CN109517212B - Preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel - Google Patents
Preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel Download PDFInfo
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Abstract
The invention relates to a preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel. The preparation method comprises the following steps: dissolving cellulose by adopting a low-temperature alkaline-urea circulating freeze thawing method, obtaining cellulose-graphene oxide composite gel by a sol-gel method, oxidizing hydroxyl in the cellulose into aldehyde groups by taking sodium periodate as an oxidant, further reacting with a chitosan solution to obtain cellulose-graphene oxide-chitosan ternary composite gel, and combining a freeze drying technology to obtain the ternary composite aerogel. The addition of the chitosan and the graphene oxide not only enhances the mechanical property of the material, but also improves the specific surface area and the porosity of the aerogel material, and has good application prospect when being used as an adsorbent for oil, dye and heavy metal ions in the field of water treatment.
Description
Technical Field
The invention belongs to the field of preparation of high-molecular nano functional materials, and particularly relates to a preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel.
Background
With the rapid development of modern industry, the excessive consumption of petroleum-based polymers causes the dual crises of shortage of non-renewable resources and environmental pollution, and simultaneously stimulates the human to create a new green material by utilizing natural high molecular materials. Water is a life source, and serious pollution to water sources in China is caused along with random discharge of industrial wastewater, mining wastewater, urban domestic sewage, industrial waste and the like, and a large amount of heavy metal ions, oil stains, dyes and toxic organic solvents in water circulate in a biological chain, so that animal, plant and human health are seriously threatened. The common wastewater treatment methods comprise a chemical precipitation method, an electrolysis method, an ion exchange method, a membrane separation method, an adsorption method and the like, wherein the adsorption method has the advantages of strong applicability, good treatment effect, recyclability and the like, and has always attracted wide attention in the environmental protection field. The adsorption method can be divided into three types of physical adsorption, chemical adsorption and ion exchange adsorption according to different adsorption mechanisms, and the three types of adsorption methods are not usually isolated and often exist simultaneously to realize synergistic adsorption. Meanwhile, in recent years, green novel efficient adsorbents prepared by taking natural biomass macromolecules as raw materials are increasingly emphasized by virtue of incomparable advantages.
Cellulose is a natural polymer raw material with the largest reserve in nature on earth, and has attracted attention due to its extremely strong renewability, wide application, low cost, good biocompatibility and easy degradability. Meanwhile, chitosan is a polysaccharide which is second to cellulose in the earth, and is a nitrogen-containing natural organic high molecular compound which is the largest in quantity except for protein in nature. The chitosan has antibacterial property, biocompatibility and biodegradability, and the molecular chain simultaneously contains active groups such as amino, hydroxyl, oxygen bridge and the like, so that reactions such as complexation, salification, basification, Schiff base reaction, arylation, alkylation, acylation, graft copolymerization and the like can be carried out, and the excellent characteristics enable the chitosan to be widely applied to the fields of textile printing and dyeing, adsorption, food and biomedicine.
Graphene oxide is a novel carbon material with excellent performance, and has a high specific surface area and rich functional groups on the surface. The graphene oxide composite material comprises a polymer composite material and an inorganic composite material, and has wide application fields. Aerogel materials are novel materials which take gas as a dispersion medium and have a continuous three-dimensional nano porous network structure, and mainly comprise ultralow density, high specific surface area, ultrahigh porosity, extremely low heat transfer coefficient, low optical refractive index, low dielectric constant and the like by virtue of unique properties of the aerogel materials, and the aerogel materials are widely applied to the aspects of military affairs, buildings, energy sources, biopharmaceuticals, environmental protection and the like. Therefore, the cellulose/chitosan/graphene oxide ternary composite aerogel material which has high adsorbability and wide sources and is not easy to cause secondary pollution to water is prepared, and the preparation method has very strong practical significance and research value.
Disclosure of Invention
The invention aims to provide a preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel, which is a green environment-friendly adsorbent for industrial wastewater treatment, and the ternary composite aerogel is prepared by compounding cellulose, graphene oxide and chitosan on the basis of research on the existing cellulose-graphene oxide aerogel and cellulose-chitosan aerogel, and has higher mechanical strength, larger specific surface area and higher porosity.
The technical scheme of the invention comprises the following steps: a preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel comprises the following specific steps:
(1) preparation of cellulose-graphene oxide gel
Dissolving cellulose with an alkaline urine solution to obtain a cellulose solution, adding a graphene oxide aqueous solution, uniformly stirring, placing the cellulose solution into a refrigerator with the temperature of-30 to-15 ℃ for precooling for at least 10-12 h, taking out the cellulose solution to be melted to the temperature of-14 to-10 ℃, stirring to obtain a transparent mixed solution of the cellulose and the graphene oxide with a large number of bubbles, placing the mixed solution into a centrifuge for centrifugation, taking out a transparent clear solution, pouring the clear solution into a container, placing the container into a coagulating bath, and standing for 6-48 h to obtain cellulose-graphene oxide gel;
(2) preparation of cellulose-graphene oxide-chitosan gel
Weighing chitosan powder, dissolving the chitosan powder in an acid solution, and stirring until the chitosan powder is completely dissolved to obtain a chitosan solution; immersing the cellulose-graphene oxide gel obtained in the step (1) into a sodium periodate solution in a brown bottle, oscillating at a low speed at 20-30 ℃, oxidizing in the dark for 12-24 h, washing the gel after reaction by deionized water, immersing the gel into a prepared chitosan solution for soaking for 12-24 h, taking out, and washing by deionized water until the pH value is 6.5-7.5;
(3) preparation of cellulose-graphene oxide-chitosan aerogel
And (3) putting the prepared cellulose-graphene oxide-chitosan ternary composite hydrogel into a freeze dryer for drying, and drying to obtain the cellulose-graphene oxide-chitosan ternary composite aerogel.
Preferably, the cellulose in the step (1) is one of cotton pulp, short stapled cotton or microcrystalline cellulose; the alkali is one of sodium hydroxide or lithium hydroxide; the urine is urea or thiourea.
Preferably, the cellulose solution in the step (1) contains 2.9-5.7% of cellulose, 4.3-20.5% of alkali, 11.6-20.5% of urine and 56.5-78.67% of deionized water by mass.
Preferably, the concentration of the graphene oxide aqueous solution in the step (1) is 2-5 mg/ml; the volume ratio of the cellulose dissolving solution to the graphene oxide aqueous solution is 4-56: 1.
preferably, the stirring speed of the transparent cellulose and graphene oxide mixed solution with a large number of bubbles obtained by stirring in the step (1) is 2000-5000 rpm, and the stirring time is 20-50 min; the centrifugal speed of the centrifugal machine is 7000-10000 r/min, and the centrifugal time is 3-7 min.
Preferably, the coagulating bath in the step (1) is one of ethanol, methanol or acetone coagulating baths.
Preferably, the acid in the step (2) is one or more of hydrochloric acid, nitric acid, formic acid or acetic acid.
Preferably, the mass concentration of the sodium periodate in the step (2) is 10-12 g/L; sodium periodate is used as an oxidant to oxidize hydroxyl groups on cellulose into aldehyde groups, and then the aldehyde groups react with amino groups of chitosan to enable the chitosan and the cellulose to be crosslinked.
Preferably, the concentration of the chitosan solution in the step (2) is 10-20 mg/ml.
Preferably, the freeze drying temperature in the step (3) is-60 to-40 ℃, the pressure is 1 to 10Pa, and the drying time is 48 to 54 hours.
Has the advantages that:
the method and the cellulose-graphene oxide-chitosan ternary composite aerogel material prepared by the method have the following characteristics:
(1) the process method is feasible and effective. The method is based on the existing research methods of cellulose-graphene oxide aerogel and cellulose-chitosan aerogel, adopts graphene oxide and cellulose composite chitosan to obtain the ternary composite aerogel, and has the main mechanism that the surfaces of cellulose, chitosan and graphene oxide are rich in a large amount of hydroxyl groups which are not only donors of hydrogen bonds but also acceptors of the hydrogen bonds, so theoretically, the three substances can be compounded and crosslinked with each other to form hydrogen bonds to obtain gel, the method firstly obtains cellulose and graphene oxide composite gel on the basis, then oxidizes the hydroxyl on the surface of the cellulose into dialdehyde by using sodium periodate as a strong oxidizer, so as to perform Schiff base reaction with chitosan to obtain cellulose-graphene oxide-chitosan ternary composite gel, and finally performing freeze-drying to obtain the cellulose-graphene oxide-chitosan ternary composite aerogel.
(2) The raw materials of cellulose and chitosan are natural polymers with abundant reserves in nature, are low in price, are green and environment-friendly, and are biodegradable and good in biocompatibility, and the cellulose and chitosan are hot spots researched in the current biodegradable high molecules. Although the price of the graphene oxide is slightly higher, the amount of the graphene oxide used in the method is small, the mechanical strength of the composite material is increased, the adsorption material can be recycled, and the use cost is reduced compared with other disposable adsorption materials.
(3) Compared with other binary composite aerogels, the cellulose-graphene oxide-chitosan ternary composite aerogel obtained by the method has the characteristics of the aerogel, has the characteristics of cellulose, graphene oxide and chitosan, enhances the mechanical property of the material, improves the specific surface area of the material, and simultaneously, a large amount of hydroxyl groups rich in the surfaces of the cellulose, graphene oxide and chitosan can be used as active sites for adsorbing heavy metal ions, thereby being beneficial to the adsorption of the heavy metal ions in water.
(4) The cellulose-graphene oxide-chitosan ternary composite aerogel sample has controllable thickness and good formability, and cracks are generated on the surface due to freeze drying, so that the adsorption efficiency and the adsorption capacity of the material applied to the adsorption field are not influenced. The specific cellulose-graphene oxide-chitosan ternary composite aerogel sample is shown in the attached drawing.
Drawings
Fig. 1 is a sample diagram of a cellulose-graphene oxide-chitosan ternary composite aerogel.
Detailed Description
Example 1
Weighing 7g of lithium hydroxide, 12g of urea and 81ml of deionized water in a 250ml conical flask, adding 3g of microcrystalline cellulose, placing the mixture on a magnetic stirrer at a rotating speed of 400rpm, and uniformly stirring, wherein the mass fraction ratio of the cellulose, alkali, urine and deionized water is 2.9%: 6.8%: 11.7%: 78.6 percent of the mixture is added with 3ml of 2mg/ml graphene oxide aqueous solution and evenly mixed, the volume ratio of the cellulose dissolving solution to the graphene oxide aqueous solution is 81:3, the mixture is put into a refrigerator with the temperature of minus 30 ℃ for precooling for at least 12h, taken out and melted to the temperature of minus 10 ℃, stirred vigorously at 2000rpm for 30min to obtain a transparent mixed solution of the cellulose and the graphene oxide with a large number of bubbles, the mixed solution is put into a centrifuge for centrifugation for 5min, the centrifugation speed is 8000r/min, taken out to obtain a transparent clear solution, poured into a prepared plastic disposable water cup, and the cup is put into an ethanol coagulation bath for 48h to obtain the cellulose-graphene oxide gel. Weighing 3g of chitosan powder, dissolving in 4mL of glacial acetic acid and 196mL of deionized water, placing the mixed solution on an electric stirrer, stirring for 2h at normal temperature, and continuously stirring until the chitosan powder is completely dissolved to obtain a uniform chitosan solution for later use. Then preparing 10.7g/L sodium periodate solution by using a 500ml volumetric flask, transferring the obtained gel into a brown bottle containing a certain volume of sodium periodate solution, oscillating at a low speed at 30 ℃, oxidizing for 24 hours in a dark place, and oxidizing the reacted gel after reactionAnd (3) washing and soaking the gel with deionized water for multiple times, removing the unreacted sodium periodate solution until the pH value is neutral, soaking the obtained composite gel into the prepared chitosan solution for 24 hours, taking out the composite gel, and washing the composite gel with deionized water for multiple times until the pH value is 6.5. And placing the prepared cellulose-graphene oxide-chitosan ternary composite gel into a refrigerator with the temperature of-30 ℃ for precooling for 12 hours, taking out the cellulose-graphene oxide-chitosan ternary composite gel, freeze-drying the cellulose-graphene oxide-chitosan ternary composite gel in a freeze-drying machine at the drying temperature of-50 ℃ for 48 hours under the pressure of 10pa, and drying to obtain the cellulose-graphene oxide-chitosan ternary composite aerogel. The specific surface area of the material is 286m2Per g, porosity 89.2%, density 0.074g/cm3. The attached figure is a sample diagram of the cellulose-graphene oxide-chitosan ternary composite aerogel material prepared in example 1. As can be seen in the figure, the composite aerogel presents black, cracks exist on the surface of the material, and the condition of powder falling does not exist.
Example 2
Weighing 4.6g of lithium hydroxide, 15g of urea and 80.4ml of deionized water in a 250ml conical flask, adding 6g of cotton pulp cypress cellulose, and uniformly stirring the mixture on a magnetic stirrer at a rotating speed of 500rpm, wherein the mass fraction ratio of the cellulose, alkali, urine and deionized water is 5.7%: 4.3%: 14.2%: 75.8 percent of the cellulose-graphene oxide gel, 20ml of 3mg/ml graphene oxide aqueous solution is added, the volume ratio of the cellulose dissolving solution to the graphene oxide aqueous solution is 80.4:20, the mixture is placed into a refrigerator with the temperature of 15 ℃ below zero for precooling for at least 10h, the mixture is taken out and melted to the temperature of 14 ℃ below zero, the mixture is stirred at 5000rpm for 20min to obtain a transparent mixed solution of the cellulose and the graphene oxide with a large number of bubbles, the mixed solution is placed into a centrifuge for centrifugation for 5min at the centrifugal speed of 9000r/min, the transparent clear solution is taken out and is free of bubbles and precipitates, the mixture is poured into a prepared plastic disposable water cup, and the cup is placed into a methanol coagulation bath for 36h to obtain. Weighing 2g of chitosan powder, dissolving the chitosan powder in 4mL of hydrochloric acid and 196mL of deionized water, placing the mixed solution on an electric stirrer, stirring for 2 hours at normal temperature, and continuously stirring until the chitosan powder is completely dissolved to obtain a uniform chitosan solution for later use. Preparing 11g/L sodium periodate solution in a 500ml volumetric flask, transferring the obtained gel into a brown bottle containing a certain volume of sodium periodate solution, oscillating at a low speed at 25 ℃, oxidizing for 12h in a dark place, and reactingAnd washing and soaking the gel with deionized water for multiple times, removing the unreacted sodium periodate solution until the pH value is neutral, soaking the obtained composite gel into the prepared chitosan solution for 12 hours, taking out the composite gel, and washing with deionized water for multiple times until the pH value is 7. And placing the prepared cellulose-graphene oxide-chitosan ternary composite gel into a refrigerator with the temperature of-30 ℃ for pre-cooling for 10 hours, taking out the cellulose-graphene oxide-chitosan ternary composite gel, freeze-drying the cellulose-graphene oxide-chitosan ternary composite gel in a freeze-drying machine at the drying temperature of-40 ℃ for 50 hours under the drying pressure of 5pa, and drying to obtain the cellulose-graphene oxide-chitosan ternary composite aerogel. The specific surface area of the material is 264m2G, porosity 85.0%, density 0.072g/cm3。
Example 3
Weighing 20g of sodium hydroxide, 20g of thiourea and 56ml of deionized water in a 250ml conical flask, adding 3g of linter cotton cellulose in a magnetic stirrer at the rotating speed of 450rpm, and uniformly stirring, wherein the mass fraction ratio of the cellulose, alkali, urine and deionized water is 3.0%: 20.2%: 20.2%: 56.6 percent of the cellulose-graphene oxide gel, 1ml of 5mg/ml graphene oxide aqueous solution is added, the volume ratio of the cellulose dissolving solution to the graphene oxide aqueous solution is 56:1, the mixture is placed into a refrigerator with the temperature of minus 20 ℃ for precooling for at least 12 hours, the mixture is taken out and melted to the temperature of minus 12 ℃, the mixture is stirred vigorously at 3000rpm for 30 minutes to obtain a transparent mixed solution of the cellulose and the graphene oxide with a large number of bubbles, the mixed solution is placed into a centrifuge for centrifugation for 3 minutes at the centrifugation speed of 10000r/min, the transparent clear solution is taken out and is free of bubbles and precipitates, the mixture is poured into a prepared plastic disposable water cup, and the cup is placed into an acetone coagulation bath and is kept stand for 24 hours to obtain. Weighing 1g of chitosan powder, dissolving in 4mL of nitric acid and 196mL of deionized water, placing the mixed solution on an electric stirrer, stirring for 1h at normal temperature, and continuously stirring until the chitosan powder is completely dissolved to obtain a uniform chitosan solution for later use. Preparing 12g/L sodium periodate solution by using a 500ml volumetric flask, transferring the obtained gel into a brown bottle containing a certain volume of sodium periodate solution, oscillating at a low speed at 25 ℃, oxidizing for 20 hours in a dark place, washing and soaking the reacted gel for multiple times by using deionized water, removing the unreacted sodium periodate solution until the pH value is neutral, soaking the obtained composite gel into the prepared chitosan solution for 20 hours, taking out the composite gel, and washing for multiple times by using the deionized waterTo a pH of 7.5. And (2) placing the prepared cellulose-graphene oxide-chitosan ternary composite gel into a refrigerator with the temperature of-30 ℃ for precooling for 36h, taking out the cellulose-graphene oxide-chitosan ternary composite gel, freeze-drying the cellulose-graphene oxide-chitosan ternary composite gel in a freeze-drying machine at the drying temperature of-48 ℃ for 52h under the pressure of 1pa, and drying to obtain the cellulose-graphene oxide-chitosan ternary composite aerogel. The specific surface area of the material is 235m2Per g, porosity 76.0%, density 0.094g/cm3。
Example 4
Weighing 4.6g of sodium hydroxide, 15g of urea and 77.6ml of deionized water into a 250ml conical flask, adding 3g of linter cotton cellulose into the conical flask, uniformly stirring the mixture on a magnetic stirrer at the rotating speed of 500rpm, wherein the mass fraction ratio of the cellulose to the alkali to the urine to the deionized water is 3.0%: 4.6%: 15%: 77.4 percent of the total weight of the solution, 10ml of 2mg/ml graphene oxide aqueous solution is added, the volume ratio of the cellulose dissolving solution to the graphene oxide aqueous solution is 77.6:10, the solution is placed into a refrigerator at minus 30 ℃ for precooling for at least 12 hours, the solution is taken out and melted to the temperature of minus 12 ℃, the solution is stirred vigorously at 2000rpm for 50 minutes to obtain a transparent mixed solution of the cellulose and the graphene oxide with a large number of bubbles, the mixed solution is placed into a centrifuge for centrifugation for 5 minutes at the centrifugation speed of 8000r/min, the transparent clear solution is taken out and is free of bubbles and precipitates, the solution is poured into a prepared plastic disposable water cup, and the cup is placed into an ethanol coagulation bath for 6 hours to obtain the cellulose-graphene oxide gel. Weighing 2.5g of chitosan powder, dissolving in 4mL of formic acid and 196mL of deionized water, wherein the mass fraction of the chitosan solution is 2.5%, placing the mixed solution on an electric stirrer, stirring for 1.5h at normal temperature, and continuously stirring until the chitosan powder is completely dissolved to obtain a uniform chitosan solution for later use. And then preparing 10g/L sodium periodate solution by using a 500ml volumetric flask, transferring the obtained gel into a brown bottle containing a certain volume of sodium periodate solution, oscillating at a low speed at 23 ℃, oxidizing for 12 hours in a dark place, washing and soaking the reacted gel for multiple times by using deionized water, removing the unreacted sodium periodate solution until the pH value is 7, soaking the obtained composite gel into the prepared chitosan solution for 24 hours, taking out the composite gel, and washing the gel for multiple times by using the deionized water until the pH value is neutral. And placing the prepared cellulose-graphene oxide-chitosan ternary composite gel into a refrigerator with the temperature of-15 ℃ for precooling for 12h, taking out the cellulose-graphene oxide-chitosan ternary composite gel, performing freeze-drying in a freeze-drying machine at the drying temperature of-60 ℃ for 54h under the pressure of 3pa, and drying to obtain the cellulose-graphene oxide-chitosan ternary composite aerogel. The material had a specific surface area of 233m2/g, a porosity of 84.0% and a density of 0.083g/cm 3.
Claims (10)
1. A preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel comprises the following specific steps:
(1) preparation of cellulose-graphene oxide gel
Dissolving cellulose with an alkaline urine solution to obtain a cellulose solution, adding a graphene oxide aqueous solution, uniformly stirring, placing the cellulose solution into a refrigerator with the temperature of-30 to-15 ℃ for precooling for 10-12 h, taking out the cellulose solution for melting to the temperature of-14 to-10 ℃, stirring to obtain a transparent mixed solution of the cellulose and the graphene oxide with a large number of bubbles, placing the mixed solution into a centrifuge for centrifugation, taking out a transparent clear solution, pouring the clear solution into a container, placing the container into a coagulating bath, and standing for 6-48 h to obtain cellulose-graphene oxide gel;
(2) preparation of cellulose-graphene oxide-chitosan gel
Weighing chitosan powder, dissolving the chitosan powder in an acid solution, and stirring to obtain a chitosan solution; immersing the cellulose-graphene oxide gel obtained in the step (1) into a sodium periodate solution in a brown bottle, oscillating at a low speed at 20-30 ℃, oxidizing in the dark for 12-24 h, washing the gel after reaction by deionized water, immersing the gel into a prepared chitosan solution for soaking for 12-24 h, taking out, and washing by deionized water until the pH value is 6.5-7.5;
(3) preparation of cellulose-graphene oxide-chitosan aerogel
And (3) putting the prepared cellulose-graphene oxide-chitosan ternary composite hydrogel into a freeze dryer for drying, and drying to obtain the cellulose-graphene oxide-chitosan ternary composite aerogel.
2. The method according to claim 1, wherein the cellulose in the step (1) is one of cotton pulp, short-staple cotton or microcrystalline cellulose; the alkali is one of sodium hydroxide or lithium hydroxide; the urine is urea or thiourea.
3. The method according to claim 1, wherein the cellulose solution in step (1) contains cellulose, alkali, urine and deionized water at 2.9-5.7%, 4.3-20.5%, 11.6-20.5% and 56.5-78.67% by weight respectively.
4. The preparation method according to claim 1, wherein the concentration of the graphene oxide aqueous solution in the step (1) is 2 to 5 mg/ml; the volume ratio of the cellulose dissolving solution to the graphene oxide aqueous solution is 4-56: 1.
5. the preparation method according to claim 1, wherein the stirring speed of the transparent mixed solution of the cellulose and the graphene oxide with a large number of bubbles obtained by stirring in the step (1) is 2000-5000 rpm, and the stirring time is 20-50 min; the centrifugal speed of the centrifugal machine is 7000-10000 r/min, and the centrifugal time is 3-7 min.
6. The method according to claim 1, wherein the coagulation bath in the step (1) is one of ethanol, methanol and acetone coagulation baths.
7. The method according to claim 1, wherein the acid in step (2) is one or more of hydrochloric acid, nitric acid, formic acid, or acetic acid.
8. The preparation method according to claim 1, wherein the mass concentration of the sodium periodate in the step (2) is 10 to 12 g/L.
9. The method according to claim 1, wherein the concentration of the chitosan solution in the step (2) is 10 to 20 mg/ml.
10. The preparation method according to claim 1, wherein the freeze-drying temperature in the step (3) is-60 to-40 ℃, the pressure is 1 to 10Pa, and the drying time is 48 to 54 hours.
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