CN114085387B - Covalent organic framework material for hydroquinone adsorption and preparation method and application thereof - Google Patents
Covalent organic framework material for hydroquinone adsorption and preparation method and application thereof Download PDFInfo
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Abstract
A covalent organic framework material for hydroquinone 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 and low maximum adsorption capacity of the existing adsorption hydroquinone. The basic structural units of the covalent organic framework material for hydroquinone adsorption of the invention are as follows:
it adopts 2- (3-trifluoromethyl phenyl) -1H-phenanthrene [9,10-d ]]Imidazole-6, 9-diamine and 5' - (4-formylphenyl) - [1,1':3',1 "-terphenyl ]]-4,4 "dicarboxaldehyde. For absorbing hydroquinone in the solution or detecting hydroquinone in the solution. The equilibrium adsorption capacity of the covalent organic framework material for hydroquinone adsorption to hydroquinone can reach 597mg.g ‑1 The adsorption equilibrium time is 240min, and can be used for adsorbing or detecting hydroquinone in solution.
Description
Technical Field
The invention relates to a covalent organic framework material, a preparation method and application thereof.
Background
With the rapid development of industrialization and city and the continuous improvement of the living standard of people, the environmental pollution problem becomes serious, and the method brings great threat to the life health of people. The phenolic substance is a common environmental pollutant, hydroquinone is a kind of phenolic substance, and also called hydroquinone, is a basic organic chemical raw material, and the product has wide application, is an important intermediate of pesticides, medicines and dyes, is commonly used for preparing azo and anthraquinone dyes, film developers, cosmetic whitening agents, petroleum anticoagulants, food antioxidants, rubber preservatives and medical intermediates, has great toxicity to human bodies, and has irritation to skin, eyes and mucous membranes. Because of the characteristics of high toxicity and difficult degradation of hydroquinone, the current treatment technology of hydroquinone mainly comprises an adsorption method, an electrochemical oxidation method, an ozone oxidation method, a photocatalysis method and the like. In recent years, the adsorption method has advantages of simple operation and low cost, and is thus widely used for removing hydroquinone in the environment. Therefore, the development of a novel adsorption material for adsorbing hydroquinone has important significance.
Covalent organic framework materials (Covalent organic frameworks, COFs) have been focused by researchers because of their advantages of ordered pore structure, large specific surface area, uniform porosity, good chemical stability, and the like, and have broad application prospects in the adsorption field. At present, the literature on the adsorption of phenols by covalent organic framework materials has been reported successively, and paper "construction of layered porous monolith from covalent organic framework and its application in bisphenol A removal" by volume 355, 5 th edition, 2018, designs and synthesizes a covalent organic framework material connected by azine, realizes the adsorption of bisphenol A with an adsorption capacity of 61.3mg g -1 . Article "simple Synthesis" in section B of J.Molecular liquid in 2020 volume 320Fe 3 O 4 The covalent organic framework for adsorbing bisphenol compounds in COF aqueous solution discloses that bisphenol A is adsorbed by using a covalent organic framework material after compounding, and the maximum adsorption amount is only 140mg g -1 . At present, the materials for adsorbing hydroquinone are few in variety and low in maximum adsorption amount, and a method for qualitatively detecting hydroquinone and measuring the maximum adsorption amount by utilizing a fluorescence emission spectrometry is not available.
According to the current literature reports, the existing materials for adsorbing hydroquinone mainly have the following defects:
1. the materials used for adsorbing hydroquinone are few in types;
2. the material has low adsorption quantity to hydroquinone and poor adsorption effect;
3. the preparation of the materials required for adsorption of hydroquinone is complex.
Disclosure of Invention
The invention aims to solve the technical problems of few types of materials and low maximum adsorption capacity of the existing hydroquinone adsorption materials, and provides a covalent organic framework material for hydroquinone adsorption, a preparation method and application thereof.
The basic structural units of the covalent organic framework material for hydroquinone adsorption of the invention are as follows:
the covalent organic framework material for hydroquinone adsorption is prepared by reacting 2- (3-trifluoromethyl phenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde, and the specific preparation method is as follows:
1. the ratio of the amounts of substances of 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde is 1: (1-5) weighing 2- (3-trifluoromethyl phenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde, adding into a pyrex tube, adding an organic solvent I and acid, and uniformly mixing;
2. vacuumizing the pyrex tube, then filling nitrogen, and repeating the vacuumizing and nitrogen filling operation for 4-5 times;
3. heating the pyrex tube to 100-300 ℃ for reaction for 1-6 days;
4. and cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using an organic solvent II, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption.
Further, the organic solvent I in the first step is one or a combination of any two of paradichlorobenzene, mesitylene, isopropanol, dioxane, dimethyl sulfoxide and N, N-dimethylformamide;
further, the ratio of the mass of the 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to the volume of the organic solvent I in the first step is (0.1-0.3) g:1mL;
further, the acid in the first step is one or a combination of any two of benzenesulfonic acid, trifluoroacetic acid, glacial acetic 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 mass of the 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to the volume of the acid in the first step is 1g (0.2-0.4) mL;
further, the organic solvent II for washing the filter cake in the fourth step is one or a combination of any two of methanol, ethanol, tetrahydrofuran, ethyl acetate, acetone, dichloromethane and N, N-dimethylformamide.
The application of the covalent organic framework material for hydroquinone adsorption is to take the covalent organic framework material for hydroquinone adsorption as an adsorbent to absorb hydroquinone in a solution.
The application of the covalent organic framework material for hydroquinone adsorption is that the covalent organic framework material for hydroquinone adsorption is used for qualitatively or quantitatively detecting hydroquinone in a solution.
The method for qualitatively detecting hydroquinone in a solution by using a covalent organic framework material for hydroquinone adsorption takes the covalent organic framework material for hydroquinone adsorption as an adsorbent, and quantitatively detects the hydroquinone in the solution by a fluorescence emission spectrum method, and specifically comprises the following steps:
1. measuring fluorescence emission spectrum of hydroquinone solution with concentration of 300mg/L by using 280nm as excitation wavelength, and recording emission intensity at emission wavelength of 338nm as T A ；
2. Adding 9mg of covalent organic framework material for hydroquinone adsorption into 10mL of solution to be detected, uniformly dispersing, stirring for 30-300 min, and filtering to remove the covalent organic framework material for hydroquinone adsorption in the solution to be detected by using a filter membrane to obtain the treated solution to be detected;
3. measuring the fluorescence emission spectrum of the treated solution to be measured by taking 280nm as an excitation wavelength, and marking the emission intensity at the emission wavelength of 338nm as T B ；
4. Comparison T A And T B If T A >T B It can be determined that hydroquinone is contained in the solution to be measured.
The method for testing the equilibrium adsorption quantity of the hydroquinone adsorbed by the covalent organic framework material used for hydroquinone adsorption as an adsorbent is measured by a fluorescence emission spectrometry, and comprises the following specific steps:
1. respectively preparing hydroquinone solutions with the concentration of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L and 100mg/L, respectively measuring the fluorescence emission spectra of the hydroquinone solutions, recording the fluorescence emission intensity when the emission wavelength is 338nm, taking the fluorescence intensity as an ordinate, taking the hydroquinone concentration as an abscissa, and drawing a standard curve between the hydroquinone concentration and the fluorescence intensity thereof;
2. measuring fluorescence emission spectrum of the solution to be measured containing hydroquinone, and recording emission intensity of the solution to be measured as Tc when the emission wavelength is 338 nm;
3. the concentration of hydroquinone corresponding to Tc is found out on a standard curve and is recorded as the initial concentration of hydroquinone in the solution to be detectedInitial concentration c 0 ；
4. Adding covalent organic framework material with the mass of m and used for hydroquinone adsorption into a solution to be detected, which contains hydroquinone, with the volume of V, adsorbing for 48 hours to reach adsorption equilibrium, filtering the covalent organic framework material used for hydroquinone adsorption, detecting the fluorescence emission spectrum of filtrate, and recording the emission intensity of the filtrate with the emission wavelength of 338nm as Td;
5. the concentration of hydroquinone corresponding to Td is found on the standard curve and is recorded as the equilibrium concentration c of hydroquinone e ；
6. According to formula q e ＝V(c 0 -c e ) M the equilibrium adsorption of hydroquinone by the covalent organic framework material for hydroquinone adsorption is calculated, where q e (mg·g -1 ) Represents the equilibrium adsorption quantity, q, of the covalent organic framework material for hydroquinone adsorption to hydroquinone e Is expressed in mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the V represents the volume of the solution to be detected containing hydroquinone in the step four, and the unit is L; c 0 Represents the initial concentration in step three, which is in mg.L -1 ；c e Represents the equilibrium concentration of hydroquinone in step five, in mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the m represents the mass of the covalent organic framework material used for hydroquinone adsorption in the fourth step, and the unit is g.
The chemical reaction formula of the covalent organic framework material for hydroquinone adsorption is as follows:
the equilibrium adsorption capacity of the covalent organic framework material for hydroquinone adsorption of the invention to hydroquinone can reach 597mg.g -1 The adsorption equilibrium time is 240min, and the covalent organic framework material for hydroquinone adsorption can be recycled for more than 5 times, has short adsorption time and higher adsorption quantity, and can be used for adsorbing hydroquinone in a solution.
Drawings
FIG. 1 is an infrared spectrum of a covalent organic framework material for hydroquinone adsorption prepared in example 1, with wavelength on the abscissa and light transmittance on the ordinate;
FIG. 2 is a graph showing fluorescence emission spectra of hydroquinone prepared in example 1 and used for adsorption of hydroquinone according to adsorption time, wherein the abscissa indicates wavelength and the ordinate indicates fluorescence intensity;
FIG. 3 is a graph showing the adsorption time of hydroquinone by the covalent organic framework material for hydroquinone adsorption prepared in example 1, wherein the abscissa indicates time and the ordinate indicates the adsorption amount of hydroquinone;
FIG. 4 is a graph showing adsorption isotherms of hydroquinone solutions of different concentrations, the concentration of the hydroquinone solution on the abscissa and the equilibrium adsorption amount on the ordinate, of the covalent organic framework material for hydroquinone adsorption prepared in example 1, detected by fluorescence emission spectrometry.
Detailed Description
The beneficial effects of the invention are verified by the following examples:
example 1: the preparation method of the covalent organic framework material for hydroquinone adsorption in the embodiment comprises the following steps:
1. 0.12g of 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 0.37g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are weighed, added to a pyrex tube, and then 0.2mL of p-dichlorobenzene and 0.8mL of glacial acetic acid are added and mixed uniformly;
2. vacuumizing the pyrex tube until the vacuum representation number reaches-0.098 MPa, and then charging nitrogen to normal pressure, wherein the vacuumizing and charging nitrogen operation is circulated for 5 times, so that the interior of the pyrex tube is kept in a nitrogen environment;
3. the pyrex tube was heated to 100 ℃ and reacted for 4 days;
4. cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake with dichloromethane for 5 times, and carrying out vacuum drying for 10 hours under the conditions that the temperature is 120 ℃ and the vacuum representation number is-0.098 MPa to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield of the covalent organic framework material is 86 percent.
The covalent organic framework material for hydroquinone adsorption obtained in this example 1 was structurally characterized by fourier infrared spectroscopy, and the obtained infrared spectrum is shown in fig. 1. As can be seen from FIG. 1, at 1604cm -1 The characteristic absorption peak of c=n appears, indicating successful preparation of the covalent organic framework material for hydroquinone adsorption.
The covalent organic framework material for hydroquinone adsorption prepared in example 1 was used as an adsorbent to determine hydroquinone adsorption by fluorescence emission spectrometry, and the specific method is as follows:
1. preparing hydroquinone solution with concentration of 300mg/L, taking 10mL of hydroquinone solution, namely a benzenediol solution I, taking 280nm as excitation wavelength, measuring fluorescence emission spectrum of the hydroquinone solution I, and taking emission intensity of the hydroquinone solution I at the emission wavelength of 338nm as T A ；
2. Adding 9mg of covalent organic framework material for hydroquinone adsorption into the hydroquinone solution I, uniformly dispersing, and stirring; sampling once after stirring for 10min, 20min, 30min, 40min, 50min, 60min, 120min, 180min, 240min and 300min respectively, filtering with a filter membrane to remove covalent organic framework materials for hydroquinone adsorption in the solution, and respectively obtaining hydroquinone solutions with different adsorption times, namely hydroquinone solution II;
3. measuring fluorescence emission spectrum of hydroquinone solution II with 280nm as excitation wavelength, and recording emission intensity at 338nm as T B ；
4. Comparison T A And T B Discovery of T A >T B It can be determined that the covalent organic framework material for hydroquinone adsorption has adsorption performance on hydroquinone.
FIG. 2 is a graph of fluorescence emission spectra of hydroquinone solution I and hydroquinone solution II, respectively, of the covalent organic framework material for hydroquinone adsorption prepared in example 1, with wavelength on the abscissa and fluorescence intensity on the ordinate. As can be seen from FIG. 2, the fluorescence intensity of hydroquinone was 105a.u., and 24a.u. at 240min of adsorption, the fluorescence intensity was reduced to 1/4 of the original value, and the fluorescence intensity was gradually reduced with the increase of time. The fact that the adsorption amount of the covalent organic framework material for hydroquinone adsorption to hydroquinone gradually increases and the concentration of hydroquinone in the hydroquinone solution II gradually decreases with the increase of time proves that the covalent organic framework material for hydroquinone adsorption can adsorb hydroquinone. Using fluorescence emission spectroscopy, hydroquinone can be detected qualitatively by a decrease in the fluorescence spectral intensity of the solution before and after adsorption of the covalent organic framework material.
FIG. 3 is a graph of the adsorption time of hydroquinone for the covalent organic framework material for hydroquinone prepared in example 1, plotted against the adsorption time of hydroquinone, plotted against time on the abscissa, and the adsorption amount of hydroquinone on the ordinate, used to calculate the maximum adsorption amount of hydroquinone for the covalent organic framework material for hydroquinone adsorption when the adsorption equilibrium is reached. According to the formula 1: q t ＝V(c 0 -c)/m, calculating the maximum adsorption of hydroquinone by the covalent organic framework material for hydroquinone adsorption, wherein c 0 Represents the initial concentration of the hydroquinone solution I (mg.L -1 ) Wherein c (mg.L) -1 ) Represents the concentration of the hydroquinone solution II at different adsorption times, m is the mass (g), q of the covalent organic framework material for hydroquinone adsorption t (mg·g -1 ) Represents the adsorption amount of hydroquinone by the covalent organic framework material for hydroquinone adsorption. As can be seen from FIG. 3, the adsorption amount of hydroquinone by the covalent organic framework material for hydroquinone adsorption reaches 181.81 mg.g at 10min -1 And reach equilibrium in 240min, and the maximum adsorption amount can reach 428 mg.g -1 。
Soaking and washing the covalent organic framework material for hydroquinone adsorption after hydroquinone adsorption with methanol for 3 times, removing hydroquinone, filtering, and vacuum drying for 48 hours, and recovering the covalent organic framework material for hydroquinone adsorption. The recovered covalent organic framework material for hydroquinone adsorption is repeatedly used for absorbing hydroquinone. After repeated recovery and use for 5 times, the removal rate of hydroquinone can still reach 80 percent.
The equilibrium adsorption amount of hydroquinone by using the covalent organic framework material for hydroquinone adsorption prepared in example 1 as an adsorbent was determined by fluorescence emission spectrometry as follows:
1. respectively preparing hydroquinone solutions with the concentration of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L and 100mg/L, respectively measuring the fluorescence emission spectra of the hydroquinone solutions, recording the fluorescence emission intensity when the emission wavelength is 338nm, taking the fluorescence intensity as an ordinate, taking the hydroquinone concentration as an abscissa, and drawing a standard curve between the hydroquinone concentration and the fluorescence intensity thereof;
2. taking 10mL of solution to be detected containing hydroquinone, measuring the fluorescence emission spectrum of the solution, and recording the emission intensity of the solution as Tc when the emission wavelength is 338 nm;
3. the hydroquinone concentration corresponding to Tc is detected on a standard curve and is recorded as the initial concentration c of the hydroquinone in the solution to be detected 0 ；
4. Adding covalent organic framework material with the mass of m=6mg for hydroquinone adsorption into a solution to be detected containing hydroquinone with the volume of V=20mL, adsorbing for 48 hours to reach adsorption equilibrium, filtering the covalent organic framework material for hydroquinone adsorption, detecting the fluorescence emission spectrum of the filtrate, and recording the emission intensity at the emission wavelength of 338nm as Td;
5. the concentration of hydroquinone corresponding to Td is found on the standard curve and is recorded as the equilibrium concentration c of hydroquinone e ；
6. According to formula q e ＝V(c 0 -c e ) M the equilibrium adsorption of hydroquinone by the covalent organic framework material for hydroquinone adsorption is calculated, where q e (mg·g -1 ) Represents the equilibrium adsorption quantity, q, of the covalent organic framework material for hydroquinone adsorption to hydroquinone e Is expressed in mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the V represents the volume of the solution to be detected containing hydroquinone in the step four, and the unit is L; c 0 Represents the initial concentration in step three, which is in mg.L -1 ；c e Represents the equilibrium concentration of hydroquinone in step five, in mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the m represents the hydroquinone used in step fourThe mass of the adsorbed covalent organic framework material is given in g.
FIG. 4 is an adsorption isotherm of a covalent organic framework material for adsorption of hydroquinone to hydroquinone of different concentrations, with the abscissa indicating the concentration of hydroquinone in solution at equilibrium of adsorption and the ordinate indicating the amount of equilibrium adsorption. As seen from fig. 4, the adsorption amount of hydroquinone by the covalent organic framework material for hydroquinone adsorption showed an increasing trend with increasing hydroquinone concentration. When the equilibrium adsorption concentration is 400mg/L, the equilibrium adsorption quantity is reached, and the equilibrium adsorption quantity can reach 597mg.g -1 。
Example 2: the preparation method of the covalent organic framework material for hydroquinone adsorption in the embodiment comprises the following steps:
1. 0.18g of 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 0.46g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde were added to a pyrex tube, followed by 0.8mL of mesitylene and 1.0mL of trifluoroacetic acid, and mixed well;
2. carrying out vacuumizing-nitrogen charging circulation operation on the pyrex tube, so that the interior of the pyrex tube is kept in a nitrogen environment;
3. the pyrex tube was heated to 150 ℃ and reacted for 3 days;
4. cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake with acetone, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 79%.
Example 3: the preparation method of the covalent organic framework material for hydroquinone adsorption in the embodiment comprises the following steps:
1. 0.12g of 2- (3-trifluoromethylphenyl) -1H-phenanthryl [9,10-d ] imidazole-6, 9-diamine and 0.36g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added to a pyrex tube, and then 0.5mL of isopropanol, 0.5mL of N, N-dimethylformamide and 1.5mL of benzenesulfonic acid are added and mixed well;
2. carrying out vacuumizing-nitrogen charging circulation operation on the pyrex tube, so that the interior of the pyrex tube is kept in a nitrogen environment;
3. the pyrex tube was heated to 180 ℃ and reacted for 2 days;
4. cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by tetrahydrofuran, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 74%.
Example 4: the preparation method of the covalent organic framework material for hydroquinone adsorption in the embodiment comprises the following steps:
1. 0.10g of 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 0.40g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added into a pyrex tube, and then 1.5mL of mesitylene, 0.2mL of dimethyl sulfoxide and 0.5mL of concentrated hydrochloric acid with the mass percentage concentration of 30% -37% are added and mixed uniformly;
2. carrying out vacuumizing-nitrogen charging circulation operation on the pyrex tube, so that the interior of the pyrex tube is kept in a nitrogen environment;
3. the pyrex tube was heated to 200 ℃ and reacted for 3 days;
4. cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake with ethanol, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 88%.
Example 5: the preparation method of the covalent organic framework material for hydroquinone adsorption in the embodiment comprises the following steps:
1. 0.25g of 2- (3-trifluoromethylphenyl) -1H-phenanthryl [9,10-d ] imidazole-6, 9-diamine and 0.73g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added into a pyrex tube, then 0.3mL of dioxane, 0.8mL of paradichlorobenzene and 1.8mL of concentrated sulfuric acid with the mass percentage concentration of 95% -98% are added, and the mixture is uniformly mixed;
2. carrying out vacuumizing-nitrogen charging circulation operation on the pyrex tube, so that the interior of the pyrex tube is kept in a nitrogen environment;
3. the pyrex tube was heated to 240 ℃ and reacted for 1 day;
4. cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using N, N-dimethylformamide and ethyl acetate, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 74%.
Example 6: the preparation method of the covalent organic framework material for hydroquinone adsorption in the embodiment comprises the following steps:
1. 0.16g of 2- (3-trifluoromethylphenyl) -1H-phenanthryl [9,10-d ] imidazole-6, 9-diamine and 0.35g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde were added to a pyrex tube, and 1.0mL of N, N-dimethylformamide and 0.2mL of glacial acetic acid were added and mixed well;
2. carrying out vacuumizing-nitrogen charging circulation operation on the pyrex tube, so that the interior of the pyrex tube is kept in a nitrogen environment;
3. the pyrex tube was heated to 140 ℃ and reacted for 5 days;
4. cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake with dichloromethane, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 79%.
Example 7: the preparation method of the covalent organic framework material for hydroquinone adsorption in the embodiment comprises the following steps:
1. 0.17g of 2- (3-trifluoromethylphenyl) -1H-phenanthryl [9,10-d ] imidazole-6, 9-diamine and 0.52g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added to a pyrex tube, followed by 0.4mL of p-dichlorobenzene, 0.5mL of dioxane and 0.5mL of benzenesulfonic acid, and mixed well;
2. carrying out vacuumizing-nitrogen charging circulation operation on the pyrex tube, so that the interior of the pyrex tube is kept in a nitrogen environment;
3. the pyrex tube was heated to 120 ℃ and reacted for 3 days;
4. cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using methanol and acetone, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 81%. .
Claims (10)
1. A covalent organic framework material for hydroquinone adsorption, characterized in that the basic structural units of the covalent organic framework material are as follows:
2. a process for preparing a covalent organic framework material for hydroquinone adsorption as claimed in claim 1, characterized in that it is carried out by the following steps:
1. the ratio of the amounts of substances of 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde is 1: (1-5) weighing 2- (3-trifluoromethyl phenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde, adding into a pyrex tube, adding an organic solvent I and acid, and uniformly mixing;
2. vacuumizing the pyrex tube, then filling nitrogen, and repeating the vacuumizing and nitrogen filling operation for 4-5 times;
3. heating the pyrex tube to 100-300 ℃ for reaction for 1-6 days;
4. and cooling to room temperature after the reaction is finished, carrying out suction filtration, repeatedly washing a filter cake by using an organic solvent II, and carrying out vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption.
3. The method for preparing the covalent organic framework material for hydroquinone adsorption as claimed in claim 2, wherein the organic solvent I in the step one is one or a combination of any two of paradichlorobenzene, mesitylene, isopropanol, dioxane, dimethyl sulfoxide and N, N-dimethylformamide.
4. A method for the preparation of a covalent organic framework material for hydroquinone adsorption according to claim 2 or 3, characterized in that in step one the ratio of the mass of 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to the volume of organic solvent I is (0.1-0.3) g:1mL.
5. The method for preparing a covalent organic framework material for hydroquinone adsorption as claimed in claim 2 or 3, wherein the acid in the step one is one or a combination of any two of benzenesulfonic acid, trifluoroacetic acid, glacial acetic acid, concentrated hydrochloric acid with a mass percentage concentration of 30% -37%, and concentrated sulfuric acid with a mass percentage concentration of 95% -98%.
6. A method for preparing a covalent organic framework material for hydroquinone adsorption as claimed in claim 2 or 3, characterized in that the ratio of the mass of 2- (3-trifluoromethylphenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to the volume of acid as described in step one is 1g (0.2-0.4) mL.
7. A method for preparing a covalent organic framework material for hydroquinone adsorption as claimed in claim 2 or 3, wherein the organic solvent II of the washed cake in step four is one or a combination of any two of methanol, ethanol, tetrahydrofuran, ethyl acetate, acetone, dichloromethane and N, N-dimethylformamide.
8. Use of a covalent organic framework material for hydroquinone adsorption as claimed in claim 1, characterized in that the use is to qualitatively detect hydroquinone in a solution using the covalent organic framework material for hydroquinone adsorption; or the covalent organic framework material for hydroquinone adsorption is used as an adsorbent to absorb the hydroquinone in the solution.
9. Use of a covalent organic framework material for hydroquinone adsorption according to claim 8, characterized by the qualitative detection of hydroquinone in solution with the covalent organic framework material for hydroquinone adsorption, in particular as follows:
1. measuring fluorescence emission spectrum of hydroquinone solution with concentration of 300mg/L by using 280nm as excitation wavelength, and recording emission intensity at emission wavelength of 338nm as T A ；
2. Adding 9mg of covalent organic framework material for hydroquinone adsorption into 10mL of solution to be detected, uniformly dispersing, stirring for 30-300 min, and filtering to remove the covalent organic framework material for hydroquinone adsorption in the solution to be detected by using a filter membrane to obtain the treated solution to be detected;
3. measuring the fluorescence emission spectrum of the treated solution to be measured by taking 280nm as an excitation wavelength, and marking the emission intensity at the emission wavelength of 338nm as T B ；
4. Comparison T A And T B If T A >T B It can be determined that hydroquinone is contained in the solution to be measured.
10. The use of a covalent organic framework material for hydroquinone adsorption according to claim 8, characterized in that the method for testing the equilibrium adsorption quantity of hydroquinone by using the covalent organic framework material for hydroquinone adsorption as adsorbent comprises the following steps:
1. respectively preparing hydroquinone solutions with the concentration of 10mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L and 100mg/L, respectively measuring the fluorescence emission spectra of the hydroquinone solutions, recording the fluorescence emission intensity when the emission wavelength is 338nm, taking the fluorescence intensity as an ordinate, taking the hydroquinone concentration as an abscissa, and drawing a standard curve between the hydroquinone concentration and the fluorescence intensity thereof;
2. measuring fluorescence emission spectrum of the solution to be measured containing hydroquinone, and recording emission intensity of the solution to be measured as Tc when the emission wavelength is 338 nm;
3. the hydroquinone concentration corresponding to Tc is detected on a standard curve and is recorded as the initial concentration c of the hydroquinone in the solution to be detected 0 ；
4. Adding covalent organic framework material with the mass of m and used for hydroquinone adsorption into a solution to be detected, which contains hydroquinone, with the volume of V, adsorbing for 48 hours to reach adsorption equilibrium, filtering the covalent organic framework material used for hydroquinone adsorption, detecting the fluorescence emission spectrum of filtrate, and recording the emission intensity of the filtrate with the emission wavelength of 338nm as Td;
5. find and Td pairs on standard curveThe corresponding hydroquinone concentration, designated as the equilibrium concentration c of hydroquinone e ；
6. According to formula q e ＝V(c 0 -c e ) M the equilibrium adsorption of hydroquinone by the covalent organic framework material for hydroquinone adsorption is calculated, where q e Represents the equilibrium adsorption quantity, q, of the covalent organic framework material for hydroquinone adsorption to hydroquinone e Is expressed in mg.g -1 The method comprises the steps of carrying out a first treatment on the surface of the V represents the volume of the solution to be detected containing hydroquinone in the step four, and the unit is L; c 0 Represents the initial concentration in step three, which is in mg.L -1 ；c e Represents the equilibrium concentration of hydroquinone in step five, in mg.L -1 The method comprises the steps of carrying out a first treatment on the surface of the m represents the mass of the covalent organic framework material used for hydroquinone adsorption in the fourth step, and the unit is g.
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