CN115709054A - Chitosan-covalent organic framework composite material and preparation method thereof - Google Patents
Chitosan-covalent organic framework composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a chitosan-covalent organic framework composite material, which is a honeycomb aerogel spherical chitosan-covalent organic framework composite material formed by chitosan and chitosan gel spheres with micro mesoporous structures formed by ZIF-8 and covalent organic frameworks attached to the inner walls of the pore channels of the chitosan gel spheres and the surfaces of the chitosan gel spheres, and is used for adsorbing mercury ions in water. The invention also provides a preparation method of the chitosan-covalent organic framework composite material. The invention provides a chitosan-covalent organic framework complexThe composite material has strong mercury ion adsorption capability, and can effectively solve Hg in water 2+ The preparation method of the composite material is simple and easy, the requirement on production conditions is low, and the cost is low.
Description
Technical Field
The invention relates to the technical field of adsorption materials, and particularly relates to a chitosan-covalent organic framework composite material and a preparation method thereof.
Background
Among heavy metal pollutants, mercury (Hg) is attracting much attention as a special, highly toxic, typical heavy metal element. Mercury is widely used in chemical industry, medicine, agriculture and daily life, about 5000 tons of mercury enters the environment every year, and mercury pollution is spread all over the world along with the movement of atmosphere and ocean current. At present, china is in the stage of rapid development of industrialization and urbanization processes, various aspects such as combustion of fossil fuels, incineration of household garbage and medical garbage, metallurgy and paper industry and the like are main sources of global artificial mercury pollution at the present stage, and wastewater of plastic industry, chlor-alkali industry, mercury-mixed gold-smelting mercury production, electronic industry and the like enters rivers, lakes and seas and the like are main pollution sources of mercury in water bodies. The main mercury industries in China include: in the fields of chemical industry (polyvinyl chloride and chemical reagents), light industry (batteries, lighting appliances and electric light sources), metallurgy (gold mining and metallurgy), medical instruments (thermometers and sphygmomanometers) and the like, about 1200 tons of mercury are consumed each year. In addition, china is also the largest coal consuming country in the world, and China has high mercury and low halogen content in coal and has different mining technology and equipment levels, so the coal-fired industry is also the largest mercury emission source in China and accounts for more than 50% of the total mercury emission amount of China atmosphere. The non-ferrous metal smelting industry mainly comprises the smelting of metals such as zinc, lead, copper and gold, and mercury is discharged in the smelting process due to the frequent accompanying of mercury elements in ores. Meanwhile, china is the largest cement producing country in the world, the production capacity accounts for more than 80% of the world, and the cement industry is one of the main mercury pollution emission sources because mercury is an associated element (mostly in coal) in limestone raw materials and fuel coal.
Mercury can migrate into the atmosphere and soil through evaporation, sedimentation and other ways, causing atmospheric pollution, soil pollution and water body pollution. In addition, mercury can migrate into bodies of fishes, birds and mammals through food chains and finally be enriched into human bodies, so that serious harm is caused to the human bodies and the ecological environment. Once mercury enters a human body in the form of organic mercury, mercury immediately reacts with enzymes in the human body to lose activity, so that functional disorders of the nervous system, the digestive tract, the oral cavity, the kidney, the liver and the like of the human body are caused, and neurasthenia syndrome is caused during chronic poisoning, and symptoms such as excitability, tremor, oral mercury lines, inflammation, renal function damage and the like are presented. In addition, mercury may also invade placenta blood supply tissue in the pregnant woman, thereby transmitting to the fetus, resulting in malformation of the infant. Because mercury and the derivatives thereof have the characteristics of durability, easy migration, biological enrichment, biological toxicity and the like. Therefore, mercury has become an important environmentally toxic and harmful substance, and poses a great threat to human health and ecological hallucinations. Therefore, the pollution is listed as a global pollutant by the environmental planning agency of the united nations, and becomes one of the pollutants for preferential control in China and even in the whole world. At present, how to effectively treat mercury pollution is one of important issues in research in fields such as environment, materials, engineering and the like.
Common methods for treating mercury-containing wastewater include chemical precipitation, ion exchange, electrolysis and adsorption. Among these methods, the adsorption method has advantages of simple process, high efficiency, low cost, and collectability of contaminants, and is considered to be one of the most effective and economical methods. The adsorbent can be divided into organic carriers and inorganic carriers according to carrier frameworks, wherein the organic carriers comprise biomass such as chitosan, cellulose and starch humic acid, and also comprise artificially synthesized polystyrene resin, polystyrene-crosslinked ethylene diene resin and the like. The natural organic carrier contains some active functional groups (-OH, -NH) 2 -COOH, etc.) and has the advantages of wide source, low cost, easy biodegradation, no secondary pollution and the like, thus becoming the green economical mercury ion adsorbent preferred by researchers.
The Chitosan (CS) is mainly derived from marine organisms, is a product of chitin in shells of shrimps, crabs and the like after partial deacetylation, and is the only basic polysaccharide in natural products. Due to the structure of the chitosan, the chitosan and the derivatives thereof have abundant active groups such as hydroxyl, amino and the like, so that the chitosan and the derivatives thereof not only have a plurality of application values in a plurality of fields such as medicine, textile, paper making, food, biology, chemical industry, agriculture and the like, but also can be widely used as an adsorbent for removing pollutants in water. The chitosan has the disadvantages of low mechanical strength and poor thermal stability, and is easily dissolved under acidic conditions to affect the removal effect. Therefore, in order to overcome the insufficient physical and chemical properties of chitosan, it is necessary to modify it to enhance its stability under acidic conditions.
As a novel porous material with the characteristics of high specific surface area, adjustable pore diameter, high porosity and the like, the metal-organic framework Material (MOF) is used. Covalent Organic Frameworks (COFs) are highly porous materials built from light elements, such as C, N, O, B, si and H, through covalent bonds, with the advantages of good thermal and chemical stability, structural diversity, permanent porosity and ease of functionalization. The MOF and COF material can be widely applied to the technical fields of catalysis and degradation, adsorption and separation, energy and sensing, drug carriers and the like.
If the chitosan, the metal-organic framework and the covalent organic framework are used as raw materials to synthesize the cellular chitosan porous composite material (CS/ZIF-8 @ COFs), the stability of the chitosan aerogel ball can be improved, the chitosan can be effectively prevented from swelling in sewage, the specific surface area and the high porosity of the material can be further increased, mercury in the sewage can be effectively adsorbed, the adsorption speed is high, the removal rate is high, the number of times of recycling is large, and secondary pollution is avoided.
Disclosure of Invention
The invention aims to solve the technical problem of providing a chitosan-covalent organic framework composite material with strong mercury ion adsorption capacity and a preparation method thereof so as to solve the problem of Hg in a water body 2+ The pollution to the environment is caused.
In order to solve the technical problems, the invention provides a chitosan-covalent organic framework composite material, which is a honeycomb aerogel spherical chitosan-covalent organic framework composite material formed by chitosan and chitosan gel spheres with micro mesoporous structures formed by ZIF-8 and covalent organic frameworks attached to the inner walls of the pore channels of the chitosan gel spheres and the surfaces of the chitosan gel spheres, and is used for adsorbing mercury ions in water.
Further, the chitosan contains hydroxyl and amino, the covalent organic framework contains N atoms, and the viscosity of the chitosan is more than 400.
Further, the chitosan gel sphere micro-mesoporous knotThe pore diameter of the structure is only 1.4-1.7nm, and the specific surface area is only 250-300m 2 /g。
The invention also provides a preparation method of the chitosan-covalent organic framework composite material, which comprises the following steps:
dissolving chitosan powder in a glacial acetic acid solution, adding zinc nitrate hexahydrate into the obtained solution, and stirring to obtain a mixed solution;
dropping the mixed solution into a sodium hydroxide solution and a 2-methylimidazole solution to form chitosan gel spheres;
filtering out the chitosan gel balls, washing and filtering to obtain CS/ZIF-8 gel balls;
adding CS/ZIF-8 gel balls into ethanol, heating and carrying out crosslinking reaction by using glutaraldehyde;
after the crosslinking reaction, filtering, washing, suction filtering and drying to obtain CS/ZIF-8 aerogel balls;
dissolving a dimethyl aldehyde compound and a 4-aminophenyl compound into ethanol, and then adding CS/ZIF-8 aerogel balls for reaction;
after the reaction is finished, the CS/ZIF-8@ COFs aerogel balls are obtained by suction filtration, washing and drying.
Further, after the chitosan powder was dissolved in a glacial acetic acid solution, it was stirred at room temperature for 24 hours to completely dissolve the chitosan powder, and then zinc nitrate hexahydrate was added to the resultant solution, which was stirred at 50 ℃ for 12 hours to obtain a mixed solution.
Further, the mixed solution was dropped into a 2-methylimidazole and 1% sodium hydroxide solution by a peristaltic pump to form chitosan gel beads, and the filtered chitosan gel beads were washed with distilled water to be neutral.
Further, adding the CS/ZIF-8 gel spheres into ethanol, heating to 50 ℃, carrying out crosslinking reaction for 4 hours by using glutaraldehyde, changing the color of the gel spheres from white to light yellow after the crosslinking reaction is finished, washing the gel spheres obtained by filtering after the crosslinking reaction is finished by using ethanol and distilled water, carrying out suction filtration, and then putting the gel spheres into a drying oven to be dried for 24 hours to obtain the CS/ZIF-8 aerogel spheres.
Further, the dimethyl aldehyde compound and the 4-aminophenyl compound are dissolved in ethanol, and then CS/ZIF-8 aerogel balls are added to react at the temperature of 50-80 ℃ for 72-96 h, so that the color of the aerogel balls is changed from light yellow to deep yellow.
And further, washing the CS/ZIF-8@ COFs aerogel balls obtained by suction filtration after the reaction is finished by using ethanol and water, and then drying for 24 hours to obtain the CS/ZIF-8@ COFs aerogel balls.
Further, the diformaldehyde compound is terephthalaldehyde, 2,5-dibromo-benzene-terephthalaldehyde, 2,5-dimethoxy-benzene-terephthalaldehyde or 2,5-dihydroxy-benzene-terephthalaldehyde, and the 4-aminophenyl compound is 1,3,5-tris (4-aminophenyl) benzene or 2,4,6-tris (4-aminophenyl) -1,3,5-triazine.
The chitosan-covalent organic framework composite material provided by the invention has a rich micro-mesoporous structure, the aperture of the chitosan-covalent organic framework composite material is about 1.4-1.7nm, the specific surface area is very high and can reach 300m 2 (ii) in terms of/g. The chitosan of the composite material contains abundant hydroxyl and amino in the structure, the viscosity of the chitosan is up to more than 400, and the covalent organic framework contains N atoms, so that the composite material has a strong chelating effect on heavy metals, can quickly adsorb various heavy metal ions, and particularly has good adsorption capacity on mercury ions in sewage.
In addition, the chitosan-covalent organic framework composite material provided by the invention not only can maintain the respective advantages of the chitosan material and the covalent organic framework material, but also can improve the stability of the chitosan gel spheres in aqueous solution, effectively avoid swelling of the chitosan gel spheres in the aqueous solution, and further improve the mechanical properties of the honeycomb-shaped chitosan gel spheres. Moreover, the composite material has strong adsorption capacity and removal rate under the acid or alkali environment, and does not cause secondary pollution to the water body.
The invention also provides a preparation method of the chitosan-covalent organic framework composite material, which comprises the steps of adding zinc ions and imidazole ligands into a chitosan raw material, generating cellular porous chitosan gel spheres in a sodium hydroxide solution, taking the cellular porous chitosan gel spheres as a carrier, and introducing covalent organic frameworks into the inner walls and the surfaces of the pore channels of the cellular structure to finally obtain the cellular chitosan-covalent organic framework composite material. The method has the advantages of simple and easy process, no need of expensive equipment and harsh production conditions, controllable appearance of the prepared composite material, no toxicity, no odor and no pollution, and can be repeatedly used as an adsorbent for mercury ions in industrial wastewater, thereby greatly reducing the adsorption cost of mercury in the wastewater, improving the economic benefit and having better application prospect.
Drawings
FIG. 1 is a flow chart of a method for preparing a chitosan-covalent organic framework composite material according to an embodiment of the present invention;
FIG. 2 is a FT-IR spectrum of a mesoporous CS/ZIF-8@ COFs composite material prepared by the method for preparing a chitosan-covalent organic framework composite material provided in embodiment 1 of the present invention;
FIG. 3 is an SEM image of a mesoporous CS/ZIF-8@ COFs composite material prepared by the method for preparing a chitosan-covalent organic framework composite material provided in example 1 of the present invention;
FIG. 4 is an SEM image of a mesoporous CS/ZIF-8@ COFs composite material prepared by the preparation method of the chitosan-covalent organic framework composite material provided in embodiment 1 of the present invention at a higher magnification;
FIG. 5 is an XRD pattern of a mesoporous CS/ZIF-8@ COFs composite material prepared by the method for preparing a chitosan-covalent organic framework composite material provided in example 1 of the present invention;
FIG. 6 is a BET diagram of a mesoporous CS/ZIF-8@ COFs composite material prepared by the method for preparing a chitosan-covalent organic framework composite material provided in embodiment 1 of the present invention;
FIG. 7 is another BET diagram of the mesoporous CS/ZIF-8@ COFs composite material prepared by the preparation method of the chitosan-covalent organic framework composite material provided in embodiment 1 of the present invention.
Detailed Description
The chitosan-covalent organic framework composite material provided by the embodiment of the invention is a honeycomb aerogel spherical chitosan-covalent organic framework composite material formed by chitosan and ZIF-8, wherein the chitosan gel spheres are formed by a micro mesoporous structure, and covalent organic frameworks are attached to the inner wall of the pore channel of the chitosan gel spheres and the surface of the chitosan gel spheres, and the chitosan-covalent organic framework composite material is used for adsorbing mercury ions in water.
Wherein the chitosan contains hydroxyl and amino, the covalent organic framework contains N atoms, and the viscosity of the chitosan is more than 400.
Wherein the pore diameter of the chitosan gel sphere micro-mesoporous structure is only 1.4-1.7nm, and the specific surface area is only 250-300m 2 /g。
Referring to fig. 1, the preparation method of the chitosan-covalent organic framework composite material provided by the invention comprises the following steps:
step 1) dissolving chitosan powder in a glacial acetic acid solution, then adding zinc nitrate hexahydrate into the obtained solution, and stirring to obtain a mixed solution.
And 2) dripping the mixed solution into a sodium hydroxide solution and a 2-methylimidazole solution to form chitosan gel spheres.
And 3) filtering the chitosan gel balls, washing and filtering to obtain CS/ZIF-8 gel balls.
And 4) adding the CS/ZIF-8 gel balls into ethanol, heating and carrying out crosslinking reaction by using glutaraldehyde.
And 5) after the crosslinking reaction, filtering, washing, carrying out suction filtration and drying to obtain the CS/ZIF-8 aerogel balls.
And 6) dissolving the dimethyl aldehyde compound and the 4-aminophenyl compound into ethanol, and then adding CS/ZIF-8 aerogel balls for reaction.
And 7) after the reaction is finished, carrying out suction filtration, washing and drying to obtain the CS/ZIF-8@ COFs aerogel balls.
After the chitosan powder is dissolved in a glacial acetic acid solution, stirring for 24 hours at room temperature to completely dissolve the chitosan powder, then adding zinc nitrate hexahydrate into the obtained solution, and stirring for 12 hours at 50 ℃ to obtain a mixed solution.
Wherein the mixed solution is dripped into 2-methylimidazole and 1% sodium hydroxide solution through a peristaltic pump to form chitosan gel spheres, and the filtered chitosan gel spheres are washed to be neutral by distilled water.
Adding the CS/ZIF-8 gel spheres into ethanol, heating to 50 ℃, carrying out crosslinking reaction for 4 hours by using glutaraldehyde, changing the color of the gel spheres from white to light yellow after the crosslinking reaction is finished, washing the gel spheres obtained by filtering after the crosslinking reaction is finished by using ethanol and distilled water, carrying out suction filtration, and then putting the gel spheres into a drying oven to be dried for 24 hours to obtain the CS/ZIF-8 aerogel spheres.
The dimethyl aldehyde compound and the 4-aminophenyl compound are dissolved in ethanol, and then CS/ZIF-8 aerogel balls are added to react at the temperature of 50-80 ℃ for 72-96 hours, so that the color of the aerogel balls is changed from light yellow to deep yellow.
And washing the CS/ZIF-8@ COFs aerogel balls obtained by suction filtration after the reaction is finished by using ethanol and water, and drying for 24 hours to obtain the CS/ZIF-8@ COFs aerogel balls.
Wherein the diformaldehyde compound is terephthalaldehyde, 2,5-dibromo terephthalaldehyde, 2,5-dimethoxy terephthalaldehyde or 2,5-dihydroxy terephthalaldehyde, and the 4-aminophenyl compound is 1,3,5-tris (4-aminophenyl) benzene or 2,4,6-tris (4-aminophenyl) -1,3,5-triazine.
The preparation method of the chitosan-covalent organic framework composite material provided by the invention is specifically described by the following embodiments.
Example 1:
(1) First, 2g of chitosan powder was dissolved in 100mL of a 3% glacial acetic acid solution and stirred at room temperature for 24h to completely dissolve it. And then 8.2g of zinc nitrate hexahydrate is added into the chitosan solution, stirring treatment is carried out for 12 hours at the temperature of 50 ℃, the solution is uniformly mixed, the chitosan solution is dropwise added into 2.6g of 2-methylimidazole ligand and 1% of sodium hydroxide solution through a peristaltic pump, then, chitosan gel balls are filtered out, the solution is washed to be neutral by distilled water, suction filtration is carried out, the solution is placed into a drying oven to be dried for 24 hours, and then sealing is carried out for standby.
(2) Adding the chitosan gel balls into a certain amount of ethanol solution, heating to 50 ℃, and carrying out crosslinking reaction for 4 hours by using glutaraldehyde. Then, filtering out chitosan gel balls, washing with ethanol and distilled water, carrying out suction filtration, putting into a drying oven for drying for 24 hours, and then sealing for later use.
(3) Sonicating a mixture of 0.03mol of terephthalaldehyde and 0.02mol of 1,3,5-tris (4-aminophenyl) benzene 3Dissolving in 100mL ethanol for 0min, adding 100g chitosan gel spheres, stirring for 2h to mix and adsorb the honeycomb chitosan gel spheres and the monomers in the solution, and reacting at 80 deg.C for 72h. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF a-1 。
Referring to FIG. 2, it can be seen from FIG. 2 that the FT-IR spectrum of the mesoporous CS/ZIF-8@ COFs composite material prepared in the embodiment of the present invention contains functional groups such as hydroxyl, amino, etc., and also contains functional groups of benzene rings in a covalent organic skeleton.
Referring to fig. 3 and 4, SEM spectrograms of the CS/ZIF-8@ cofs composite material prepared in the embodiment of the present invention are shown in fig. 3 and 4, and it can be seen from fig. 3 and 4 that the CS/ZIF-8@ cofs composite material prepared in the embodiment of the present invention has a honeycomb structure.
Referring to FIG. 5, an XRD spectrum of the mesoporous CS/ZIF-8@ COFs composite material prepared in the embodiment of the present invention is shown in FIG. 5, and it can be seen that the formation of the ZIF-8 crystal in the mesoporous CS/ZIF-8@ COFs composite material prepared in the embodiment of the present invention is shown.
Referring to FIGS. 6 and 7, BET spectrograms of the mesoporous CS/ZIF-8@ COFs composite material prepared in the embodiment of the present invention are shown in FIGS. 6 and 7, and it can be seen from FIGS. 6 and 7 that the mesoporous CS/ZIF-8@ COFs composite material prepared in the embodiment of the present invention has a porous property.
The following instruments were used to determine the adsorption capacity and removal rate of the composite material prepared in the examples of the present invention:
(1) FT-IR was tested using a Spectrum One infrared spectrometer from PE, USA. The solid sample is tabletted by KBr, the liquid sample is coated on a KBr wafer, and the wave number range scanned by absorption spectrum is 4000-500 cm -1 And 3 times of scanning.
(2) X-ray diffractometer (XRD) adopted Bruker D8 ADVANCE Germany wide-angle X-ray diffractometer and Cu target
The scanning range is 0-10 degrees.
(3) Scanning Electron Microscopy (SEM) scanned sample images were recorded using hitachi SU 8010.
(4) In the experiment, an SL58-CG-1C intelligent mercury meter is used for measuring the Hg (II) concentration in the solution after the composite material prepared in the embodiment is adsorbed.
The specific measurement method is as follows:
putting 5mL of mercury nitrate standard solution (with the concentration of 1000 mg/L) into a 50mL beaker, adding a proper amount of deionized water into the beaker, adjusting the pH of the solution to 2-8, then putting a small amount of deionized water into the beaker for constant volume to prepare a solution containing mercury ions, finally adding 20-50 mg of the chitosan-covalent organic framework composite material prepared in the embodiment into the solution, stirring for 30-4 h, centrifuging the adsorbed solution at a high speed for 10min, taking 1mL of centrifuged supernatant into a 50mL volumetric flask, and performing constant volume with absolute ethyl alcohol and shaking uniformly. The amount of adsorption and removal rate of Hg (II) adsorbed by the composite material prepared in this example were measured according to the following formulas (1) and (2).
In the formula, Q e An adsorption amount (mg/g) of Hg (II) adsorbed by the adsorbent; c 0 And C e The concentration (mg/L) of Hg (II) in the solution before the adsorbent is not adsorbed and the concentration (mg/L) of Hg (II) in the solution after the adsorbent is adsorbed are respectively obtained; m is the mass (g) of the adsorbent; v is the volume of the solution (L); r is the Hg (II) removing rate (%) in the solution.
Through calculation, the adsorption amount of the composite material prepared in the embodiment is 124.14mg/g, and the removal rate is 99.17%.
Example 2:
(1) The synthesis was the same as in step (1) in example 1.
(2) The synthesis was the same as in step (2) in example 1.
(3) 0.03mol of 2,5, -dibromo terephthalaldehyde and 0.02mol of1,3,5-tris (4-aminophenyl) benzene was dissolved in 100mL of ethanol, and then 100g of chitosan gel beads were added, stirred for 2 hours to sufficiently mix and adsorb the honeycomb-shaped chitosan gel beads and the monomers in the solution, and then reacted at a temperature of 75 ℃ for 78 hours. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF a-2 。
The adsorption amount of the composite material prepared in the example of the present invention was 124.42mg/g and the removal rate was 99.56% as measured by the same measurement method as in example 1.
Example 3:
(1) The synthesis was the same as in step (1) in example 1.
(2) The synthesis was the same as in step (2) in example 1.
(3) Dissolving 0.03mol of 2,5, -dimethoxyterephthalaldehyde and 0.02mol of 1,3,5-tris (4-aminophenyl) benzene mixture in 100mL of ethanol by ultrasonic wave for 30min, then adding 100g of chitosan gel spheres, stirring for 2h to fully mix and adsorb the honeycomb-shaped chitosan gel spheres and the monomers in the solution, and then reacting for 84h at the temperature of 70 ℃. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF a-3 。
The adsorption amount of the composite material prepared in the example of the present invention was 124.73mg/g and the removal rate was 99.79% as measured by the same measurement method as in example 1.
Example 4:
(1) The synthesis was the same as in step (1) in example 1.
(2) The synthesis was the same as in step (2) in example 1.
(3) Dissolving 0.03mol of 2,5, -dihydroxy terephthalaldehyde and 0.02mol of 1,3,5-tris (4-aminophenyl) benzene mixture in 100mL of ethanol by ultrasonic wave for 30min, then adding 100g of chitosan gel spheres, stirring for 2h to fully mix and adsorb the honeycomb chitosan gel spheres with the monomers in the solution, and then reacting for 90h at 55 ℃. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF a-4 。
The adsorption amount of the composite material prepared in the example of the present invention was 124.70mg/g and the removal rate was 99.72%, which was determined by the same determination method as in example 1.
Example 5:
(1) The synthesis was the same as in step (1) in example 1.
(2) The synthesis was the same as in step (2) in example 1.
(3) Dissolving 0.03mol of terephthalaldehyde and 0.02mol of 2,4,6-tris (4-aminophenyl) -1,3,5-triazine mixture in 100mL ethanol by ultrasonic wave for 30min, adding 100g of chitosan gel spheres, stirring for 2h to fully mix and adsorb the honeycomb chitosan gel spheres and the monomers in the solution, and then reacting for 96h at the temperature of 50 ℃. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF b-1 。
The adsorption amount of the composite material prepared in the example of the present invention was 124.68mg/g and the removal rate was 99.69%, which was determined by the same determination method as in example 1.
Example 6:
(1) The synthesis was the same as in step (1) in example 1.
(2) The synthesis was the same as in step (2) in example 1.
(3) A mixture of 0.03mol of 2,5-dibromoterephthalaldehyde and 0.02mol of 2,4,6-tris (4-aminophenyl) -1,3,5-triazine was dissolved in 100mL of ethanol by sonication for 30min, followed by addition of 100g of chitosan gel beads and reaction at 70 ℃ for 78h. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF b-2 。
The adsorption amount of the composite material prepared in the example of the present invention was 124.56mg/g and the removal rate was 99.52% as measured by the same measurement method as in example 1.
Example 7:
(1) The synthesis was the same as in step (1) in example 1.
(2) The synthesis was the same as in step (2) in example 1.
(3) 0.03mol of 2,5-dimethoxyterephthalaldehyde and 0.02mol of2,4,6-tris (4-aminophenyl) -1,3,5-triazine mixture was dissolved in 100mL of ethanol by sonication for 30min, then 100g of chitosan gel spheres were added, stirred for 2h to mix and adsorb the honeycomb chitosan gel spheres with the monomers in the solution thoroughly, and then reacted at 65 ℃ for 84h. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF b-3 。
The adsorption amount of the composite material prepared in the example of the present invention was 124.65mg/g and the removal rate was 99.68% by the same measurement method as in example 1.
Example 8:
(1) The synthesis was the same as in step (1) in example 1.
(2) The synthesis was the same as in step (2) in example 1.
(3) 0.03mol of 2,5-dihydroxyterephthalaldehyde and 0.02mol of 2,4,6-tris (4-aminophenyl) -1,3,5-triazine are ultrasonically dissolved in 100mL of ethanol for 30min, then 100g of chitosan gel spheres are added, stirred for 2h to fully mix and adsorb the honeycomb chitosan gel spheres and the monomers in the solution, and then reacted at a temperature of 55 ℃ for 90h. After the reaction is finished, filtering out the chitosan gel balls, washing the chitosan gel balls by using ethanol and water, and drying the chitosan gel balls for 24 hours to obtain CS/ZIF-8@ COF b-4 。
The adsorption amount of the composite material prepared in the example of the present invention was 124.69mg/g and the removal rate was 99.70% as measured by the same measurement method as in example 1.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A chitosan-covalent organic framework composite material is characterized in that: the chitosan gel ball with the micro-mesoporous structure is formed by chitosan and ZIF-8, and the honeycomb aerogel spherical chitosan-covalent organic framework composite material is formed by covalent organic frameworks attached to the inner wall of a pore passage of the chitosan gel ball and the surface of the chitosan gel ball, and is used for adsorbing mercury ions in water.
2. The chitosan-covalent organic framework composite of claim 1, wherein: the chitosan contains hydroxyl and amino, the covalent organic framework contains N atoms, and the viscosity of the chitosan is more than 400.
3. The chitosan-covalent organic framework composite of claim 1, wherein: the chitosan gel sphere micro-mesoporous structure has the aperture of only 1.4-1.7nm and the specific surface area of only 250-300m 2 /g。
4. A preparation method of a chitosan-covalent organic framework composite material is characterized by comprising the following steps:
dissolving chitosan powder in a glacial acetic acid solution, adding zinc nitrate hexahydrate into the obtained solution, and stirring to obtain a mixed solution;
dropping the mixed solution into a sodium hydroxide solution and a 2-methylimidazole solution to form chitosan gel spheres;
filtering out the chitosan gel balls, washing and filtering to obtain CS/ZIF-8 gel balls;
adding CS/ZIF-8 gel balls into ethanol, heating and carrying out crosslinking reaction by using glutaraldehyde;
after the crosslinking reaction, filtering, washing, suction filtering and drying to obtain CS/ZIF-8 aerogel balls;
dissolving a dimethyl aldehyde compound and a 4-aminophenyl compound into ethanol, and then adding CS/ZIF-8 aerogel balls for reaction;
after the reaction is finished, the CS/ZIF-8@ COFs aerogel balls are obtained by suction filtration, washing and drying.
5. The method of preparing a chitosan-covalent organic framework composite material of claim 4, wherein: after the chitosan powder is dissolved in the glacial acetic acid solution, the mixture is stirred for 24 hours at room temperature to completely dissolve the chitosan powder, then zinc nitrate hexahydrate is added into the obtained solution, and the mixture is stirred for 12 hours at 50 ℃ to obtain a mixed solution.
6. The method of preparing a chitosan-covalent organic framework composite material of claim 4, wherein: and dripping the mixed solution into 1% sodium hydroxide solution and 2-methylimidazole through a peristaltic pump to form chitosan gel spheres, and washing the filtered chitosan gel spheres to be neutral by using distilled water.
7. The method of preparing a chitosan-covalent organic framework composite material of claim 4, wherein: and adding the CS/ZIF-8 gel spheres into ethanol, heating to 50 ℃, carrying out crosslinking reaction for 4 hours by using glutaraldehyde, changing the color of the gel spheres from white to light yellow after the crosslinking reaction is finished, washing the filtered gel spheres by using ethanol and distilled water after the crosslinking reaction is finished, carrying out suction filtration, and then putting the gel spheres into a drying oven to be dried for 24 hours to obtain the CS/ZIF-8 aerogel spheres.
8. The method of preparing a chitosan-covalent organic framework composite material of claim 4, wherein: the dimethyl aldehyde compound and the 4-aminophenyl compound are dissolved in ethanol, and then CS/ZIF-8 aerogel balls are added to react at the temperature of 50-80 ℃ for 72-96 h, so that the color of the aerogel balls is changed from light yellow to dark yellow.
9. The method of preparing a chitosan-covalent organic framework composite material of claim 8, wherein: and after the reaction is finished, washing the CS/ZIF-8@ COFs aerogel balls obtained by suction filtration by using ethanol and water, and then drying for 24 hours to obtain the CS/ZIF-8@ COFs aerogel balls.
10. The method of preparing a chitosan-covalent organic framework composite material of claim 8, wherein: the diformaldehyde compound is terephthalaldehyde, 2,5-dibromo terephthalaldehyde, 2,5-dimethoxy terephthalaldehyde or 2,5-dihydroxy terephthalaldehyde, and the 4-aminophenyl compound is 1,3,5-tris (4-aminophenyl) benzene or 2,4,6-tris (4-aminophenyl) -1,3,5-triazine.
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