CN115709054B - 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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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a chitosan-covalent organic framework composite material, which is a chitosan gel sphere with a micro-mesoporous structure formed by chitosan and ZIF-8 and a honeycomb aerogel sphere chitosan-covalent organic framework composite material formed by covalent organic frameworks attached to the inner wall of a pore canal of the chitosan gel sphere and the surface of the chitosan gel sphere, wherein the chitosan-covalent organic framework composite material is used for adsorbing mercury ions in water. The invention also provides a preparation method of the chitosan-covalent organic framework composite material. The chitosan-covalent organic framework composite material provided by the invention has strong mercury ion adsorption capacity, and can effectively solve Hg in water body 2+ The preparation method of the composite material is simple and feasible, the production condition requirement is low, and the cost is low.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a chitosan-covalent organic framework composite material and a preparation method thereof.
Background
Among heavy metal contaminants, mercury (Hg) is attracting attention as a specific, extremely toxic, typical heavy metal element. Mercury is widely used in chemical, pharmaceutical, agricultural and daily life, about 5000 tons of mercury are introduced into the environment each year, and mercury pollution is worldwide with movement of the atmosphere and ocean currents. At present, the aspects of combustion of fossil fuel, incineration of household garbage and medical garbage, metallurgy, paper industry and the like are the main sources of global artificial mercury pollution at present, and the aspects of plastic industry, chlor-alkali industry, mixed mercury gold-smelting mercury production, wastewater of electronic industry entering rivers, lakes and the like are the main sources of mercury in water bodies. The main mercury industry in China comprises: the mercury consumption is about 1200 tons each year in the aspects of chemical industry (polyvinyl chloride, chemical reagent), light industry (battery, lighting electric appliance and electric light source), metallurgy (gold mining and metallurgy), medical appliances (thermometer and sphygmomanometer) and the like. In addition, china is the largest coal consumption country in the world, and the coal in China has high mercury and low halogen, the mining technology and equipment level are uneven, so the coal burning industry is the largest mercury emission source in China, and the maximum mercury emission source accounts for more than 50% of the total amount of the atmospheric mercury emission in China. The nonferrous metal smelting industry mainly comprises smelting of metals such as zinc, lead, copper, gold and the like, and mercury is discharged in the smelting process due to the common associated mercury element in ores. Meanwhile, china is the largest cement producing country in the world, the production amount is more than 80% of the world, and mercury is an associated element (mostly in coal) in limestone raw materials and fuel coal, so that the cement industry is also one of main mercury pollution emission sources.
Mercury can migrate to the atmosphere and soil by evaporation, sedimentation, etc., causing atmospheric pollution, soil pollution, and water pollution. In addition, mercury can migrate into the bodies of fishes, birds and mammals through the food chain and finally enrich and enter the human body, so that serious harm is caused to the human body and the ecological environment. Mercury is one of toxic heavy metal elements, and once the mercury enters a human body in the form of organic mercury, the mercury reacts with enzymes in the human body immediately to lose activity, so that functional disorders such as nervous system, digestive tract, oral cavity, kidney and liver of the human body are caused, and neurasthenia syndrome is caused when the mercury is chronically poisoned, and the symptoms such as excitation, tremors, oral mercury lines, inflammation, kidney function damage and the like are very easy to occur. In addition, mercury can invade placenta blood supply tissue in pregnant women, and thus be transferred to the fetus, resulting in infant malformation. Because mercury and its derivatives have the characteristics of durability, easy migration, biological enrichment, biological toxicity, etc. Thus, mercury has become an important environmental toxic and harmful substance, posing a great threat to human health and ecological niches. Therefore, it is listed by the united nations environmental planning agency as a global pollutant, and has become one of the pollutants for national and even global priority control. At present, how to effectively treat mercury pollution is one of important subjects in the fields of environmental, material, engineering and the like.
Common mercury-containing wastewater treatment methods include chemical precipitation, ion exchange, electrolysis and adsorption. Among these methods, adsorption has advantages of simple process, high efficiency, low cost, and capability of collecting pollutants, and is considered to be one of the most efficient and economical methods. The adsorbent can be divided into organic carriers and inorganic carriers according to carrier skeleton, and the organic carriers comprise biomass such as chitosan, cellulose, starch humic acid, synthetic polystyrene resin, polystyrene-crosslinked ethylene resin, etc. The natural organic carrier itself contains some active functional groups (-OH, -NH) 2 -COOH, etc.), and has the advantages of wide sources, low cost, easy biodegradation, no secondary pollution, etc., thus becoming the preferred green saving type mercury ion adsorbent for researchers.
Chitosan (CS) is mainly derived from marine organisms, and is a partially deacetylated product of chitin in shells of shrimps, crabs and the like, and is also the only basic polysaccharide in natural products. Because of the abundant hydroxyl, amino and other active groups in the structure, the chitosan and the derivatives thereof have a plurality of application values in the fields of medicine, textile, paper making, food, biology, chemical industry, agriculture and the like, and are widely used as adsorbents for removing pollutants in water bodies. The chitosan has the disadvantages of low mechanical strength and poor thermal stability, and is easy to dissolve under acidic conditions to influence the removal effect. Therefore, in order to overcome the deficiency of the physicochemical properties of chitosan, it is necessary to modify it in order to enhance the stability of its acidic condition.
The metal-organic framework Material (MOF) is used as a novel porous material with the characteristics of high specific surface area, adjustable pore diameter, high porosity and the like. Covalent Organic Frameworks (COFs) are highly porous materials constructed from light elements such as C, N, O, B, si and H by covalent bonds, and have the advantages of good thermal and chemical stability, structural diversity, permanent porosity, ease of functionalization, and the like. The MOF and COF materials 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 balls can be improved, the swelling of chitosan in sewage can be effectively prevented, the specific surface area and the high void ratio of the material can be further increased, mercury in the sewage can be adsorbed more effectively, the adsorption speed is high, the removal rate is high, the recycling times are high, 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 water body 2+ Pollution to the environment.
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 a chitosan gel sphere with a micro-mesoporous structure formed by ZIF-8 and covalent organic frameworks attached to the inner wall of a pore canal of the chitosan gel sphere and the surface of the chitosan gel sphere, wherein the chitosan-covalent organic framework composite material is used for adsorbing mercury ions in water.
Further, the chitosan contains hydroxyl and amino groups, the covalent organic framework contains N atoms, and the viscosity of the chitosan is more than 400.
Further, 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。
The invention also provides a preparation method of the chitosan-covalent organic framework composite material, which comprises the following steps:
dissolving chitosan powder in glacial acetic acid solution, adding zinc nitrate hexahydrate into the obtained solution, and stirring to obtain a mixed solution;
dripping the mixed solution into a sodium hydroxide and 2-methylimidazole solution to form chitosan gel spheres;
filtering out the chitosan gel ball, washing and suction filtering to obtain CS/ZIF-8 gel ball;
adding CS/ZIF-8 gel balls into ethanol, heating and carrying out crosslinking reaction by glutaraldehyde;
after the crosslinking reaction, filtering, washing, suction filtering and drying to obtain CS/ZIF-8 aerogel balls;
dissolving a dicarboxaldehyde compound and a 4-aminophenyl compound into ethanol, and then adding CS/ZIF-8 aerogel balls to react;
and after the reaction is finished, carrying out suction filtration, washing and drying to obtain the CS/ZIF-8@COFs aerogel balls.
Further, after the chitosan powder was dissolved in the glacial acetic acid solution, stirring was performed at room temperature for 24 hours to completely dissolve the chitosan powder, and then zinc nitrate hexahydrate was added to the obtained solution, and stirring was performed at 50 ℃ for 12 hours to obtain a mixed solution.
Further, 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 through distilled water.
Further, the CS/ZIF-8 gel balls are added into ethanol, heated to 50 ℃ and subjected to crosslinking reaction for 4 hours by glutaraldehyde, the color of the gel balls is changed from white to light yellow after the crosslinking reaction is finished, the gel balls obtained by filtering after the crosslinking reaction are washed by ethanol and distilled water, filtered by suction, and then placed into a drying box for drying for 24 hours, so that the CS/ZIF-8 aerogel balls are obtained.
Further, the dicarboxaldehyde compound and the 4-aminophenyl compound are dissolved in ethanol, then CS/ZIF-8 aerogel balls are added for reaction at 50-80 ℃ for 72-96 hours, and the color of the gel balls is changed from light yellow to dark yellow.
Further, after the reaction is finished, the CS/ZIF-8@COFs aerogel balls obtained through suction filtration are washed by using ethanol and water, and then are dried for 24 hours to obtain the CS/ZIF-8@COFs aerogel balls.
Further, the dicarboxaldehyde compound is terephthalaldehyde, 2, 5-dibromoterephthalaldehyde, 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 chitosan-covalent organic framework composite material provided by the invention has a rich micro-mesoporous structure, the pore diameter is about 1.4-1.7nm, the specific surface area is very high, and the specific surface area can reach 300m 2 And/g. The chitosan of the composite material contains abundant hydroxyl and amino in its own 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 rapidly adsorb various heavy metal ions, and 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 keep the respective advantages of the chitosan material and the covalent organic framework material, but also can improve the stability of the chitosan gel ball in the aqueous solution, effectively avoid swelling of the chitosan gel ball in the aqueous solution, and further improve the mechanical properties of the honeycomb chitosan aerogel ball. In addition, the composite material has strong adsorption capacity and removal rate in acid or alkali environment, and does not cause secondary pollution of water.
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 chitosan raw materials, generating cellular porous chitosan gel balls in sodium hydroxide solution, taking the cellular porous chitosan gel balls as carriers, and introducing covalent organic frameworks into the inner walls and the surfaces of pore canals of a cellular structure to finally obtain the cellular chitosan-covalent organic framework composite material. The process is simple and easy to operate, expensive equipment and harsh production conditions are not needed, the prepared composite material is controllable in appearance, nontoxic, odorless and pollution-free, and meanwhile, the composite material can be used as an adsorbent for mercury ions in industrial wastewater repeatedly, so that the adsorption cost of mercury in the wastewater is greatly reduced, the economic benefit is improved, and the composite material has a good application prospect.
Drawings
FIG. 1 is a flow chart of a preparation method of a chitosan-covalent organic framework composite material provided by an embodiment of the invention;
FIG. 2 is a FT-IR spectrum of a mesoporous CS/ZIF-8@COFs composite material prepared by a preparation method of a chitosan-covalent organic framework composite material provided by an embodiment 1 of the invention;
FIG. 3 is an SEM image of a mesoporous CS/ZIF-8@COFs composite material prepared by a preparation method of a chitosan-covalent organic framework composite material provided by the embodiment 1 of the invention;
FIG. 4 is a SEM image with higher magnification of a mesoporous CS/ZIF-8@COFs composite material prepared by the preparation method of the chitosan-covalent organic framework composite material provided by the embodiment 1 of the invention;
FIG. 5 is an XRD pattern of a mesoporous CS/ZIF-8@COFs composite material prepared by the preparation method of the chitosan-covalent organic framework composite material provided by the embodiment 1 of the invention;
FIG. 6 is a BET diagram of a mesoporous CS/ZIF-8@COFs composite material prepared by a preparation method of a chitosan-covalent organic framework composite material provided by the embodiment 1 of the invention;
FIG. 7 is another BET plot of the mesoporous CS/ZIF-8@COFs composite material prepared by the preparation method of the chitosan-covalent organic framework composite material provided by the embodiment 1 of the invention.
Detailed Description
The chitosan-covalent organic framework composite material provided by the embodiment of the invention is a honeycomb aerogel ball chitosan-covalent organic framework composite material formed by chitosan and a chitosan gel ball with a micro-mesoporous structure formed by ZIF-8 and a covalent organic framework attached to the inner wall of a chitosan gel ball pore canal and the surface of the chitosan gel ball, and 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 glacial acetic acid solution, then adding zinc nitrate hexahydrate into the obtained solution, and stirring to obtain a mixed solution.
Step 2) dripping the mixed solution into a sodium hydroxide and 2-methylimidazole solution to form chitosan gel spheres.
And 3) filtering out the chitosan gel balls, washing and filtering to obtain CS/ZIF-8 gel balls.
Step 4) adding CS/ZIF-8 gel balls into ethanol, heating and carrying out crosslinking reaction by glutaraldehyde.
And 5) after the crosslinking reaction, filtering, washing, suction filtering and drying to obtain the CS/ZIF-8 aerogel balls.
Step 6) dissolving the dicarboxaldehyde compound and the 4-aminophenyl compound into ethanol, and then adding CS/ZIF-8 aerogel balls to react.
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 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.
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 through distilled water.
The CS/ZIF-8 gel balls are added into ethanol, heated to 50 ℃ and subjected to crosslinking reaction by glutaraldehyde for 4 hours, the color of the gel balls is changed from white to light yellow after the crosslinking reaction is finished, the gel balls obtained by filtering after the crosslinking reaction are washed by ethanol and distilled water, filtered by suction, and then placed into a drying oven for drying for 24 hours, so that CS/ZIF-8 aerogel balls are obtained.
Wherein the dicarboxaldehyde compound and the 4-aminophenyl compound are dissolved in ethanol, then CS/ZIF-8 aerogel balls are added for reaction at 50-80 ℃ for 72-96 hours, and the color of the gel balls is changed from light yellow to dark yellow.
And washing the CS/ZIF-8@COFs aerogel ball 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 ball.
Wherein the dicarboxaldehyde compound is terephthalaldehyde, 2, 5-dibromoterephthalaldehyde, 2, 5-dimethoxy terephthalaldehyde or 2, 5-dihydroxyterephthalaldehyde, and the 4-aminophenyl compound is 1,3, 5-tri (4-aminophenyl) benzene or 2,4, 6-tri (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 examples.
Example 1:
(1) First, 2g of chitosan powder was dissolved in 100mL of 3% glacial acetic acid solution, and stirred at room temperature for 24 hours to completely dissolve. Then 8.2g of zinc nitrate hexahydrate is added into the chitosan solution, and stirred at 50 ℃ for 12 hours until the solution is uniformly mixed, the chitosan solution is dripped into 2.6g of 2-methylimidazole ligand and 1% sodium hydroxide solution through a peristaltic pump, then the chitosan gel balls are filtered out, washed to be neutral through distilled water, filtered by suction, dried in a drying box for 24 hours, and then sealed for standby.
(2) The chitosan gel balls are added into a certain amount of ethanol solution, heated to 50 ℃ and subjected to crosslinking reaction for 4 hours by glutaraldehyde. Then filtering out the chitosan gel balls, washing with ethanol and distilled water, filtering, putting into a drying oven for drying for 24 hours, and sealing for later use.
(3) A mixture of 0.03mol of terephthalaldehyde and 0.02mol of 1,3, 5-tris (4-aminophenyl) benzene was sonicated for 30min to dissolve in 100mL of ethanol, followed by adding 100g of chitosan gel beads and stirring for 2h to give a honeycomb shellThe gel-like spheres were thoroughly mixed with the monomers in solution and adsorbed, and then reacted at 80℃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, the FT-IR spectrum of the mesoporous CS/ZIF-8@cofs composite material prepared by the embodiment of the present invention, as can be seen from fig. 2, the mesoporous CS/ZIF-8@cofs composite material prepared by the embodiment of the present invention contains functional groups such as hydroxyl groups, amino groups, and the like, and also contains functional groups of benzene rings in covalent organic frameworks.
Referring to fig. 3 and 4, SEM spectra of the mesoporous CS/ZIF-8@cofs composite material prepared by the embodiment of the present invention can be seen from fig. 3 and 4, and the mesoporous CS/ZIF-8@cofs composite material prepared by the embodiment of the present invention has a honeycomb structure.
Referring to FIG. 5, the XRD spectrum of the mesoporous CS/ZIF-8@COFs composite material prepared by the embodiment of the invention can be seen from FIG. 5, and ZIF-8 crystals are formed in the mesoporous CS/ZIF-8@COFs composite material prepared by the embodiment of the invention.
Referring to fig. 6 and 7, the BET spectra of the mesoporous CS/ZIF-8@cofs composite material prepared by the embodiment of the present invention can be seen from fig. 6 and 7, and the mesoporous CS/ZIF-8@cofs composite material prepared by the embodiment of the present invention has a porous property.
The apparatus used for measuring the adsorption capacity and the removal rate of the composite material prepared by the embodiment of the invention is as follows:
(1) FT-IR was measured using a Spectrum One IR spectrometer from PE, USA. The solid sample adopts KBr tabletting, the liquid sample is coated on KBr wafer, and the wave number range of absorption spectrum scanning is 4000-500 cm -1 Scanning 3 times.
(2) X-ray diffractometer (XRD) with Bruker D8 ADVANCE wide angle X-ray diffractometer, germany, cu targetThe scanning range is 0-10 degrees.
(3) Scanning Electron Microscopy (SEM) was used to record scan images using japanese SU 8010.
(4) In the experiment, the concentration of Hg (II) in the solution after the composite material prepared in the embodiment is adsorbed is measured by using an SL58-CG-1C intelligent mercury instrument.
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 adding a small amount of deionized water for constant volume to prepare a mercury ion-containing solution, 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 supernatant after centrifugation into a 50mL volumetric flask, and carrying out constant volume and shaking uniformly by using absolute ethyl alcohol. The adsorption amount 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 which Q e Adsorption amount (mg/g) of Hg (II) to the adsorbent; c (C) 0 And C e Hg (II) concentration (mg/L) in the solution before the adsorbent is not adsorbed and Hg (II) concentration (mg/L) in the solution after the adsorbent is adsorbed respectively; m is the mass (g) of the adsorbent; v is the volume of the solution (L); r is Hg (II) removal (%) from the solution.
The adsorption capacity of the composite material prepared in the embodiment is 124.14mg/g and the removal rate is 99.17% by calculation.
Example 2:
(1) The same procedure as in step (1) of example 1 was followed.
(2) The same procedure as in step (2) of example 1 was followed.
(3) 0.03mol of 2, 5-dibromoterephthalaldehyde and 0.02mol of 1,3, 5-tris (4-aminophenyl) benzene were dissolved in 100mL of ethanol, followed by addition of 100g of chitosan gel beads,the cellular chitosan gel spheres were thoroughly mixed with the monomers in the solution and adsorbed by stirring for 2h, and then reacted at 75 ℃ 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 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% by the same measurement method as in example 1.
Example 3:
(1) The same procedure as in step (1) of example 1 was followed.
(2) The same procedure as in step (2) of example 1 was followed.
(3) A mixture of 0.03mol of 2, 5-dimethoxy terephthalaldehyde and 0.02mol of 1,3, 5-tris (4-aminophenyl) benzene was ultrasonically dissolved in 100mL of ethanol for 30min, followed by adding 100g of chitosan gel beads, stirring for 2h to allow the honeycomb chitosan gel beads to be well mixed with the monomers in the solution and adsorbed, and then reacting at 70℃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 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% by the same measurement method as in example 1.
Example 4:
(1) The same procedure as in step (1) of example 1 was followed.
(2) The same procedure as in step (2) of example 1 was followed.
(3) A mixture of 0.03mol of 2, 5-dihydroxyterephthalaldehyde and 0.02mol of 1,3, 5-tris (4-aminophenyl) benzene was sonicated for 30min to dissolve in 100mL of ethanol, followed by adding 100g of chitosan gel beads, stirring for 2h to allow the honeycomb chitosan gel beads to be thoroughly mixed with the monomers in the solution and adsorbed, and then reacting at 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 a-4 。
The adsorption capacity of the composite material prepared in the example of the present invention was 124.70mg/g and the removal rate was 99.72% by the same measurement method as in example 1.
Example 5:
(1) The same procedure as in step (1) of example 1 was followed.
(2) The same procedure as in step (2) of example 1 was followed.
(3) A mixture of 0.03mol of terephthalaldehyde and 0.02mol of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine was ultrasonically dissolved in 100mL of ethanol for 30min, followed by adding 100g of chitosan gel beads, stirring for 2h to allow the honeycomb chitosan gel beads to be well mixed with the monomers in the solution and adsorbed, and then reacting at 50℃for 96h. 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% by the same measurement method as in example 1.
Example 6:
(1) The same procedure as in step (1) of example 1 was followed.
(2) The same procedure as in step (2) of example 1 was followed.
(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 sonicated for 30min to 100mL of ethanol, 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% by the same measurement method as in example 1.
Example 7:
(1) The same procedure as in step (1) of example 1 was followed.
(2) The same procedure as in step (2) of example 1 was followed.
(3) A mixture of 0.03mol of 2, 5-dimethoxy terephthalaldehyde and 0.02mol of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine was sonicated for 30min to dissolve in 100mL of ethanol, followed by100g of chitosan gel balls were added, and the mixture was stirred for 2 hours to allow the honeycomb chitosan gel balls to be thoroughly mixed with the monomers in the solution and adsorbed, and then reacted at 65℃for 84 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 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 same procedure as in step (1) of example 1 was followed.
(2) The same procedure as in step (2) of example 1 was followed.
(3) A mixture of 0.03mol of 2, 5-dihydroxyterephthalaldehyde and 0.02mol of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine was sonicated for 30min to dissolve in 100mL of ethanol, followed by adding 100g of chitosan gel beads, stirring for 2 hours to allow the honeycomb chitosan gel beads to be thoroughly mixed with the monomers in the solution and adsorbed, and then reacted at 55℃for 90 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 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% by the same measurement method as in example 1.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, 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 and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (9)
1. The preparation method of the chitosan-covalent organic framework composite material is characterized by comprising the following steps of:
dissolving chitosan powder in glacial acetic acid solution, adding zinc nitrate hexahydrate into the obtained solution, and stirring to obtain a mixed solution;
dripping the mixed solution into a sodium hydroxide and 2-methylimidazole solution to form chitosan gel spheres;
filtering out the chitosan gel ball, washing and suction filtering to obtain CS/ZIF-8 gel ball;
adding CS/ZIF-8 gel balls into ethanol, heating and carrying out crosslinking reaction by glutaraldehyde;
after the crosslinking reaction, filtering, washing, suction filtering and drying to obtain CS/ZIF-8 aerogel balls;
dissolving a dicarboxaldehyde compound and a 4-aminophenyl compound into ethanol, and then adding CS/ZIF-8 aerogel balls to react;
after the reaction is finished, carrying out suction filtration, washing and drying to obtain CS/ZIF-8@COFs aerogel balls;
the dicarboxaldehyde compound is terephthalaldehyde, 2, 5-dibromoterephthalaldehyde, 2, 5-dimethoxy terephthalaldehyde or 2, 5-dihydroxy terephthalaldehyde, and the 4-aminophenyl compound is 1,3, 5-tri (4-aminophenyl) benzene or 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine.
2. The method for preparing the chitosan-covalent organic framework composite material according to claim 1, wherein the method comprises the following steps: after the chitosan powder was dissolved in glacial acetic acid solution, the chitosan powder was completely dissolved by stirring at room temperature for 24 and h, and then zinc nitrate hexahydrate was added to the obtained solution, and stirring at 50 ℃ for 12 and h was performed to obtain a mixed solution.
3. The method for preparing the chitosan-covalent organic framework composite material according to claim 1, wherein the method comprises the following steps: the mixed solution is dripped into 1% sodium hydroxide solution and 2-methylimidazole through a peristaltic pump to form chitosan gel spheres, and the filtered chitosan gel spheres are washed to be neutral through distilled water.
4. The method for preparing the chitosan-covalent organic framework composite material according to claim 1, wherein the method comprises the following steps: the CS/ZIF-8 gel balls are added into ethanol, heated to 50 ℃, subjected to crosslinking reaction by glutaraldehyde for 4h, the color of the gel balls is changed from white to light yellow after the crosslinking reaction is finished, the gel balls obtained by filtering after the crosslinking reaction is finished are washed by ethanol and distilled water, filtered by suction, and then placed into a drying box for drying for 24h, so that the CS/ZIF-8 aerogel balls are obtained.
5. The method for preparing the chitosan-covalent organic framework composite material according to claim 1, wherein the method comprises the following steps: the dicarboxaldehyde compound and the 4-aminophenyl compound are dissolved in ethanol, CS/ZIF-8 aerogel balls are added for reaction at 50-80 ℃ for 72-96 hours, and the color of the gel balls is changed from light yellow to dark yellow.
6. The method for preparing a chitosan-covalent organic framework composite material according to claim 5, wherein: and washing the CS/ZIF-8@COFs aerogel ball obtained by suction filtration after the reaction is finished by using ethanol and water, and then drying 24h to obtain the CS/ZIF-8@COFs aerogel ball.
7. The method for preparing a chitosan-covalent organic framework composite material according to claim 6, wherein: the CS/ZIF-8@COFs aerogel ball is a honeycomb aerogel ball chitosan-covalent organic framework composite material formed by chitosan and ZIF-8, wherein the chitosan gel ball is provided with a micro-mesoporous structure, and the covalent organic framework is attached to the inner wall of a pore canal of the chitosan gel ball and the surface of the chitosan gel ball, and the chitosan-covalent organic framework composite material is used for adsorbing mercury ions in water.
8. The method for preparing a chitosan-covalent organic framework composite material according to claim 7, wherein: the chitosan contains hydroxyl and amino, the covalent organic framework contains N atoms, and the viscosity of the chitosan is more than 400.
9. The method for preparing a chitosan-covalent organic framework composite material according to claim 7, wherein: the pore diameter of the chitosan gel sphere micro-mesoporous structure is 1.4-1.7-nm, and the ratio is thatSurface area of 250-300m 2 /g。
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