CN113549185A - Covalent organic framework material for crystal violet adsorption and preparation method and application thereof - Google Patents
Covalent organic framework material for crystal violet adsorption and preparation method and application thereof Download PDFInfo
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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- C08G12/06—Amines
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Abstract
A covalent organic framework material for crystal violet adsorption and a preparation method and application thereof relate to a covalent organic framework material and a preparation method and application thereof. The method aims to solve the technical problems of few types of materials with high adsorption performance on crystal violet, long adsorption time, low maximum adsorption capacity and poor material recycling performance in the prior art. The basic building blocks of the covalent organic framework materials of the invention are as follows:it is thatIs obtained by reacting biphenyl tetra-aldehyde with 4,4 '-diaminobiphenyl-3, 3' -disulfonic acid. It can be used as an adsorbent for qualitative detection of crystal violet in wastewater by naked eye or ultraviolet spectroscopy. The adsorption equilibrium time of the covalent organic framework material of the invention on crystal violet is 120min, and the maximum adsorption capacity is 961mg g‑1The adsorption effect is good, and the material can be recycled. Can be used for identifying and removing crystal violet in wastewater.
Description
Technical Field
The invention relates to a high-efficiency covalent organic framework material for crystal violet adsorption and a preparation method and application thereof.
Background
With the development of the national light industry, tens of tons of dyes are used for printing and dyeing, papermaking, leather and the like of textiles every year, so that a large amount of dye wastewater is generated, and the environment is polluted. Crystal violet is one of toxic cationic dyes, has high chroma, difficult degradation and poor biodegradability, and causes great pollution to the environment by crystal violet dye wastewater. The efficient and cost-effective removal of crystal violet and other organic dyes from wastewater is a problem that is sought to be solved by the environment and health of the world. At present, the methods for treating dye wastewater mainly comprise a photodegradation method, an electrochemical degradation method, a chemical oxidation method, a biological method, an ultrafiltration membrane, an adsorption method and the like. Among them, the adsorption method is attracting much attention because of its advantages such as easy operation, reliable effect, and easy maintenance. The adsorption method is used for removing organic dyes in wastewater, and the main principle is that the adsorption of organic micromolecular dyes is realized by utilizing the properties of large specific surface area, high porosity, ordered pore structure and the like of high polymer materials with good thermal stability and chemical stability. Document functional Material in 7 th 49 of 2018The volume reports that a Metal Organic Framework (MOFs) material adsorbs methylene blue dye, and a Zn-MOFs material with good thermal stability and chemical stability is adopted to realize the adsorption of the methylene blue, the dye removal rate reaches 62.3%, and the maximum adsorption quantity of the methylene blue is 342mg g-1. In 2020, the document "Neijiang science and technology" No. 2 discloses a list of reports on the good adsorption effect of a ZIF-8 material on a cationic dye methylene blue, but 480min is required to reach adsorption equilibrium, and the adsorption equilibrium time is long. In addition, chinese patent publication No. CN 104117339 a discloses a method for synthesizing a carbon-coated ferromagnetic nanoparticle adsorbent by decomposing glucose with an iron catalyst by a hydrothermal method, which can be used for dye adsorption, wherein the adsorbent and dye wastewater need to be uniformly dispersed for 10-36 hours, and the adsorption time is long.
In recent years, research on Covalent Organic Frameworks (COFs) materials, which exhibit excellent performance in the fields of gas separation and storage, catalysis, photoelectricity, and medicine, has been drawing attention. In 2018, the document "applied chemistry" at volume 5, 35 reports that a magnetic Covalent Organic Framework (COF) material is used as an adsorbent, a static adsorption method is used for realizing the adsorption behavior of methyl orange and alizarin green, the material realizes the adsorption balance of two dyes in 180min, and the equilibrium adsorption amounts are 997 mg/g and 1313 mg/g respectively-1. The invention of Chinese patent with publication number CN 111729650A constructs a magnetic covalent organic framework nano-composite (Fe) with a core-shell structure3O4@ COF), realizes adsorption of Congo red and alizarin red, effectively reduces the adsorption time of dye as composite material, but has complex material synthesis and separation process, and the maximum adsorption amount of Congo red is only 46.72 mg.g-1。
According to the current literature reports, the existing functional materials for adsorbing organic dyes in wastewater mainly have the following defects:
1. the material used for adsorbing the organic dye is less in variety;
2. the adsorption time required by most materials for adsorbing the dye is longer;
3. the material has low adsorption quantity to organic dye and poor adsorption effect;
4. the materials required for adsorbing the organic dye are complex to prepare and poor in cyclic usability;
5. there are fewer types of materials that have specific adsorption for crystal violet.
Disclosure of Invention
The invention provides a covalent organic framework material for crystal violet adsorption and a preparation method and application thereof, aiming at solving the technical problems of few types of materials with high adsorption performance on crystal violet, long adsorption time, low maximum adsorption capacity and poor material recycling performance in the prior art. The covalent organic framework material has the advantages of short adsorption time for crystal violet, high adsorption quantity and cyclic use.
The basic structural unit of the covalent organic framework material for adsorbing the crystal violet is as follows:
the covalent organic framework material for adsorbing the crystal violet is obtained by reacting biphenyl tetra-aldehyde and 4,4 '-diaminobiphenyl-3, 3' -disulfonic acid, and the specific preparation method comprises the following steps:
firstly, adding biphenyl tetra-aldehyde, 4 '-diaminobiphenyl-3, 3' -disulfonic acid, an organic solvent I and acid into a dixophone in sequence; wherein the mass ratio of the biphenyl tetra-aldehyde to the 4,4 '-diaminobiphenyl-3, 3' -disulfonic acid is 1: (1-5);
secondly, freezing, vacuumizing and unfreezing the park wire by liquid nitrogen, repeating the operation for 4-5 times, and sealing;
and thirdly, heating the pixellate to 100-180 ℃, reacting for 72-168 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with an organic solvent II, and carrying out vacuum drying to obtain the covalent organic framework material for crystal violet adsorption.
Further, in the first step, the organic solvent I is a mixture of any two solvents of mesitylene, tetrahydrofuran, o-dichlorobenzene, N-butanol, N-dimethylformamide, p-dimethylaminopyridine and dioxane.
Further, the ratio of the amount of the substance of biphenyltetra-aldehyde to the volume of the organic solvent i was 1 mmol: (5-25) mL;
further, the acid in the step one is one or a combination of any two of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with the mass percentage concentration of 30% -37%, and concentrated sulfuric acid with the mass percentage concentration of 95% -98%;
further, the ratio of the amount of substance of biphenyltetra-aldehyde to the volume of acid was 1 mmol: (2.5-10) mL;
further, the organic solvent II for washing the filter cake in the third step is methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, o-dichlorobenzene, N-butanol, N-dimethylacetamide or acetone.
The preparation process of the covalent organic framework material for crystal violet adsorption of the invention is represented by the following formula:
the covalent organic framework material for adsorbing the crystal violet is used as an adsorbent, and the crystal violet in the wastewater is qualitatively detected by naked eyes or ultraviolet spectroscopy.
The method for detecting crystal violet in water by naked eyes by using a covalent organic framework material for crystal violet adsorption as an adsorbent comprises the following steps:
and adding the covalent organic framework material for adsorbing the crystal violet into the solution to be detected, standing in sunlight for 5min, observing the color change of the solution by naked eyes, and if the color of the solution is gradually changed from dark purple to colorless, judging that the solution to be detected contains the crystal violet.
The method for qualitatively detecting the crystal violet in the water by using a covalent organic framework material for adsorbing the crystal violet as an adsorbent and using an ultraviolet spectroscopy comprises the following steps:
firstly, measuring the ultraviolet absorption light of a solution to be measuredSpectrum, absorption wavelength 587nm, absorbance A1;
Secondly, adding a covalent organic framework material for crystal violet adsorption into the solution to be measured, uniformly mixing, standing for 5min, and measuring the ultraviolet absorption spectrum of the solution, wherein the absorption wavelength is 587nm, and the absorbance is A2;
Third, comparison A1And A2If A is1>A2And judging that the solution to be detected contains crystal violet.
A method for quantitatively detecting crystal violet in water by using a covalent organic framework material for crystal violet adsorption as an adsorbent through an ultraviolet spectroscopy method comprises the following steps:
firstly, preparing crystal violet standard solutions with different concentrations;
adding a covalent organic framework material for adsorbing the crystal violet into the crystal violet standard solution, after adsorption balancing, testing the ultraviolet spectroscopy of the solution, and drawing a standard curve between the crystal violet concentration of the solution and the absorbance of the solution by taking the absorbance at the position of 587nm absorption wavelength as a longitudinal standard and taking the crystal violet concentration as a transverse standard;
and thirdly, adding a covalent organic framework material for adsorbing the crystal violet into the solution to be detected, testing the ultraviolet spectroscopy of the solution after adsorption balance, reading the absorbance at the position of 587nm of absorption wavelength, and finding out the crystal violet concentration in the solution to be detected from the standard curve.
And separating the covalent organic framework material which adsorbs the crystal violet and is used for adsorbing the crystal violet from the solution by centrifugal separation, and finishing regeneration after soaking, centrifuging and vacuum drying for 48 hours for multiple times by adopting an alcohol solvent. The regenerated covalent organic framework material for crystal violet adsorption can be reused.
Further, the alcohol solvent for analysis is any one of methanol, ethanol, n-butanol, benzyl alcohol, and ethylene glycol.
The method for adsorbing the crystal violet by the covalent organic framework material for adsorbing the crystal violet is simple, efficient and easy to operate, the adsorption equilibrium time is 120min, and the maximum adsorption capacity is 961mg g-1The adsorption effect is good, and the material can be recycled.
Drawings
FIG. 1 is an infrared spectrum of the covalent organic framework material for crystal violet adsorption prepared in example 1, plotted with wavelength on the horizontal scale and light transmittance on the vertical scale.
Fig. 2 is a color change diagram of the crystal violet solution detected by naked eyes of the covalent organic framework material for crystal violet adsorption prepared in example 1.
FIG. 3 is a graph of the UV spectrum of the covalent organic framework material for crystal violet adsorption prepared in example 1, plotted with wavelength in the horizontal axis and absorbance in the vertical axis, as a function of adsorption time for crystal violet detection by UV spectroscopy.
FIG. 4 is a standard curve of concentration of crystal violet solution II and its absorbance for different concentrations in example 1, with the abscissa being the concentration of crystal violet (mg. L)-1) The abscissa is absorbance.
FIG. 5 is the adsorption isotherms of crystal violet solutions of different concentrations when crystal violet was detected by UV spectroscopy using a covalent organic framework material for crystal violet adsorption in example 1, with the abscissa being the concentration of the dye solution and the ordinate being the equilibrium adsorption amount.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the covalent organic framework material for crystal violet adsorption of the embodiment comprises the following steps:
firstly, adding 50mg of biphenyl tetra-aldehyde, 70mg of 4,4 ' -diaminobiphenyl-3, 3 ' -disulfonic acid, 0.5mL of mesitylene, 0.5mL of n-butyl alcohol and 0.1mL of trifluoroacetic acid into a dix's nest in turn;
secondly, freezing, vacuumizing and unfreezing the park by liquid nitrogen, repeating the operation for 5 times, and sealing;
and thirdly, heating the Paex tube to 120 ℃, reacting for 120h, cooling to room temperature after the reaction is finished, performing suction filtration, washing a filter cake with tetrahydrofuran, and drying in vacuum to obtain the covalent organic framework material for crystal violet adsorption with the yield of 75%.
The co-polymer prepared in this example for crystal violet adsorptionThe IR spectrum of the organic framework material is shown in FIG. 1. 3264 and 3385cm-1Is represented by-NH2Absorption peak of stretching vibration, 3495cm-1The peak is an O-H stretching vibration absorption peak of 1645cm-1Absorption peak of stretching vibration at C ═ C, 1104 and 1042cm-1The position is the stretching vibration absorption peak of O-S. Indicating that the covalent organic framework material for crystal violet adsorption is successfully prepared.
The covalent organic framework material for crystal violet adsorption prepared in example 1 is used as an adsorbent, and crystal violet in wastewater is detected by naked eyes, and the specific method is as follows:
firstly, taking 10mL of wastewater solution I containing crystal violet dye, wherein the solution is purple;
secondly, adding 5mg of the covalent organic framework material for crystal violet adsorption prepared in the example 1 into the wastewater solution I to obtain a solution II;
and thirdly, observing the color change conditions of the solution II in 0min, 1min, 3min, 5min, 10min, 30min, 60min, 120min and 180min by naked eyes under sunlight as shown in figure 2, wherein the color of the solution II is dark purple at 0min, the color of the solution II is obviously light after 5min, and the solution II becomes colorless at 120 min. With the increase of the adsorption time, the color of the wastewater solution is dark purple and gradually changed into colorless, so that the covalent organic framework material for adsorbing the crystal violet, which is prepared in example 1, can be used as a reminder for qualitatively detecting the crystal violet in the wastewater. Meanwhile, the covalent organic framework material adsorbed by the crystal violet can be used for adsorbing the crystal violet in wastewater.
The covalent organic framework material for crystal violet adsorption prepared in example 1 is used as an adsorbent, and crystal violet in wastewater is qualitatively detected by ultraviolet spectroscopy, and the specific method is as follows:
firstly, taking 10mL of wastewater solution I containing crystal violet dye, and measuring the ultraviolet absorption spectrum of the solution I, wherein the absorption wavelength is 587nm, and the absorbance is A1;
Secondly, adding 5mg of a high-efficiency covalent organic framework material for crystal violet adsorption into the wastewater solution I to prepare a solution II;
measuring the ultraviolet absorption spectrum of the solution II after 5min, wherein the absorption wavelength is 587nm, absorbance is A2Discovery A1>A2And if so, indicating that the dye wastewater contains the crystal violet, and qualitatively detecting the crystal violet in the wastewater by using a covalent organic framework material for adsorbing the crystal violet.
The covalent organic framework material for crystal violet adsorption prepared in example 1 is used as an adsorbent, and crystal violet in wastewater is qualitatively detected by ultraviolet spectroscopy, and the specific method is as follows:
firstly, taking 10mL of wastewater solution I containing crystal violet dye, and measuring the ultraviolet absorption spectrum of the solution I, wherein the absorption wavelength is 587nm, and the absorbance is A1;
Secondly, adding 5mg of a high-efficiency covalent organic framework material for crystal violet adsorption into the wastewater solution I to prepare a solution II;
and thirdly, measuring the ultraviolet absorption spectrum of the solution II at intervals, wherein the obtained ultraviolet absorption spectrum is shown in figure 3, the horizontal mark is the wavelength, and the vertical coordinate is the absorbance. As can be seen from FIG. 3, the absorbance at 587nm of solution II at 0min was 1.28A. The absorbance gradually decreased with increasing time. At 5min, the absorbance of solution II dropped significantly to 0.45A, and at 120min the absorbance of solution II was close to zero. The new efficient covalent organic framework material for adsorbing the crystal violet gradually increases the adsorption amount of the crystal violet in the wastewater along with the increase of time, the concentration of the crystal violet in the solution II gradually decreases, the absorbance gradually decreases, and the adsorption balance is reached in 120 min. Then, the method proves that the crystal violet in the wastewater can be qualitatively detected by using a high-efficiency covalent organic framework material for crystal violet adsorption.
The method for quantitatively detecting crystal violet in water by using the covalent organic framework material for crystal violet adsorption prepared in example 1 as an adsorbent through an ultraviolet spectroscopy method comprises the following specific steps:
firstly, preparing 0mg/L, 2mg/L, 4mg/L, 6mg/L and 8mg/L of crystal violet standard solutions respectively;
secondly, adding 5mg of covalent organic framework material for adsorbing the crystal violet into 100mL of crystal violet standard solution, adsorbing for 120min, and testing the ultraviolet spectroscopy of the solution by taking the absorbance at the position of 587nm as vertical workMarking, namely drawing a standard curve between the crystal violet concentration of the solution and the absorbance of the solution by taking the crystal violet concentration as a horizontal mark; as shown in fig. 4, the deviation R of the standard curve20.9967, and the relationship between the concentration of the crystal violet and the absorbance of the solution can be determined through the standard curve;
adding 5mg of covalent organic framework material for adsorbing crystal violet into 100mL of solution to be detected, adsorbing for 120min to obtain an ultraviolet spectrum method of the solution II to be detected, reading the absorbance at the absorption wavelength of 587nm, and finding out the equilibrium concentration c of crystal violet in the solution II to be detected from a standard curvee. According to the formulaCalculating the equilibrium concentration ceThe equilibrium adsorption quantity q of the covalent organic framework material for adsorbing the crystal violet to the crystal violet in the solutione(mg·g-1) Wherein v represents the volume of solution II, coIndicates the initial concentration (mg. L) of crystal violet in solution II-1) And m is the mass (g) of the covalent organic framework material used for crystal violet adsorption. The maximum adsorption amount of crystal violet at the time of equilibrium adsorption was 961mg g-1. Using the same mass of material for different concentrations coAdsorbing the solution to be detected, and searching for adsorption balance through a standard curve ceBy the formulaCalculating qeI.e. the ordinate, fig. 5 is plotted. Fig. 5 is an adsorption isotherm of a covalent organic framework material for adsorption of crystal violet to crystal violet of different concentrations, with the abscissa being the concentration of crystal violet in the solution at equilibrium of adsorption and the ordinate being the equilibrium adsorption amount. The figure demonstrates the adsorption capacity of a highly efficient covalent organic framework material for crystal violet adsorption on crystal violet in solution II. The figure shows that the equilibrium adsorption amount of the high-efficiency covalent organic framework material with the same mass for adsorbing the crystal violet to crystal violet solutions with different concentrations is different, the increase value of the equilibrium adsorption amount of the material to the crystal violet is accelerated along with the increase of the equilibrium adsorption concentration, and when the equilibrium adsorption concentration reaches the equilibrium adsorption concentration100mg·g-1When the adsorption is carried out, the equilibrium adsorption capacity is slowly increased, and the maximum adsorption capacity can reach 961mg g-1。
Example 2: the preparation method of the covalent organic framework material for crystal violet adsorption of the embodiment comprises the following steps:
first, 50mg of biphenyltetra-aldehyde and 75mg of 4,4 '-diaminobiphenyl-3, 3' -disulfonic acid, 0.2mL of mesitylene, 0.8mL of dioxane, and 0.1mL of glacial acetic acid were added to a park in that order.
Secondly, freezing, vacuumizing and unfreezing the park Keystone by liquid nitrogen, repeating the operation for five times, and sealing;
and thirdly, heating the park wire to 130 ℃, reacting for 144h, cooling to room temperature after the reaction is finished, performing suction filtration, using acetonitrile to prepare a filter cake, and performing vacuum drying to obtain the covalent organic framework material for crystal violet adsorption with the yield of 70%.
Example 3: the preparation method of the covalent organic framework material for crystal violet adsorption of the embodiment comprises the following steps:
first, 50mg of biphenyltetra-aldehyde and 50mg of 4,4 ' -diaminobiphenyl-3, 3 ' -disulfonic acid, 0.3mL of n-butanol, 0.7mL of dioxane, and 0.1mL of benzenesulfonic acid were added to a dix's flask in this order.
Secondly, freezing, vacuumizing and unfreezing the park Keystone by liquid nitrogen, repeating the operation for five times, and sealing;
and thirdly, heating the dixophone to 110 ℃, reacting for 168 hours, cooling to room temperature after the reaction is finished, performing suction filtration, using acetone to filter a filter cake, and performing vacuum drying to obtain the efficient covalent organic framework material for crystal violet adsorption with the yield of 68%.
Example 4: the preparation method of the covalent organic framework material for crystal violet adsorption of the embodiment comprises the following steps:
first, 50mg of biphenyltetra-aldehyde and 100mg of 4,4 '-diaminobiphenyl-3, 3' -disulfonic acid, 0.3mL of n-butanol, 0.7mL of mesitylene and 0.1mL of p-toluenesulfonic acid were added to a park in this order.
Secondly, freezing, vacuumizing and unfreezing the park Keystone by liquid nitrogen, repeating the operation for five times, and sealing;
and thirdly, heating the park Kernel to 140 ℃, reacting for 120h, cooling to room temperature after the reaction is finished, performing suction filtration, and performing vacuum drying on a filter cake by using methanol to obtain the covalent organic framework material for crystal violet adsorption with the yield of 68%.
Example 5: the preparation method of the covalent organic framework material for crystal violet adsorption of the embodiment comprises the following steps:
firstly, 50mg of biphenyl tetra-aldehyde, 80mg of 4,4 ' -diaminobiphenyl-3, 3 ' -disulfonic acid, 0.8mL of N, N-dimethylformamide, 0.2mL of mesitylene and 0.1mL of concentrated sulfuric acid with the mass percentage concentration of 95% are sequentially added into a dix's nest.
Secondly, freezing, vacuumizing and unfreezing the park Keystone by liquid nitrogen, repeating the operation for five times, and sealing;
and thirdly, heating the park Kernel to 150 ℃, reacting for 120h, cooling to room temperature after the reaction is finished, performing suction filtration, and performing vacuum drying on a filter cake by using tetrahydrofuran to obtain the covalent organic framework material for crystal violet adsorption with the yield of 72%.
Example 6: the preparation method of the covalent organic framework material for crystal violet adsorption of the embodiment comprises the following steps:
firstly, 50mg of biphenyl tetra-aldehyde, 80mg of 4,4 ' -diaminobiphenyl-3, 3 ' -disulfonic acid, 0.8mL of N, N-dimethylformamide, 0.2mL of mesitylene and 0.1mL of concentrated sulfuric acid with the mass percentage concentration of 95% are sequentially added into a dix's nest.
Secondly, freezing, vacuumizing and unfreezing the park Keystone by liquid nitrogen, repeating the operation for five times, and sealing;
and thirdly, heating the park Kernel to 150 ℃, reacting for 120h, cooling to room temperature after the reaction is finished, performing suction filtration, and performing vacuum drying on a filter cake by using ethanol to obtain the covalent organic framework material for crystal violet adsorption with the yield of 72%.
Example 7: the preparation method of the covalent organic framework material for crystal violet adsorption of the embodiment comprises the following steps:
firstly, 50mg of biphenyltetra-aldehyde, 90mg of 4,4 ' -diaminobiphenyl-3, 3 ' -disulfonic acid, 0.8mL of N, N-dimethylformamide, 0.2mL of o-dichlorobenzene and 0.1mL of concentrated hydrochloric acid with the mass percentage concentration of 37% are added into a dix's pipe in sequence.
Secondly, freezing, vacuumizing and unfreezing the park Keystone by liquid nitrogen, repeating the operation for five times, and sealing;
and thirdly, heating the park Kernel to 140 ℃, reacting for 130h, cooling to room temperature after the reaction is finished, performing suction filtration, and performing vacuum drying on a filter cake by using ethanol to obtain the covalent organic framework material for crystal violet adsorption with the yield of 66%.
Claims (10)
2. a method of preparing the covalent organic framework material for crystal violet adsorption of claim 1, comprising the steps of:
firstly, adding biphenyl tetra-aldehyde, 4 '-diaminobiphenyl-3, 3' -disulfonic acid, an organic solvent I and acid into a dixophone in sequence; wherein the mass ratio of the biphenyl tetra-aldehyde to the 4,4 '-diaminobiphenyl-3, 3' -disulfonic acid is 1: (1-5);
secondly, freezing, vacuumizing and unfreezing the park wire by liquid nitrogen, repeating the operation for 4-5 times, and sealing;
and thirdly, heating the pixellate to 100-180 ℃, reacting for 72-168 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing a filter cake with an organic solvent II, and carrying out vacuum drying to obtain the covalent organic framework material for crystal violet adsorption.
3. The method for preparing a covalent organic framework material for crystal violet adsorption according to claim 2, wherein the organic solvent I in the step one is a mixture of any two solvents selected from mesitylene, tetrahydrofuran, o-dichlorobenzene, N-butanol, N-dimethylformamide, p-dimethylaminopyridine and dioxane.
4. The method for preparing a covalent organic framework material for crystal violet adsorption according to claim 2 or 3, wherein the ratio of the amount of biphenyltetra-aldehyde substance to the volume of organic solvent I in step one is 1 mmol: (5-25) mL.
5. The method according to claim 2 or 3, wherein the acid in the step one is one of glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, concentrated hydrochloric acid with a mass percentage concentration of 30-37%, concentrated sulfuric acid with a mass percentage concentration of 95-98%, or a combination of any two of them.
6. The method for preparing a covalent organic framework material for crystal violet adsorption according to claim 2 or 3, wherein the ratio of the amount of biphenyltetra-aldehyde substance to the volume of acid in step one is 1 mmol: (2.5-10) mL.
7. The method for preparing a covalent organic framework material for crystal violet adsorption according to claim 2 or 3, wherein the organic solvent II for washing filter cakes in the third step is methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, o-dichlorobenzene, N-butanol, N-dimethylacetamide or acetone.
8. Use of a covalent organic framework material for crystal violet adsorption according to claim 1, characterized in that the covalent organic framework material for crystal violet adsorption is used as an adsorbent for the qualitative detection of crystal violet in wastewater by naked eye or uv spectroscopy.
9. The use of a covalent organic framework material for crystal violet adsorption according to claim 8, wherein the covalent organic framework material for crystal violet adsorption is used as an adsorbent, and the method for detecting crystal violet in water by naked eyes is as follows:
and adding the covalent organic framework material for adsorbing the crystal violet into the solution to be detected, standing in sunlight for 5min, observing the color change of the solution by naked eyes, and if the color of the solution is gradually changed from dark purple to colorless, judging that the solution to be detected contains the crystal violet.
10. The use of a covalent organic framework material for crystal violet adsorption according to claim 8, wherein the covalent organic framework material for crystal violet adsorption is used as an adsorbent, and the method for qualitatively detecting crystal violet in water by ultraviolet spectroscopy is as follows:
firstly, measuring the ultraviolet absorption spectrum of the solution to be measured, wherein the absorption wavelength is 587nm, and the absorbance is A1;
Secondly, adding a covalent organic framework material for crystal violet adsorption into the solution to be measured, uniformly mixing, standing for 5min, and measuring the ultraviolet absorption spectrum of the solution, wherein the absorption wavelength is 587nm, and the absorbance is A2;
Third, comparison A1And A2If A is1>A2And judging that the solution to be detected contains crystal violet.
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