together with the filter membrane in a 100 ℃ oven to obtain the one-dimensional organic nano material.
Fig. 6 is a transmission electron micrograph of the one-dimensional organic nanomaterial in this embodiment, and it can be seen from fig. 6 that the one-dimensional organic nanomaterial obtained in this embodiment has a radial size distribution of about 15nm to 35nm, an axial size distribution of 0.5 μm to 2.0 μm, and a good uniformity of size distribution.
Fig. 7 is a transmission electron micrograph of the one-dimensional organic nanomaterial in this embodiment, and it can be seen from fig. 7 that the one-dimensional organic nanomaterial obtained in this embodiment is an organic nanofiber.
Example 4
7mL of 92% pure trifluoromethanesulfonic acid was added to a three-necked flask, the temperature was raised to 105 ℃ and the stirring speed was adjusted to 300 rpm. Dissolving 1.5g of tetrafluoroterephthalonitrile in 100mL of dichloromethane to obtain a mixed solution, then slowly adding the mixed solution into a three-neck flask to mix with trifluoromethanesulfonic acid, and reacting at a stirring speed of 300rpm for 8 hours to obtain a mixed solution containing organic nanosheets.
And (3) closing the heating switch, cooling the three-neck flask to 50 ℃, measuring a mixed solution of 25mL of methanol, 50mL of absolute ethyl alcohol and 25mL of deionized water, slowly adding the mixed solution into the three-neck flask, and continuously stirring for 10min to obtain a suspension.
And filtering the obtained suspension through a tetrafluoroethylene filter membrane, washing solid powder on the filter membrane with deionized water, and finally drying the solid powder together with the filter membrane in a 150 ℃ oven to obtain the one-dimensional organic nano material.
FIG. 8 is a transmission electron micrograph of the one-dimensional organic nanomaterial in this embodiment, and it can be seen from FIG. 8 that the radial size distribution of the one-dimensional organic nanomaterial obtained in this embodiment is about 5nm to 25nm, the axial size distribution is 1.5 μm to 3.0 μm, and the size distribution uniformity is good.
Application example 1
The one-dimensional organic nano material in the embodiment 1 is used for photocatalytic degradation of methylene blue dye, and the result shows that the degradation removal rate of 20ppm of methylene blue in water can reach more than 95% under the condition of no oxidant for 30min illumination. The result shows that under the premise of adding the one-dimensional organic nano material, the methylene blue in the water can be rapidly degraded and removed through photocatalysis by illumination.
Application example 2
The one-dimensional organic nano material in example 1 is used for adsorbing and removing heavy metal salt ions in water, and the result shows that 10mg of the one-dimensional organic nano material is added into 1L of water containing 1ppm of chromium ions, and the complete adsorption and removal of the heavy metal ions in the water can be realized only by stirring for 5 min. The results show that the one-dimensional organic nano material has excellent adsorption and removal capacity on heavy metal salt ions in water.
Application example 3
The one-dimensional organic nanomaterial in example 1 is used for modifying a high molecular material. When the polysulfone separation membrane is prepared, 0.5 percent of the one-dimensional organic nano material in mass ratio is added into a membrane casting solution, so that the strength of the membrane material can be improved by 20 percent; when the adding mass of the one-dimensional organic nano material reaches 40% of the mass of the polysulfone, the membrane casting solution can still keep good stability, and after standing for 24 hours, the one-dimensional organic nano material does not have obvious bad precipitation phenomenon. The results show that the one-dimensional organic nano material not only can obviously enhance the strength of the high polymer material, but also has excellent compatibility with the high polymer material.
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 shall be subject to the appended claims.

Claims (10)

1. The one-dimensional organic nanomaterial is characterized in that the one-dimensional organic nanomaterial is a covalent triazine organic framework material.
2. The one-dimensional organic nanomaterial according to claim 1, wherein the one-dimensional organic nanomaterial comprises at least one of an organic nanotube and an organic nanofiber.
3. A one-dimensional organic nanomaterial according to claim 1, characterized in that the axial dimension of the one-dimensional organic nanomaterial is 10-1000 times the radial dimension; the axial size of the one-dimensional organic nano material is 0.5-5 mu m, and the radial size of the one-dimensional organic nano material is 5-100 nm.
4. A method for preparing one-dimensional organic nanomaterials as claimed in any one of claims 1 to 3, comprising:
mixing polycyanobenzene, a catalyst and a solvent, and carrying out polymerization reaction at a first temperature to obtain an intermediate product containing a covalent triazine organic framework material, wherein the covalent triazine organic framework material is a two-dimensional organic nanosheet;
and cooling the intermediate product to a second temperature and mixing the intermediate product with an inducer to obtain the one-dimensional organic nano material.
5. The method according to claim 4, wherein the inducing agent is selected from an alcohol or an aqueous alcohol solution, wherein the alcohol comprises at least one of methanol, ethanol, isopropanol, and n-propanol.
6. The method according to claim 4, wherein the first temperature is 80 ℃ to 120 ℃ and the second temperature is less than or equal to 60 ℃.
7. The method according to claim 4, wherein the polycyanobenzene comprises at least one of dicyanobenzene and tricyanobenzene; wherein the dicyanobenzene comprises at least one of 4, 4' -biphenylcarbonitrile, tetrafluoroterephthalonitrile and 2, 5-dichloroterephthalonitrile, and the tricyanobenzene comprises at least one of 1,3, 4-benzenetricyano group and 1,3, 5-benzenetricyano group.
8. The method according to claim 4, wherein the solvent comprises at least one of dimethylformamide, dimethylsulfoxide, acetone, dichloromethane, and tetrahydrofuran.
9. The method according to claim 4, wherein the catalyst comprises at least one of trifluoromethanesulfonic acid, fluorosulfonic acid, trifluoroacetic acid, pentafluoroacetic acid, heptafluoropropionic acid.
10. The method for preparing one-dimensional organic nano-materials according to claim 4, wherein the solvent, the catalyst, the polycyanobenzene and the inducer are mixed in the following ratio: 3mL-10mL of the catalyst, 0.5g-2g of the polycyanobenzene and 10mL-100mL of the inducer are prepared for every 100mL of the solvent.
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