CN114085387A - 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 PDF

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CN114085387A
CN114085387A CN202111515003.5A CN202111515003A CN114085387A CN 114085387 A CN114085387 A CN 114085387A CN 202111515003 A CN202111515003 A CN 202111515003A CN 114085387 A CN114085387 A CN 114085387A
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赵冰
郑旺
李志刚
赵立杰
阚伟
王丽艳
孙立
王秀文
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Qiqihar University
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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 for adsorbing hydroquinone and low maximum adsorption capacity in the prior art. The basic structural units of the covalent organic framework material for adsorbing hydroquinone are as follows:
Figure DDA0003406590120000011
it is prepared from 2- (4-aminophenyl) -1H-phenanthrene [9,10-d]Imidazole-6, 9-diamine and 5'- (4-formylphenyl) - [1,1':3', 1' -terphenyl]4, 4' dimethyl aldehyde. For absorbing hydroquinone in solution or for detecting hydroquinone in solution. The equilibrium adsorption quantity of the covalent organic framework material for adsorbing the hydroquinone to the hydroquinone can reach 597mg g‑1The adsorption equilibrium time is 240min, and the method can be used for adsorbing or detecting hydroquinone in a solution.

Description

Covalent organic framework material for hydroquinone adsorption and preparation method and application thereof
Technical Field
The invention relates to a covalent organic framework material and a preparation method and application thereof.
Background
With the rapid development of industrialization and urbanization and the continuous improvement of the living standard of people, the problem of environmental pollution is getting more serious, and great threat is brought to the life health of human beings. The phenol substance is a common environmental pollutant, hydroquinone is one of the phenol substances, is also called hydroquinone, is a basic organic chemical raw material, has wide application, is an important intermediate of pesticide, medicine and dye, is commonly used for preparing azo and anthraquinone dye, film developer, cosmetic whitening agent, petroleum anticoagulant, food antioxidant, rubber preservative and medical intermediate, has great toxicity to human body, and has irritation to skin, eyes and mucous membrane. Due to the characteristics of high toxicity and difficult degradation of hydroquinone, the prior hydroquinone treatment technology mainly comprises an adsorption method, an electrochemical oxidation method, an ozone oxidation method, a photocatalysis method and the like. In recent years, adsorption methods have been widely used for removing hydroquinone from the environment because of their advantages such as easy operation and low cost. Therefore, the development of a novel adsorbent for adsorbing hydroquinone is of great significance.
Covalent Organic Framework (COFs) materials have a wide application prospect in the field of adsorption due to the advantages of ordered pore structures, large specific surface area, uniform porosity, good chemical stability and the like, and thus have become a focus of attention of researchers. At present, documents about covalent organic framework materials adsorbing phenolic substances are reported in succession, and an azine-linked covalent organic framework material is designed and synthesized in an article of 'harmful substances' in No. 5 of 355 volume in 2018, namely 'layered porous monoliths constructed by covalent organic frameworks and application thereof in removing bisphenol A', so that the bisphenol A is adsorbed, and the adsorption capacity of the covalent organic framework material is 61.3mg g-1. Simple synthesis of Fe in article of molecular liquid journal of 320 volume B part 20203O4The following publication discloses the adsorption of bisphenol A using a complexed covalent organic framework material, in which the maximum adsorption amount is only 140mg g-1. At present, the material for adsorbing hydroquinone is few in types and low in maximum adsorption quantity, and a method for qualitatively detecting hydroquinone and measuring the maximum adsorption quantity by using a fluorescence emission spectroscopy is not available.
According to the current literature reports, the existing materials for adsorbing hydroquinone mainly have the following defects:
1. the material used for adsorbing hydroquinone is less in variety;
2. the material has low adsorption quantity to the hydroquinone and poor adsorption effect;
3. the materials required for the adsorption of hydroquinone are complex to prepare.
Disclosure of Invention
The invention provides a covalent organic framework material for hydroquinone adsorption and a preparation method and application thereof, aiming at solving the technical problems of few types and low maximum adsorption capacity of the existing material for hydroquinone adsorption.
The basic structural units of the covalent organic framework material for hydroquinone adsorption of the invention are as follows:
Figure BDA0003406590100000021
the covalent organic framework material for hydroquinone adsorption is obtained by reacting 2- (4-aminophenyl) -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:
the ratio of the amount of 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to that of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde is 1: (1-5) weighing 2- (4-aminophenyl) -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 an acid, and uniformly mixing;
secondly, vacuumizing the pyrex tube, filling nitrogen, and repeating the operations of vacuumizing and filling nitrogen for 4-5 times;
thirdly, heating the pyrex tube to 100-300 ℃ and reacting for 1-6 days;
and fourthly, 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 adsorbing the hydroquinone.
Further, the organic solvent I in the first step is one or a combination of any two of p-dichlorobenzene, mesitylene, isopropanol, dioxane, dimethyl sulfoxide and N, N-dimethylformamide;
further, the ratio of the mass of the 2- (4-aminophenyl) -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: 1 mL;
further, the acid in the step one is one of 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%;
furthermore, the ratio of the mass of the 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to the volume of the acid in the step one 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 adsorbing hydroquinone is to use the covalent organic framework material for adsorbing hydroquinone as an adsorbent to absorb the hydroquinone in a solution.
The application of the covalent organic framework material for adsorbing the hydroquinone is to use the covalent organic framework material for adsorbing the hydroquinone for qualitatively or quantitatively detecting the hydroquinone in a solution.
The method for qualitatively detecting the hydroquinone in the solution by using the covalent organic framework material for adsorbing the hydroquinone comprises the following steps of using the covalent organic framework material for adsorbing the hydroquinone as an adsorbent and qualitatively detecting the hydroquinone in the solution by a fluorescence emission spectroscopy method:
measuring the fluorescence emission spectrum of hydroquinone solution with the concentration of 300mg/L by taking 280nm as an excitation wavelength, and recording the emission intensity when the emission wavelength is 338nm as TA；
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 by using a filter membrane to remove the covalent organic framework material for hydroquinone adsorption from the solution to be detected to obtain the treated solution to be detected;
thirdly, measuring the fluorescence emission spectrum of the treated solution to be measured by taking 280nm as the excitation wavelength, and recording the emission intensity when the emission wavelength is 338nm as TB；
Fourthly, comparing TAAnd TBIf T isA>TBAnd determining that the solution to be detected contains hydroquinone.
The method for testing the equilibrium adsorption quantity of hydroquinone adsorbed by a covalent organic framework material used for hydroquinone adsorption as an adsorbent is determined by fluorescence emission spectrometry, and comprises the following specific steps:
preparing hydroquinone solutions with the concentrations 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 spectrum of the hydroquinone solutions respectively, recording the fluorescence emission intensity when the emission wavelength is 338nm, and drawing a standard curve between the hydroquinone concentration and the fluorescence intensity by taking the fluorescence intensity as a vertical coordinate and the hydroquinone concentration as a horizontal coordinate;
secondly, taking the solution to be detected containing hydroquinone, measuring the fluorescence emission spectrum of the solution, and recording the emission intensity of the solution with the emission wavelength of 338nm as Tc;
thirdly, finding out the hydroquinone concentration corresponding to Tc on the standard curve, and recording the hydroquinone concentration as the initial concentration c of the hydroquinone in the solution to be detected0；
Fourthly, adding m mass of covalent organic framework materials for hydroquinone adsorption into the solution to be detected containing hydroquinone with the volume of V, adsorbing for 48 hours to achieve adsorption balance, filtering the covalent organic framework materials for hydroquinone adsorption, detecting the fluorescence emission spectrum of the filtrate, and recording the emission intensity as Td when the emission wavelength is 338 nm;
fifthly, finding out the hydroquinone concentration corresponding to Td on the standard curve, and marking the hydroquinone concentration as the equilibrium concentration ce；
Sixthly, according to a formula qe＝V(c0-ce) Calculating the equilibrium adsorption capacity of the covalent organic framework material for hydroquinone adsorption on hydroquinone, wherein qe(mg·g-1) Represents the equilibrium adsorption quantity of the covalent organic framework material for adsorbing the hydroquinone, qeIn mg g-1(ii) a V represents the volume of the solution to be measured containing hydroquinone in the fourth step, and the unit of V is L; c. C0Represents the initial concentration in step three, and the unit is mg.L-1；ceRepresents the equilibrium concentration of hydroquinone in the fifth step, and the unit is mg.L-1(ii) a m represents the mass of the covalent organic framework material used for hydroquinone adsorption in step four and is given in g.
The chemical reaction formula of the covalent organic framework material for adsorbing hydroquinone is as follows:
Figure BDA0003406590100000041
the equilibrium adsorption capacity of the covalent organic framework material for adsorbing the hydroquinone of the invention to the hydroquinone can reach 597mg g-1The adsorption equilibrium time is 240min, and the covalent organic framework material for adsorbing hydroquinone can be used for adsorbing hydroquinone for more than 5 times, has short adsorption time and higher adsorption capacity, 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 fluorescence emission spectrum of the covalent organic framework material for hydroquinone adsorption prepared in example 1, which varies with adsorption time when hydroquinone is detected by fluorescence emission spectrometry, with the abscissa being wavelength and the ordinate being fluorescence intensity;
FIG. 3 is a graph of the adsorption time of the covalent organic framework material for hydroquinone adsorption prepared in example 1 to hydroquinone, with time on the abscissa and the amount of hydroquinone adsorbed on the ordinate;
fig. 4 is a graph of adsorption isotherms of hydroquinone solutions of different concentrations, with the abscissa being the concentration of the hydroquinone solution and the ordinate being the equilibrium adsorption amount, of the covalent organic framework material for hydroquinone adsorption prepared in example 1, detected by fluorescence emission spectroscopy.
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 hydroquinone adsorption of the embodiment comprises the following steps:
firstly, 0.12g of 2- (4-aminophenyl) -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 and added into a pyrex tube, and then 0.2mL of p-dichlorobenzene and 0.8mL of glacial acetic acid are added and mixed evenly;
secondly, vacuumizing the pyrex pipe until the vacuum representation number reaches-0.098 MPa, then filling nitrogen to the normal pressure, and circulating the vacuumizing and nitrogen filling operation for 5 times to keep the nitrogen environment in the pyrex pipe;
thirdly, heating the pyrex tube to 100 ℃ and reacting for 4 days;
and fourthly, cooling to room temperature after the reaction is finished, performing suction filtration, repeatedly washing a filter cake for 5 times by using dichloromethane, and performing 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 adsorbing the hydroquinone, wherein the yield of the covalent organic framework material is 86 percent by calculation.
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, the distance is 1604cm-1The characteristic absorption peak of C ═ N appears, which indicates that the covalent organic framework material for hydroquinone adsorption is successfully prepared.
The covalent organic framework material for hydroquinone adsorption prepared in example 1 is used as an adsorbent, and the adsorption of hydroquinone is determined by fluorescence emission spectroscopy, and the specific method is as follows:
preparing a hydroquinone solution with the concentration of 300mg/L, taking 10mL of the hydroquinone solution as the hydroquinone solution I, measuring the fluorescence emission spectrum of the hydroquinone solution I by taking 280nm as an excitation wavelength, and recording the emission intensity when the emission wavelength is 338nm as TA；
Adding 9mg of covalent organic framework material for hydroquinone adsorption into the hydroquinone solution I, uniformly dispersing, and stirring; respectively sampling once after stirring for 10min, 20min, 30min, 40min, 50min, 60min, 120min, 180min, 240min and 300min, 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, which are marked as hydroquinone solution II;
thirdly, measuring the fluorescence of the hydroquinone solution II by taking 280nm as the excitation wavelengthLight emission spectrum, emission intensity at an emission wavelength of 338nm, denoted TB；
Fourthly, comparing TAAnd TBDiscovery of TA>TBThe covalent organic framework material for hydroquinone adsorption can be judged to have adsorption performance on hydroquinone.
Fig. 2 shows fluorescence emission spectra of the covalent organic framework material for hydroquinone adsorption prepared in example 1, hydroquinone solution I and hydroquinone solution II, 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., the fluorescence intensity at 240min of adsorption was 24a.u., the fluorescence intensity decreased to 1/4, and the fluorescence intensity gradually decreased with the increase of time. The covalent organic framework material for adsorbing the hydroquinone is proved to be capable of adsorbing the hydroquinone by increasing the adsorption amount of the hydroquinone and gradually reducing the concentration of the hydroquinone in the hydroquinone solution II along with the increase of the time. Using fluorescence emission spectroscopy, hydroquinone can be detected qualitatively by a decrease in 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 the covalent organic framework material for hydroquinone adsorption prepared in example 1, wherein the abscissa represents time and the ordinate represents the adsorption amount of hydroquinone, and the curve is used for calculating the maximum adsorption amount of the covalent organic framework material for hydroquinone adsorption to hydroquinone when the adsorption equilibrium is reached. According to equation 1: q. q.st＝V(c0C)/m, calculating the maximum adsorption capacity of the covalent organic framework material for hydroquinone adsorption on hydroquinone, wherein c0Denotes the initial concentration (mg. L) of the hydroquinone solution I-1) Wherein c (mg. L)-1) Representing the concentration of hydroquinone solution II at different adsorption times, m is the mass (g) of the covalent organic framework material used for hydroquinone adsorption, qt(mg·g-1) Represents the adsorption amount of the covalent organic framework material for adsorbing hydroquinone on hydroquinone. As can be seen from FIG. 3, at 10min, the pair of covalent organic framework materials for hydroquinone adsorptionThe adsorption capacity of the benzenediol reaches 181.81mg g-1And reaches equilibrium in 240min, and the maximum absorption amount can reach 428mg g when the absorption amount is balanced-1。
Soaking and washing the covalent organic framework material for adsorbing the hydroquinone after adsorbing the hydroquinone for 3 times by using methanol, removing the hydroquinone, filtering, and recovering the covalent organic framework material for adsorbing the hydroquinone after vacuum drying for 48 hours. And (3) repeatedly using the obtained covalent organic framework material for adsorbing the hydroquinone for absorbing the hydroquinone. After the catalyst is repeatedly recycled for 5 times, the removal rate of the p-dihydroxybenzene can still reach 80 percent.
The equilibrium adsorption amount of hydroquinone adsorbed by the covalent organic framework material for hydroquinone adsorption prepared in example 1 as an adsorbent was determined by fluorescence emission spectrometry, and the specific method was as follows:
preparing hydroquinone solutions with the concentrations 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 spectrum of the hydroquinone solutions respectively, recording the fluorescence emission intensity when the emission wavelength is 338nm, and drawing a standard curve between the hydroquinone concentration and the fluorescence intensity by taking the fluorescence intensity as a vertical coordinate and the hydroquinone concentration as a horizontal coordinate;
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 with the emission wavelength of 338nm as Tc;
thirdly, finding out the hydroquinone concentration corresponding to Tc on the standard curve, and recording the hydroquinone concentration as the initial concentration c of the hydroquinone in the solution to be detected0；
Fourthly, adding a covalent organic framework material with the mass m of 6mg for hydroquinone adsorption into a solution to be detected containing hydroquinone with the volume V of 20mL, carrying out adsorption for 48h to achieve adsorption equilibrium, filtering the covalent organic framework material for hydroquinone adsorption, detecting the fluorescence emission spectrum of the filtrate, and recording the emission intensity as Td when the emission wavelength is 338 nm;
fifthly, finding out the hydroquinone concentration corresponding to Td on the standard curve, and marking the hydroquinone concentration as the equilibrium concentration ce；
Sixthly, according to a formula qe＝V(c0-ce) Calculating the equilibrium adsorption capacity of the covalent organic framework material for hydroquinone adsorption on hydroquinone, wherein qe(mg·g-1) Represents the equilibrium adsorption quantity of the covalent organic framework material for adsorbing the hydroquinone, qeIn mg g-1(ii) a V represents the volume of the solution to be measured containing hydroquinone in the fourth step, and the unit of V is L; c. C0Represents the initial concentration in step three, and the unit is mg.L-1；ceRepresents the equilibrium concentration of hydroquinone in the fifth step, and the unit is mg.L-1(ii) a m represents the mass of the covalent organic framework material used for hydroquinone adsorption in step four and is given in g.
Fig. 4 is an adsorption isotherm of a covalent organic framework material for hydroquinone adsorption on hydroquinone of different concentrations, the abscissa is the hydroquinone concentration in the solution at equilibrium of adsorption, and the ordinate is the equilibrium adsorption capacity. As seen in fig. 4, the covalent organic framework material used for hydroquinone adsorption exhibited an increasing tendency to adsorb hydroquinone as the concentration of hydroquinone increased. When the equilibrium adsorption concentration is 400mg/L, the equilibrium adsorption capacity is achieved, and the equilibrium adsorption capacity can reach 597mg g-1。
Example 2: the preparation method of the covalent organic framework material for hydroquinone adsorption of the embodiment comprises the following steps:
firstly, 0.18g of 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 0.46g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added into a pyrex tube, and then 0.8mL of mesitylene and 1.0mL of trifluoroacetic acid are added and mixed evenly;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the pyrex pipe to keep the pyrex pipe in a nitrogen environment;
thirdly, heating the pyrex tube to 150 ℃ and reacting for 3 days;
and fourthly, cooling to room temperature after the reaction is finished, performing suction filtration, repeatedly washing a filter cake with acetone, and performing vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 79 percent.
Example 3: the preparation method of the covalent organic framework material for hydroquinone adsorption of the embodiment comprises the following steps:
firstly, 0.12g of 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 0.36g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added into 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 uniformly;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the pyrex pipe to keep the pyrex pipe in a nitrogen environment;
thirdly, heating the pyrex tube to 180 ℃ and reacting for 2 days;
and fourthly, cooling to room temperature after the reaction is finished, performing suction filtration, repeatedly washing a filter cake with tetrahydrofuran, and performing vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 74 percent.
Example 4: the preparation method of the covalent organic framework material for hydroquinone adsorption of the embodiment comprises the following steps:
firstly, 0.10g of 2- (4-aminophenyl) -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;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the pyrex pipe to keep the pyrex pipe in a nitrogen environment;
thirdly, heating the pyrex tube to 200 ℃ and reacting for 3 days;
and fourthly, cooling to room temperature after the reaction is finished, performing suction filtration, repeatedly washing a filter cake with ethanol, and performing vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 88 percent.
Example 5: the preparation method of the covalent organic framework material for hydroquinone adsorption of the embodiment comprises the following steps:
firstly, 0.25g of 2- (4-aminophenyl) -1H-phenanthrene [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 p-dichlorobenzene and 1.8mL of concentrated sulfuric acid with the mass percentage concentration of 95-98 percent are added, and the mixture is uniformly mixed;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the pyrex pipe to keep the pyrex pipe in a nitrogen environment;
thirdly, heating the pyrex tube to 240 ℃ and reacting for 1 day;
and fourthly, cooling to room temperature after the reaction is finished, performing suction filtration, repeatedly washing a filter cake by using N, N-dimethylformamide and ethyl acetate, and performing vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 74 percent.
Example 6: the preparation method of the covalent organic framework material for hydroquinone adsorption of the embodiment comprises the following steps:
firstly, 0.16g of 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 0.35g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added into a pyrex tube, 1.0mL of N, N-dimethylformamide and 0.2mL of glacial acetic acid are added, and the mixture is uniformly mixed;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the pyrex pipe to keep the pyrex pipe in a nitrogen environment;
thirdly, heating the pyrex tube to 140 ℃ and reacting for 5 days;
and fourthly, cooling to room temperature after the reaction is finished, performing suction filtration, repeatedly washing a filter cake by using dichloromethane, and performing vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 79 percent.
Example 7: the preparation method of the covalent organic framework material for hydroquinone adsorption of the embodiment comprises the following steps:
firstly, 0.17g of 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and 0.52g of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde are added into a pyrex tube, and then 0.4mL of p-dichlorobenzene, 0.5mL of dioxane and 0.5mL of benzenesulfonic acid are added and mixed uniformly;
secondly, performing cycle operation of vacuumizing and filling nitrogen into the pyrex pipe to keep the pyrex pipe in a nitrogen environment;
thirdly, heating the pyrex tube to 120 ℃ and reacting for 3 days;
and fourthly, cooling to room temperature after the reaction is finished, performing suction filtration, repeatedly washing a filter cake by using methanol and acetone, and performing vacuum drying to obtain the covalent organic framework material for hydroquinone adsorption, wherein the yield is as follows: 81 percent.

Claims (10)

1. A covalent organic framework material for hydroquinone adsorption, characterized in that the basic building blocks of the covalent organic framework material are as follows:
Figure FDA0003406590090000011
2. a process for the preparation of a covalent organic framework material for hydroquinone adsorption according to claim 1, characterized in that it is carried out by the following steps:
the ratio of the amount of 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to that of 5' - (4-formylphenyl) - [1,1':3', 1' -terphenyl ] -4,4 ' dicarboxaldehyde is 1: (1-5) weighing 2- (4-aminophenyl) -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 an acid, and uniformly mixing;
secondly, vacuumizing the pyrex tube, filling nitrogen, and repeating the operations of vacuumizing and filling nitrogen for 4-5 times;
thirdly, heating the pyrex tube to 100-300 ℃ and reacting for 1-6 days;
and fourthly, 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 adsorbing the hydroquinone.
3. The method for preparing covalent organic framework material for hydroquinone adsorption according to claim 2, wherein the organic solvent I in step one is one or a combination of any two of p-dichlorobenzene, mesitylene, isopropanol, dioxane, dimethyl sulfoxide and N, N-dimethylformamide.
4. The method for preparing the covalent organic framework material for hydroquinone adsorption according to claim 2 or 3, characterized in that the ratio of the mass of the 2- (4-aminophenyl) -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: 1 mL.
5. The method according to claim 2 or 3, wherein the acid in the step one is one of benzenesulfonic acid, trifluoroacetic acid, glacial acetic acid, concentrated hydrochloric acid with a concentration of 30-37% by mass, concentrated sulfuric acid with a concentration of 95-98% by mass, or a combination of any two of them.
6. The method for preparing the covalent organic framework material for hydroquinone adsorption according to claim 2 or 3, wherein the ratio of the mass of the 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine to the volume of the acid in the step one is 1g (0.2-0.4) mL.
7. The method for preparing covalent organic framework material for hydroquinone adsorption according to claim 2 or 3, wherein the organic solvent II for washing filter 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. The use of a covalent organic framework material for hydroquinone adsorption as claimed in claim 1, wherein the covalent organic framework material for hydroquinone adsorption is used as a sorbent to absorb hydroquinone in solution.
9. The use of the covalent organic framework material for hydroquinone adsorption according to claim 8, wherein the covalent organic framework material for hydroquinone adsorption is used in a method for qualitative detection of hydroquinone in solution, which comprises the following steps:
measuring the fluorescence emission spectrum of hydroquinone solution with the concentration of 300mg/L by taking 280nm as an excitation wavelength, and recording the emission intensity when the emission wavelength is 338nm as TA；
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 by using a filter membrane to remove the covalent organic framework material for hydroquinone adsorption from the solution to be detected to obtain the treated solution to be detected;
thirdly, measuring the fluorescence emission spectrum of the treated solution to be measured by taking 280nm as the excitation wavelength, and recording the emission intensity when the emission wavelength is 338nm as TB；
Fourthly, comparing TAAnd TBIf T isA>TBAnd determining that the solution to be detected contains hydroquinone.
10. The use of the covalent organic framework material for hydroquinone adsorption according to claim 8, characterized in that the test method for the equilibrium adsorption capacity of hydroquinone adsorbed by the covalent organic framework material for hydroquinone adsorption as adsorbent is as follows:
preparing hydroquinone solutions with the concentrations 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 spectrum of the hydroquinone solutions respectively, recording the fluorescence emission intensity when the emission wavelength is 338nm, and drawing a standard curve between the hydroquinone concentration and the fluorescence intensity by taking the fluorescence intensity as a vertical coordinate and the hydroquinone concentration as a horizontal coordinate;
secondly, taking the solution to be detected containing hydroquinone, measuring the fluorescence emission spectrum of the solution, and recording the emission intensity of the solution with the emission wavelength of 338nm as Tc;
third, finding out Tc pairs on the standard curveThe hydroquinone concentration is recorded as the initial concentration c of hydroquinone in the solution to be measured0；
Fourthly, adding m mass of covalent organic framework materials for hydroquinone adsorption into the solution to be detected containing hydroquinone with the volume of V, adsorbing for 48 hours to achieve adsorption balance, filtering the covalent organic framework materials for hydroquinone adsorption, detecting the fluorescence emission spectrum of the filtrate, and recording the emission intensity as Td when the emission wavelength is 338 nm;
fifthly, finding out the hydroquinone concentration corresponding to Td on the standard curve, and marking the hydroquinone concentration as the equilibrium concentration ce；
Sixthly, according to a formula qe＝V(c0-ce) Calculating the equilibrium adsorption capacity of the covalent organic framework material for hydroquinone adsorption on hydroquinone, wherein qeRepresents the equilibrium adsorption quantity of the covalent organic framework material for adsorbing the hydroquinone, qeIn mg g-1(ii) a V represents the volume of the solution to be measured containing hydroquinone in the fourth step, and the unit of V is L; c. C0Represents the initial concentration in step three, and the unit is mg.L-1；ceRepresents the equilibrium concentration of hydroquinone in the fifth step, and the unit is mg.L-1(ii) a m represents the mass of the covalent organic framework material used for hydroquinone adsorption in step four and is given in g.
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