CN113578274A - Covalent organic framework material for rapidly detecting methylene blue and preparation method and application thereof - Google Patents
Covalent organic framework material for rapidly detecting methylene blue and preparation method and application thereof Download PDFInfo
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- CN113578274A CN113578274A CN202110911619.8A CN202110911619A CN113578274A CN 113578274 A CN113578274 A CN 113578274A CN 202110911619 A CN202110911619 A CN 202110911619A CN 113578274 A CN113578274 A CN 113578274A
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229960000907 methylthioninium chloride Drugs 0.000 title claims abstract description 144
- 239000000463 material Substances 0.000 title claims abstract description 92
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- PAYGAVVJLIFANV-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarbaldehyde Chemical compound O=CC1=C(C=O)C(C=O)=CC(C=2C=CC=CC=2)=C1C=O PAYGAVVJLIFANV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 14
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 238000002835 absorbance Methods 0.000 claims description 20
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- 238000001514 detection method Methods 0.000 claims description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
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- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
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- KGNUXSSLTONYAW-UHFFFAOYSA-N 1,6-dichlorocyclohexa-2,4-dien-1-amine Chemical compound NC1(Cl)C=CC=CC1Cl KGNUXSSLTONYAW-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
A covalent organic framework material for rapidly detecting methylene blue and a preparation method and application thereof relate to a covalent organic framework material and a preparation method and application thereof. The material aims to solve the technical problems that the existing material has weak methylene blue adsorption capacity, overlong time response of adsorption action and lower single selective adsorption capacity. The basic structural units of the covalent organic framework material of the invention are:
the covalent organic framework material is prepared by reacting biphenyl tetra-aldehyde with 2, 5-diaminobenzene sulfonic acid. The covalent organic framework material is used as an adsorbent, and methylene blue in water can be detected by naked eyes or ultraviolet spectroscopy. The method for detecting the methylene blue is simple and convenient, is easy to operate, achieves adsorption balance in 3min, and has the maximum adsorption quantity of 1565.8 mg.g for the methylene blue‑1And can be recycled. Can be used in the field of identification and removal of methylene blue in water.
Description
Technical Field
The invention relates to a covalent organic framework material and a preparation method and application thereof.
Background
The organic dye Methylene Blue (MB) has been classified as a serious pollutant in surface water due to its wide application in textile, leather, paper, printing and other industries. These dyes can cause environmental pollution problems and their release in the environment can lead to health disorders in humans and animals, such as eye burns or permanent eye injuries. Methylene blue is difficult to remove completely because its stable aromatic structure consists of chromophores and polar groups. Various techniques have been developed to improve the efficiency of MB removal, including adsorption, chemical oxidation, and electrocoagulation. Among these, adsorption has proven to be particularly effective, mainly because of its simplicity and high efficiency. Covalent Organic Frameworks (COFs) are crystalline porous polymeric organic two-or three-dimensional materials formed by reversible chemical reactions that covalently link some elements (carbon, nitrogen, oxygen, boron, etc.) that are relatively light in atomic mass. COFs are crystalline materials made by covalently linking organic building blocks into extended structures, and show great potential in various applications such as gas storage and OPC.
In recent years, more and more families have been developedResearchers have conducted research on the adsorption of methylene blue dyes. A magnetic biochar composite material (SBMB) prepared by a one-step hydrothermal method in an article of magnetic biochar synthesized by waterworks sludge and sewage sludge and methylene blue removing potential thereof in the environmental chemistry engineering newspaper of No. 5 of 9 of 2021 is used for removing methylene blue in water, the methylene blue removing process of the compound is rapid, but the maximum Methylene Blue (MB) adsorption capacity is only 186.003mg/g-1. The synthesis of iron-based metal organic frameworks (MOF-Fe) by solvothermal method was reported in the article "Functionalization of methylene blue adsorption by Fe-type MOF" on the 11 th phase of Saudi chemical society, Vol.24, Vol.2020, p.896-905, wherein the optimum loading of MOF-Fe was 312.5mg/g-1However, it takes about one hour to exhibit the adsorption effect. An article in journal of molecular liquid, volume 36, 2021, that is, beta-cyclodextrin and magnetic graphene oxide modified porous composite hydrogel is used as a super absorbent for adsorbing cationic dye: the adsorption property, adsorption mechanism and hydrogel column process research reports that a polyacrylic acid-based porous superabsorbent composite hydrogel adsorbent beta-CD/MGO/PAA is prepared by a one-pot polymerization method, and methylene blue has good removal capacity but is not used for singly adsorbing methylene blue dye.
According to the reports of the current literature, the materials for adsorbing methylene blue in wastewater mainly have the following defects:
1. the material with the adsorption function on methylene blue is less in variety;
2. the currently reported material has weak adsorption capacity to methylene blue and low equilibrium adsorption capacity;
3. the adsorption time of the material on methylene blue is too long;
4. the material has low single selective adsorption capacity to methylene blue.
Disclosure of Invention
The invention provides a covalent organic framework material for rapidly detecting methylene blue, a preparation method and application thereof, aiming at solving the technical problems that the existing material has weak adsorption capacity to methylene blue, overlong time response of adsorption action and lower single selective adsorption capacity. The covalent organic framework material is a high-efficiency covalent organic framework material which has high adsorption capacity and short adsorption response time and can singly adsorb methylene blue.
The basic structural unit of the covalent organic framework material for rapidly detecting methylene blue is shown as the following formula:
the preparation method of the covalent organic framework material for rapidly detecting methylene blue comprises the following steps:
according to the mass ratio of biphenyl tetra-aldehyde to 2, 5-diaminobenzene sulfonic acid, the ratio is 1: (1-5) dispersing biphenyl tetra-aldehyde and 2, 5-diaminobenzene sulfonic acid in an organic solvent I, adding acid serving as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to below-40 ℃, and then vacuumizing;
thirdly, heating the reaction liquid to 100-200 ℃ and reacting for 72-168 hours; and after the reaction is finished, cooling to room temperature, washing the solid phase substance obtained by centrifugal separation with an organic solvent II, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting methylene blue.
Further, the organic solvent I in the first step is a combination of any two or three of azomethylpyrrolidone, mesitylene, dioxane, o-dichlorobenzene, N-dimethylformamide and N-butanol;
further, the ratio of the amount of the substance of biphenyltetra-aldehyde to the volume of the organic solvent i in step one was 1 mmol: (5-25) mL.
Furthermore, the acid in the step one is concentrated sulfuric acid with the mass percent of 95-98%, concentrated hydrochloric acid with the mass percent of 30-37%, benzenesulfonic acid, p-toluenesulfonic acid, glacial acetic acid or trifluoroacetic acid.
Further, the ratio of the amount of the substance of biphenyltetra-aldehyde to the volume of the acid in step one was 1 mmol: (2.5-10) mL;
furthermore, the organic solvent II in the third step is methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, N-butanol, N-dimethylacetamide or acetone.
The preparation process of the covalent organic framework material for rapidly detecting methylene blue is represented by the following formula:
the application of the covalent organic framework material for rapidly detecting the methylene blue is to use the covalent organic framework material for rapidly detecting the methylene blue as an adsorbent and detect the methylene blue in water by naked eyes or ultraviolet spectroscopy.
The method for qualitatively detecting the methylene blue in the water by using a covalent organic framework material for quickly detecting the methylene blue as an adsorbent and a naked eye method comprises the following steps:
firstly, taking a water solution I to be detected, wherein the color of the solution I is dark blue;
secondly, adding a covalent organic framework material for rapidly detecting methylene blue into the aqueous solution I to prepare a solution II;
and thirdly, observing the color of the solution II after 3min, and if the color of the solution is changed from dark blue to colorless, judging that the aqueous solution I to be detected contains methylene blue.
The method for qualitatively detecting the methylene blue in the water by using the covalent organic framework material for quickly detecting the methylene blue as the adsorbent and adopting the ultraviolet spectroscopy comprises the following steps:
firstly, taking a water solution I to be detected, and measuring the ultraviolet absorption spectrum of the water solution I to be detected, wherein the absorption wavelength is 669nm, and the absorbance is A1；
Secondly, adding a covalent organic framework material for rapidly detecting methylene blue into the aqueous solution I to be detected to prepare a solution II;
measuring the ultraviolet absorption spectrum of the solution II after 3min, wherein the absorption wavelength is 669nm, and the absorbance is A2(ii) a If A1>A2Then it can be judgedThe aqueous solution I to be tested contains methylene blue.
The covalent organic framework material for rapidly detecting the methylene blue is used as an adsorbent, and the method for quantitatively detecting the methylene blue in water by using an ultraviolet spectroscopy method uses a standard curve method.
The covalent organic framework material absorbed with methylene blue is firstly separated by centrifugation, the separated solid phase substance is soaked and washed by alcohol solvent, and vacuum drying is carried out after separation, thus completing regeneration.
Wherein the alcohol solvent is methanol, ethanol, n-butanol, benzyl alcohol or ethylene glycol.
The covalent organic framework material for rapidly detecting methylene blue disclosed by the invention has a pore structure, can be rapidly adsorbed in an aqueous solution containing methylene blue, is simple and convenient in detection method of methylene blue and easy to operate, achieves adsorption balance within 3min, and has the maximum adsorption capacity of 1565.8mg g for methylene blue-1The adsorption effect is good, and the material can be recycled. The adsorbent can remove methylene blue in wastewater.
Drawings
FIG. 1 is an infrared spectrum of a covalent organic framework material for rapid detection of methylene blue prepared in example 1 with wavelength on the abscissa and light transmittance on the ordinate.
FIG. 2 is a color change diagram of methylene blue solution detected by naked eyes of the covalent organic framework material for rapid detection of methylene blue prepared in example 1.
Fig. 3 is a uv spectrum of the covalent organic framework material for rapid detection of methylene blue prepared in example 1, plotted with wavelength in the horizontal axis and absorbance in the vertical axis, as a function of adsorption time during detection of methylene blue by uv spectroscopy.
FIG. 4 is a standard curve of concentration of methylene blue solution II and its absorbance in example 1 at different concentrations, with the abscissa representing the concentration of methylene blue and the abscissa representing the absorbance.
Fig. 5 is an adsorption isotherm of methylene blue solutions of different concentrations when methylene blue is detected by ultraviolet spectroscopy on the covalent organic framework material for rapid detection of methylene blue prepared in example 1, wherein the abscissa is the concentration of the methylene blue solution and the ordinate is the equilibrium adsorption amount.
Detailed Description
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the preparation method of the covalent organic framework material for rapidly detecting methylene blue provided by the embodiment comprises the following steps:
firstly, 50mg of biphenyl tetra-aldehyde and 75mg of 2, 5-diaminobenzene sulfonic acid are dispersed in 0.5mL of mesitylene and 1mL of 1, 4-dioxane mixed solvent, 0.3mL of glacial acetic acid is added as a catalyst, and the mixture is uniformly mixed to obtain a reaction solution;
secondly, sealing the reaction container, cooling to-45 ℃, and then vacuumizing to the vacuum degree of 0.095 MPa;
thirdly, heating the reaction solution to 100 ℃ and reacting for 72 hours; and after the reaction is finished, cooling to room temperature, washing the brown solid obtained by centrifugal separation with tetrahydrofuran, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting methylene blue. The yield was 53%.
The infrared spectrum of a covalent organic framework material for rapidly detecting methylene blue prepared in this example is shown in fig. 1. 3429cm-1Is treated with-SO3O-H in H has a peak of 1622cm in extension vibration absorption-1Is the absorption peak of C ═ N for stretching vibration, 1171cm-1The position is the stretching vibration absorption peak of O-S. The stretching vibration absorption peak of-C ═ O in the spectrum has disappeared. The successful preparation of the covalent organic framework material for rapidly detecting the methylene blue is shown.
The method for qualitatively detecting the methylene blue dye in the wastewater by naked eyes by using the covalent organic framework material for quickly detecting the methylene blue prepared in the embodiment 1 as an adsorbent comprises the following steps:
firstly, taking 10mL of a wastewater solution I of methylene blue dye, wherein the color of the solution I is dark blue;
secondly, adding 5mg of covalent organic framework material for rapidly detecting methylene blue into the wastewater solution I to prepare solution II;
and thirdly, observing the color change conditions of the solution II at 0min, 1min, 3min, 120min and 180min by naked eyes under sunlight as shown in figure 2, wherein the color of the solution II is dark blue at 0min, the color of the solution II is obviously light after 1min, and the solution II becomes colorless at 3 min. With the increase of the adsorption time, the color of the wastewater solution is dark blue and gradually changed into colorless, so that the covalent organic framework material for rapidly detecting methylene blue prepared in example 1 can be used as a prompting agent for qualitatively detecting methylene blue in wastewater. Meanwhile, the covalent organic framework material for rapidly detecting methylene blue can be used for adsorbing methylene blue in wastewater.
The method for qualitatively detecting the methylene blue dye in the wastewater by using the covalent organic framework material for quickly detecting the methylene blue prepared in the example 1 as the adsorbent and by using the ultraviolet spectroscopy comprises the following steps:
firstly, taking 10mL of wastewater solution I of methylene blue dye, and measuring the ultraviolet absorption spectrum of the solution I, wherein the absorption wavelength is 669nm, and the absorbance is A1；
Secondly, adding 5mg of covalent organic framework material for rapidly detecting methylene blue into the wastewater solution I to prepare solution II;
thirdly, after 1min, measuring the ultraviolet absorption spectrum of the solution II, wherein the absorption wavelength is 669nm, and the absorbance is A2Discovery A1>A2And then, indicating that the dye wastewater contains methylene blue. The covalent organic framework material for rapidly detecting methylene blue prepared in the embodiment is proved to be capable of qualitatively detecting the methylene blue in wastewater.
The method for qualitatively detecting the methylene blue dye in the wastewater by using the covalent organic framework material for quickly detecting the methylene blue prepared in the example 1 as the adsorbent and by using the ultraviolet spectroscopy comprises the following steps:
firstly, taking 10mL of wastewater solution I of methylene blue dye, and measuring the ultraviolet absorption spectrum of the solution I, wherein the absorption wavelength is 669nm, and the absorbance is A1；
Secondly, adding 5mg of covalent organic framework material for rapidly detecting methylene blue 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 669nm of solution II at 0min was 2.12A. The absorbance gradually decreased with increasing time. At 1min, the absorbance of the solution II is remarkably reduced to 0.40A, and at 3min, the absorbance of the solution II is close to 0, and the adsorption equilibrium is basically achieved. The result shows that the adsorption capacity of the covalent organic framework material for rapidly detecting methylene blue to methylene blue in wastewater is gradually increased along with the increase of time, the concentration of the methylene blue in the solution II is gradually reduced, the absorbance is gradually reduced, and the adsorption balance can be achieved within 3 min. Then it was demonstrated that methylene blue in wastewater can be qualitatively detected using covalent organic framework materials that rapidly detect methylene blue.
The method for quantitatively detecting methylene blue in water by using the covalent organic framework material for rapidly detecting methylene blue prepared in example 1 as an adsorbent through an ultraviolet spectroscopy method comprises the following specific steps:
firstly, preparing methylene blue standard solutions of 0mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L, 5mg/L, 6mg/L, 7mg/L and 8mg/L respectively;
adding 5mg of covalent organic framework material for rapidly detecting methylene blue into 100mL of methylene blue standard solution, and after absorbing for 3min, testing the ultraviolet spectroscopy of the solution, wherein the absorbance at the absorption wavelength of 669nm is taken as a longitudinal standard, the methylene blue concentration is taken as a transverse standard, and a standard curve between the methylene blue concentration of the solution and the absorbance is drawn; as shown in fig. 4, the deviation R of the standard curve20.9949, and the relationship between the concentration of methylene blue in the solution and the absorbance of the solution can be determined through the standard curve;
adding 5mg of covalent organic framework material for rapidly detecting methylene blue into 100mL of solution to be detected, adsorbing for 3min to obtain an ultraviolet spectrum method of the solution II to be detected, reading the absorbance at the absorption wavelength of 669nm, and finding out the equilibrium concentration c of methylene blue in the solution II to be detected from a standard curvee。
According to the formula
Calculating the equilibrium concentration ceCovalent organic framework material pair for rapidly detecting methylene blue in solutionEquilibrium adsorption capacity q of bluee(mg·g-1) Wherein v represents the volume of solution II, coRepresents the initial concentration (mg. L) of methylene blue in the solution II-1) And m is the mass (g) of the covalent organic framework material for rapid detection of methylene blue. The maximum adsorption amount of methylene blue when the adsorption equilibrium is reached is 1565.8mg 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 formula
Calculating qeI.e. the ordinate, fig. 5 is plotted. Fig. 5 is an adsorption isotherm of a covalent organic framework material for rapidly detecting methylene blue on methylene blue with different concentrations, wherein the abscissa is the concentration of methylene blue in a solution when adsorption equilibrium is reached, and the ordinate is the equilibrium adsorption amount. The figure demonstrates the adsorption capacity of the covalent organic framework material for rapid detection of methylene blue on methylene blue in solution II. As seen from the figure, the covalent organic framework material for quickly detecting methylene blue with the same mass has different equilibrium adsorption amounts to methylene blue solutions with different concentrations, the increase value of the equilibrium adsorption amount of the material to the methylene blue is accelerated along with the increase of the equilibrium adsorption concentration, and when the equilibrium adsorption concentration reaches 200 mg.L-1When the adsorption is carried out, the equilibrium adsorption capacity is slowly increased, and the maximum adsorption capacity can reach 1565.8mg g-1。
Example 2: the preparation method of the covalent organic framework material for rapidly detecting methylene blue provided by the embodiment comprises the following steps:
firstly, dispersing 50mg of biphenyl tetra-aldehyde and 90mg of 2, 5-diaminobenzene sulfonic acid in a mixed solvent of 0.5mL of N-methyl pyrrolidone and 0.5mL of n-butyl alcohol, adding 0.3mL of benzene sulfonic acid as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to-45 ℃, and then vacuumizing to the vacuum degree of 0.092 MPa;
thirdly, heating the reaction liquid to 170 ℃ and reacting for 120 h; and after the reaction is finished, cooling to room temperature, washing the brown solid obtained by centrifugal separation with tetrahydrofuran, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting methylene blue. The yield was 72%.
Example 3: the preparation method of the covalent organic framework material for rapidly detecting methylene blue provided by the embodiment comprises the following steps:
firstly, dispersing 50mg of biphenyl tetra-aldehyde and 100mg of 2, 5-diaminobenzene sulfonic acid in a mixed solvent of 0.2mL of azomethyl pyrrolidone and 0.8mL of mesitylene, adding 0.3mL of p-toluenesulfonic acid as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to-45 ℃, and then vacuumizing to the vacuum degree of 0.090 MPa;
thirdly, heating the reaction system to 150 ℃ and reacting for 96 hours. And after the reaction is finished, cooling to room temperature, centrifuging to obtain a brown solid, repeatedly washing with acetone, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting the methylene blue, wherein the yield is 68%.
Example 4: the preparation method of the covalent organic framework material for rapidly detecting methylene blue provided by the embodiment comprises the following steps:
firstly, dispersing 50mg of biphenyltetra-aldehyde and 115mg of 2, 5-diaminobenzene sulfonic acid in 0.7mL of mixed solvent of N, N-dimethylformamide and 0.3mL of o-dichlorobenzene, adding 0.3mL of sulfuric acid with the mass percent of 95% as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to-45 ℃, and then vacuumizing to the vacuum degree of 0.095 MPa;
thirdly, heating the reaction system to 200 ℃ and reacting for 96 hours. And after the reaction is finished, cooling to room temperature, centrifuging to obtain a brown solid, repeatedly washing with ethanol, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting the methylene blue, wherein the yield is 60%.
Example 5: the preparation method of the covalent organic framework material for rapidly detecting methylene blue provided by the embodiment comprises the following steps:
firstly, dispersing 50mg of biphenyltetra-aldehyde and 50mg of 2, 5-diaminobenzene sulfonic acid in 0.5mL of n-butanol and 1.0mL of dioxane mixed solvent, adding 0.3mL of hydrochloric acid with the mass percent of 37% as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to-45 ℃, and then vacuumizing to 0.085MPa of vacuum degree;
thirdly, heating the reaction system to 100 ℃ and reacting for 168 hours. And after the reaction is finished, cooling to room temperature, centrifuging to obtain a brown solid, repeatedly washing with methanol, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting the methylene blue, wherein the yield is 70%.
Example 6: the preparation method of the covalent organic framework material for rapidly detecting methylene blue provided by the embodiment comprises the following steps:
firstly, dispersing 50mg of biphenyltetra-aldehyde and 50mg of 2, 5-diaminobenzene sulfonic acid in a mixed solvent of 0.5mL of N-butanol and 1.0mL of N, N-dimethylformamide, adding 0.3mL of trifluoroacetic acid as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to-45 ℃, and then vacuumizing to 0.085MPa of vacuum degree;
thirdly, heating the reaction system to 150 ℃ and reacting for 72 h. And after the reaction is finished, cooling to room temperature, centrifuging to obtain a brown solid, repeatedly washing with dichloromethane, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting the methylene blue, wherein the yield is 75%.
Example 7: the preparation method of the covalent organic framework material for rapidly detecting methylene blue provided by the embodiment comprises the following steps:
firstly, dispersing 50mg of biphenyl tetra-aldehyde and 100mg of 2, 5-diaminobenzene sulfonic acid in a mixed solvent of 0.5mL of dioxane and 0.5mL of o-dichloroaniline, adding 0.3mL of glacial acetic acid serving as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to-45 ℃, and then vacuumizing to the vacuum degree of 0.092 MPa;
thirdly, heating the reaction system to 180 ℃ and reacting for 168 hours. After the reaction is finished, the reaction product is cooled to room temperature, and is centrifuged to obtain a brown solid, the brown solid is repeatedly washed by dichloromethane and is dried in vacuum, and the covalent organic framework material for rapidly detecting methylene blue is obtained, wherein the yield is 59%.
Claims (10)
1. A covalent organic framework material for rapidly detecting methylene blue is characterized in that basic structural units of the covalent organic framework material are as follows:
2. the method for preparing the covalent organic framework material for rapidly detecting methylene blue as claimed in claim 1, which is characterized by comprising the following steps:
according to the mass ratio of biphenyl tetra-aldehyde to 2, 5-diaminobenzene sulfonic acid, the ratio is 1: (1-5) dispersing biphenyl tetra-aldehyde and 2, 5-diaminobenzene sulfonic acid in an organic solvent I, adding acid serving as a catalyst, and uniformly mixing to obtain a reaction solution;
secondly, sealing the reaction container, cooling to below-40 ℃, and then vacuumizing;
thirdly, heating the reaction liquid to 100-200 ℃ and reacting for 72-168 hours; and after the reaction is finished, cooling to room temperature, washing the solid phase substance obtained by centrifugal separation with an organic solvent II, and drying in vacuum to obtain the covalent organic framework material for rapidly detecting methylene blue.
3. The method for rapidly detecting the covalent organic framework material of methylene blue as claimed in claim 2, wherein the organic solvent I in the step one is any two or three of azomethyl pyrrolidone, mesitylene, dioxane, o-dichlorobenzene, N-dimethylformamide and N-butanol.
4. The method for rapidly detecting the covalent organic framework material of methylene blue as claimed in claim 2 or 3, wherein the ratio of the amount of the substance of biphenyl tetra-aldehyde to the volume of the organic solvent I in the step one is 1 mmol: (5-25) mL.
5. The method for rapidly detecting the covalent organic framework material of methylene blue as claimed in claim 2 or 3, characterized in that the acid in step one is concentrated sulfuric acid with a mass percent of 95% -98%, concentrated hydrochloric acid with a mass percent of 30% -37%, benzenesulfonic acid, p-methylbenzenesulfonic acid, glacial acetic acid or trifluoroacetic acid.
6. The method for rapidly detecting the covalent organic framework material of methylene blue as claimed in claim 2 or 3, wherein the ratio of the amount of the substance of biphenyl tetra-aldehyde to the volume of the acid in the first step is 1 mmol: (2.5-10) mL.
7. The method for rapidly detecting the covalent organic framework material of methylene blue as claimed in claim 2 or 3, characterized in that the organic solvent II in step three is methanol, ethanol, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, N-butanol, N-dimethylacetamide or acetone.
8. The use of the covalent organic framework material for rapid detection of methylene blue as claimed in claim 1, wherein the covalent organic framework material for rapid detection of methylene blue is used as adsorbent for detection of methylene blue in water by naked eye or ultraviolet spectroscopy.
9. The application of the covalent organic framework material for rapidly detecting methylene blue as claimed in claim 8, characterized in that the covalent organic framework material for rapidly detecting methylene blue is used as an adsorbent, and the method for qualitatively detecting methylene blue in water by naked eye method is carried out according to the following steps:
firstly, taking a water solution I to be detected, wherein the color of the solution I is dark blue;
secondly, adding a covalent organic framework material for rapidly detecting methylene blue into the aqueous solution I to prepare a solution II;
and thirdly, observing the color of the solution II after 3min, and if the color of the solution is changed from dark blue to colorless, judging that the aqueous solution I to be detected contains methylene blue.
10. The use of the covalent organic framework material for rapid detection of methylene blue as claimed in claim 8, wherein the covalent organic framework material for rapid detection of methylene blue is used as an adsorbent, and the method for qualitative detection of methylene blue in water by ultraviolet spectroscopy is carried out according to the following steps:
firstly, taking a water solution I to be detected, and measuring the ultraviolet absorption spectrum of the water solution I to be detected, wherein the absorption wavelength is 669nm, and the absorbance is A1；
Secondly, adding a covalent organic framework material for rapidly detecting methylene blue into the aqueous solution I to be detected to prepare a solution II;
measuring the ultraviolet absorption spectrum of the solution II after 3min, wherein the absorption wavelength is 669nm, and the absorbance is A2(ii) a If A1>A2Then, it can be determined that the aqueous solution I to be detected contains methylene blue.
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| CN105107463A (en) * | 2015-08-21 | 2015-12-02 | 湖北师范学院 | Preparation of phosphotungstic acid composite material and experimental method for testing adsorbing performance of phosphotungstic acid composite material to methylene blue |
| WO2016019128A1 (en) * | 2014-08-01 | 2016-02-04 | Avertica Inc. | Polymers, substrates, methods for making such, and devices comprising the same |
| CN113024754A (en) * | 2021-03-29 | 2021-06-25 | 南昌大学 | Preparation method and application of iron oxyhydroxide covalent organic framework composite material |
| CN113198423A (en) * | 2021-04-22 | 2021-08-03 | 浙江工业大学 | Covalent organic framework material and preparation method and application thereof |
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| WO2016019128A1 (en) * | 2014-08-01 | 2016-02-04 | Avertica Inc. | Polymers, substrates, methods for making such, and devices comprising the same |
| CN105107463A (en) * | 2015-08-21 | 2015-12-02 | 湖北师范学院 | Preparation of phosphotungstic acid composite material and experimental method for testing adsorbing performance of phosphotungstic acid composite material to methylene blue |
| CN113024754A (en) * | 2021-03-29 | 2021-06-25 | 南昌大学 | Preparation method and application of iron oxyhydroxide covalent organic framework composite material |
| CN113198423A (en) * | 2021-04-22 | 2021-08-03 | 浙江工业大学 | Covalent organic framework material and preparation method and application thereof |
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