CN109174023B - Nano-cellulose crosslinked graphene/chitosan aerogel and preparation method and application thereof - Google Patents
Nano-cellulose crosslinked graphene/chitosan aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nano-cellulose cross-linked graphene/chitosan aerogel, and a preparation method and application thereof, and belongs to the field of dye adsorption of aerogels. The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan. The nano-cellulose crosslinked graphene/chitosan aerogel disclosed by the invention has excellent adsorption performance of graphene and chitosan, avoids using a toxic cross-linking agent, can exert the advantage of large specific surface area of nano-cellulose, is easy to realize separation from a water body, does not cause secondary pollution, is an environment-friendly novel adsorption material, and is proved by organic dye adsorption performance tests to have a good adsorption effect on congo red and amino black, the removal rate is up to more than 92%, the adsorption process is fast, the nano-cellulose crosslinked graphene/chitosan aerogel is easy to separate after adsorption, and the nano-cellulose crosslinked graphene/chitosan aerogel has a good application prospect.
Description
Technical Field
The invention relates to a nano-cellulose cross-linked graphene/chitosan aerogel, and a preparation method and application thereof, and belongs to the field of dye adsorption of aerogels.
Background
With the rapid development of the domestic printing and dyeing industry, a large amount of sewage containing dye is discharged into the water environment to cause water pollution, the water safety of China is seriously threatened, a plurality of water treatment methods are provided, and the adsorption method is a simple and efficient method. Aerogels are often used as adsorption for the treatment of sewage due to their own high specific surface area and ultra-high pore volume rate.
In the prior art, a chinese patent with an issued publication number of CN105566659B discloses a graphene oxide/nanocellulose aerogel, which is prepared by preparing hydrogel from nanocellulose and graphene oxide through a hydrothermal reaction, and further performing freeze drying. The aerogel can be used for removing organic dye molecules or other impurities in sewage to purify the sewage, but the aerogel can enhance the adsorption capacity of the aerogel on organic pollutants only by virtue of hydroxyl and carboxyl groups on a graphene molecular chain and oxygen-containing groups on a cellulose chain, and has poor adsorption effect; and no chemical bond crosslinking exists between the graphene oxide and the polymer matrix, so that the stability is low, the graphene oxide is easy to migrate from an adsorbent system to a water system in the adsorption swelling process, the adsorption effect of the adsorption material is reduced, and the nano toxicity of the graphene oxide can be caused.
Disclosure of Invention
The invention aims to provide the nano-cellulose cross-linked graphene/chitosan aerogel which is high in stability and good in organic pollutant adsorption effect.
The invention also provides a preparation method of the crosslinked graphene/chitosan aerogel of the fiber and application of the crosslinked graphene/chitosan aerogel of the fiber in removing organic dyes in wastewater.
In order to achieve the above purpose, the technical scheme adopted by the nanocellulose crosslinked graphene/chitosan aerogel provided by the invention is as follows:
a nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan.
The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan, the chitosan is used as a natural water-soluble biodegradable high polymer material and has the characteristics of low price, rich sources and reproducibility, a molecular chain of the nano-cellulose crosslinked graphene/chitosan aerogel contains a large amount of amino and hydroxyl, and the amino and hydroxyl can act with organic dyes through electrostatic attraction and hydrogen bond action force, so that the adsorption effect is improved. The graphene is a nano material with a monoatomic layer structure, has a large specific surface area, contains organic groups after being modified, and improves the water dispersibility of the graphene; in addition, the modifier of the graphene contains a large number of amino groups, and can react with aldehyde groups of dialdehyde nano-cellulose, so that chemical crosslinking of graphene oxide sheets and polymer groups is realized, and the stability and the adsorption performance of the aerogel are improved. Dialdehyde nano-cellulose keeps the advantage of large specific surface area of nano-cellulose, the obtained aerogel has excellent adsorption performance of graphene and chitosan, the use of toxic cross-linking agents is avoided, the advantage of large specific surface area of nano-cellulose can be exerted, the separation from water is easy to realize, no secondary pollution is caused, the aerogel is an environment-friendly novel adsorption material, and the novel adsorption material has high research and practical application values. The adsorption performance test on organic dye shows that the nano-cellulose crosslinked graphene/chitosan aerogel disclosed by the invention has a good adsorption effect on Congo red and amino black, the removal rate is up to more than 92%, the adsorption process is fast, the adsorption is easy to separate, and the application prospect is good.
The dialdehyde nanocellulose adopted by the invention is not particularly limited, and the dialdehyde nanocellulose in the prior art can be used in the invention. Preferably, the dialdehyde nano-crystalline cellulose is dialdehyde nano-crystalline cellulose.
Preferably, the dialdehyde nanofiber is prepared by a method comprising the following steps: mixing the nano-cellulose and sodium periodate according to the mass ratio of 1: 1-5, and reacting in a dark place to obtain the sodium periodate.
Preferably, the reaction time is 4-24 h. The nanocellulose is nanocrystalline cellulose (NCC).
Preferably, the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide is 1: 0.25-3.
Preferably, the mass ratio of the dialdehyde nano cellulose to the chitosan is 1: 0.5-3.
Preferably, the temperature of the mixed crosslinking is 15-40 ℃. Further preferably, the temperature of the hybrid crosslinking is room temperature.
Preferably, the time of mixing and crosslinking is 2-8 h.
The amino-modified graphene oxide adopted by the invention is not particularly limited, and the amino-modified graphene oxide in the prior art is all suitable for the technical scheme of the invention. Preferably, the amino-modified graphene oxide is polyethyleneimine-modified graphene oxide.
Preferably, the amino-modified graphene oxide is prepared by a method comprising the following steps: mixing the amino modifier with graphite oxide according to the mass ratio of 1-8: 1, and reacting at 85-90 ℃ for 4-6 hours to obtain the modified graphite. More preferably, the mass ratio of the amino modifier to the graphene oxide is 2-5.5: 1.
Preferably, the amine-based modifier is polyethyleneimine.
The preparation method of the nano-cellulose crosslinked graphene/chitosan aerogel adopts the technical scheme that:
a preparation method of the nano-cellulose crosslinked graphene/chitosan aerogel comprises the following steps: and (3) reacting and drying the mixed solution of the dialdehyde nano-cellulose, the amino modified graphene oxide and the chitosan in a mould to obtain the modified amino modified graphene oxide chitosan.
The preparation method of the nano-cellulose crosslinked graphene/chitosan aerogel has the advantages of simple preparation process and easily obtained raw materials, the obtained aerogel has good adsorption effect on Congo red and amino black, the removal rate reaches more than 92%, and the adsorption process block is easy to separate after adsorption and has good application prospect.
Preferably, the drying is freeze drying. The freeze drying time is 12-48 h.
Preferably, the mixed solution is prepared by a method comprising the following steps: providing a composite solution of dialdehyde nano-cellulose and amino modified graphene oxide; and adding the composite solution into a chitosan solution, and uniformly mixing to obtain the chitosan/chitosan composite material.
Preferably, the mass fraction of the dialdehyde nano cellulose in the composite solution is 0.2-2%.
Preferably, the mass fraction of chitosan in the chitosan solution is 0.02-3%. Further preferably, the mass fraction of chitosan in the chitosan solution is 3%.
Preferably, the chitosan solution is obtained by dissolving chitosan in an aqueous acetic acid solution. The mass fraction of acetic acid in the acetic acid aqueous solution is 0.5-2%.
The application of the nano-cellulose crosslinked graphene/chitosan aerogel in the aspect of removing organic dyes in wastewater adopts the following technical scheme:
an application of the nano-cellulose cross-linked graphene/chitosan aerogel in removing organic dyes in wastewater.
The nano-cellulose crosslinked graphene/chitosan aerogel disclosed by the invention has a good adsorption effect on organic dyes, particularly has a Congo red removal rate of more than 92%, and has a wide application prospect in the aspect of printing and dyeing wastewater treatment.
Drawings
FIG. 1 is an XRD pattern of the nanocellulose before and after oxidation in example 1; in the figure, NCC is nanocrystalline cellulose; DAC dialdehyde nano-cellulose;
fig. 2 is an SEM image of the nanocellulose-crosslinked graphene/chitosan aerogel of example 1.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
The nanocellulose employed in the specific embodiment is nanocrystalline cellulose (NCC).
Example 1
The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan; the amino modified graphene oxide is polyethyleneimine modified graphene oxide; the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide to the chitosan is 3:1: 3.
The preparation method of the nanocellulose crosslinked graphene/chitosan aerogel comprises the following steps:
1) dissolving 1.2g of sodium periodate in 20mL of distilled water, adding 1M sulfuric acid to adjust the pH value to 4, then adding 0.6g of nano-cellulose to react for 4 hours at 40 ℃ in a dark place, filtering, washing, and removing the unreacted sodium periodate to obtain dialdehyde nano-cellulose;
2) mixing 1g of polyethyleneimine and 0.2g of graphene oxide, heating at 90 ℃ for reaction for 4 hours, filtering with a membrane, and removing unreacted polyethyleneimine to obtain polyethyleneimine-modified graphene oxide;
3) dispersing dialdehyde nano-cellulose in distilled water to prepare dialdehyde nano-cellulose solution with the mass fraction of 2%; dispersing polyethyleneimine modified graphene oxide in distilled water to prepare an amino modified graphene oxide solution with the mass fraction of 1%;
mixing a dialdehyde nano cellulose solution and an amino modified graphene oxide solution according to the mass ratio of 3:1 of dialdehyde nano cellulose to polyethyleneimine modified graphene oxide, and performing ultrasonic treatment to obtain a uniform composite solution;
4) weighing 0.6g of chitosan, adding the chitosan into 19.4g of 1% acetic acid solution, and heating at 50 ℃ to completely dissolve the chitosan to obtain a chitosan solution;
dropwise adding the composite solution obtained in the step 3) into a chitosan solution according to the mass ratio of 3:1:3 of the dialdehyde nanocellulose, the amino modified graphene oxide and the chitosan, and uniformly stirring and mixing to obtain a dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution;
5) and (3) filling the dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution into a mold, performing crosslinking reaction for 4 hours at room temperature, and then freeze-drying for 12 hours to obtain the dialdehyde nanocellulose crosslinked graphene/chitosan composite aerogel.
XRD tests were performed on the nanocellulose used in this example and the dialdehyde nanocellulose prepared in step 1) of the above preparation method, respectively, and the obtained XRD patterns are shown in fig. 1, from which it can be seen that nanocellulose NCC exhibits diffraction peaks at 2 θ ═ 16 ° and 2 θ ═ 22 °, indicating that the sample is cellulose type I crystal. In contrast, the above diffraction peak intensity of dialdehyde nanocellulose DAC was greatly reduced, indicating that the crystallinity of DAC was significantly reduced due to the conversion of hydroxyl groups in NCC to aldehyde groups. Due to the generation of aldehyde groups in DAC, the chemical crosslinking of dialdehyde nano-cellulose, modified graphene oxide and chitosan is facilitated.
The nano-cellulose crosslinked graphene/chitosan aerogel of the present embodiment is subjected to SEM test, and the obtained SEM photograph is shown in fig. 2, and as can be seen from fig. 2, the obtained aerogel presents a three-dimensional network structure and has a large specific surface area. The graphene oxide lamellae are uniformly dispersed in the polymer matrix and do not significantly agglomerate.
Example 2
The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan; the amino modified graphene oxide is polyethyleneimine modified graphene oxide; the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide to the chitosan is 2:1: 3.
The preparation method of the nanocellulose crosslinked graphene/chitosan aerogel comprises the following steps:
1) dissolving 1.0g of sodium periodate in 20mL of distilled water, adding 1M sulfuric acid to adjust the pH value to 4, then adding 0.6g of nano-cellulose to react for 6 hours at 40 ℃ in a dark place, filtering, washing, and removing the unreacted sodium periodate to obtain dialdehyde nano-cellulose;
2) mixing 1g of polyethyleneimine and 0.3g of graphene oxide, heating at 90 ℃ for reaction for 4 hours, filtering with a membrane, and removing unreacted polyethyleneimine to obtain polyethyleneimine-modified graphene oxide;
3) dispersing dialdehyde nano-cellulose in distilled water to prepare 1% dialdehyde nano-cellulose solution by mass fraction;
dispersing polyethyleneimine modified graphene oxide in distilled water to prepare an amino modified graphene oxide solution with the mass fraction of 1%;
mixing a dialdehyde nano cellulose solution and an amino modified graphene oxide solution according to the mass ratio of 2:1 of dialdehyde nano cellulose to polyethyleneimine modified graphene oxide, and performing ultrasonic treatment to obtain a uniform composite solution;
4) weighing 0.9g of chitosan, adding the chitosan into 29.1g of 1% acetic acid solution, and heating at 50 ℃ to completely dissolve the chitosan to obtain a chitosan solution;
dropwise adding the composite solution obtained in the step 3) into a chitosan solution according to the mass ratio of the dialdehyde nanocellulose, the amino modified graphene oxide and the chitosan of 2:1:3, and uniformly stirring and mixing to obtain a dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution;
5) and (3) filling the dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution into a mold, performing crosslinking reaction for 6 hours at room temperature, and then freeze-drying for 20 hours to obtain the dialdehyde nanocellulose crosslinked graphene/chitosan composite aerogel.
Example 3
The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan; the amino modified graphene oxide is polyethyleneimine modified graphene oxide; the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide to the chitosan is 1:2: 3.
The preparation method of the nanocellulose crosslinked graphene/chitosan aerogel comprises the following steps:
1) dissolving 1.0g of sodium periodate in 20mL of distilled water, adding 1M sulfuric acid to adjust the pH value to 4, then adding 0.5g of nano-cellulose, reacting for 8 hours at 40 ℃ in a dark place, filtering, washing, and removing the unreacted sodium periodate to obtain dialdehyde nano-cellulose;
2) mixing 4g of polyethyleneimine and 1g of graphene oxide, heating at 90 ℃ for reaction for 4 hours, filtering with a membrane, and removing unreacted polyethyleneimine to obtain polyethyleneimine-modified graphene oxide;
3) dispersing dialdehyde nano-cellulose in distilled water to prepare dialdehyde nano-cellulose solution with the mass fraction of 2%;
dispersing polyethyleneimine modified graphene oxide in distilled water to prepare an amino modified graphene oxide solution with the mass fraction of 1%;
mixing a dialdehyde nano cellulose solution and an amino modified graphene oxide solution according to the mass ratio of 1:2 of the dialdehyde nano cellulose to the polyethyleneimine modified graphene oxide, and performing ultrasonic treatment to obtain a uniform composite solution;
4) weighing 1.5g of chitosan, adding the chitosan into 48.5g of 1% acetic acid solution, and heating at 50 ℃ to completely dissolve the chitosan to obtain a chitosan solution;
dropwise adding the composite solution obtained in the step 3) into a chitosan solution according to the mass ratio of 1:2:3 of the dialdehyde nano-cellulose, the amino modified graphene oxide and the chitosan, and uniformly stirring and mixing to obtain a dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution;
5) and (3) filling the dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution into a mold, performing crosslinking reaction for 8 hours at room temperature, and then freeze-drying for 40 hours to obtain the dialdehyde nanocellulose crosslinked graphene/chitosan composite aerogel.
Example 4
The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan; the amino modified graphene oxide is polyethyleneimine modified graphene oxide; the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide to the chitosan is 1:3: 3.
The preparation method of the nanocellulose crosslinked graphene/chitosan aerogel comprises the following steps:
1) dissolving 2.5g of sodium periodate in 40mL of distilled water, adding 1M sulfuric acid to adjust the pH value to 4, then adding 0.5g of nano-cellulose to react for 24 hours at 40 ℃ in a dark place, filtering, washing, and removing the unreacted sodium periodate to obtain dialdehyde nano-cellulose;
2) mixing 8g of polyethyleneimine and 1.5g of graphene oxide, heating at 85 ℃ for reaction for 6 hours, filtering with a membrane, and removing unreacted polyethyleneimine to obtain polyethyleneimine-modified graphene oxide;
3) dispersing dialdehyde nano cellulose in distilled water to prepare 1.5 percent dialdehyde nano cellulose solution;
dispersing polyethyleneimine modified graphene oxide in distilled water to prepare an amino modified graphene oxide solution with the mass fraction of 1%;
mixing a dialdehyde nano cellulose solution and an amino modified graphene oxide solution according to the mass ratio of 1:3 of the dialdehyde nano cellulose to the polyethyleneimine modified graphene oxide, and performing ultrasonic treatment to obtain a uniform composite solution;
4) weighing 1.5g of chitosan, adding the chitosan into 48.5g of 1% acetic acid solution, and heating at 50 ℃ to completely dissolve the chitosan to obtain a chitosan solution;
dropwise adding the composite solution obtained in the step 3) into a chitosan solution according to the mass ratio of 1:3:3 of the dialdehyde nano-cellulose, the amino modified graphene oxide and the chitosan, and uniformly stirring and mixing to obtain a dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution;
5) and (3) filling the dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution into a mold, performing crosslinking reaction for 2 hours at room temperature, and then freeze-drying for 48 hours to obtain the dialdehyde nanocellulose crosslinked graphene/chitosan composite aerogel.
Example 5
The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan; the amino modified graphene oxide is polyethyleneimine modified graphene oxide; the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide to the chitosan is 4:1: 12.
The preparation method of the nanocellulose crosslinked graphene/chitosan aerogel comprises the following steps:
1) dissolving 2.0g of sodium periodate in 40mL of distilled water, adding 1M sulfuric acid to adjust the pH value to 4, then adding 0.5g of nano-cellulose to react for 16h at 40 ℃ in a dark place, filtering, washing, and removing the unreacted sodium periodate to obtain dialdehyde nano-cellulose;
2) mixing 0.5g of polyethyleneimine and 0.125g of graphene oxide, heating at 85 ℃ for reaction for 5 hours, filtering with a membrane, and removing unreacted polyethyleneimine to obtain polyethyleneimine-modified graphene oxide;
3) dispersing dialdehyde nano-cellulose in distilled water to prepare dialdehyde nano-cellulose solution with the mass fraction of 2%;
dispersing polyethyleneimine modified graphene oxide in distilled water to prepare an amino modified graphene oxide solution with the mass fraction of 1%;
mixing a dialdehyde nano cellulose solution and an amino modified graphene oxide solution according to the mass ratio of 4:1 of dialdehyde nano cellulose to polyethyleneimine modified graphene oxide, and performing ultrasonic treatment to obtain a uniform composite solution;
4) weighing 1.5g of chitosan, adding the chitosan into 48.5g of 1% acetic acid solution, and heating at 50 ℃ to completely dissolve the chitosan to obtain a chitosan solution;
dropwise adding the composite solution obtained in the step 3) into the chitosan solution according to the mass ratio of 4:1:12 of the dialdehyde nano-cellulose, the amino modified graphene oxide and the chitosan, and uniformly stirring and mixing to obtain a dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution;
5) and (3) filling the dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution into a mold, performing crosslinking reaction for 5 hours at room temperature, and then freeze-drying for 30 hours to obtain the dialdehyde nanocellulose crosslinked graphene/chitosan composite aerogel.
Example 6
The nano-cellulose crosslinked graphene/chitosan aerogel is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan; the amino modified graphene oxide is polyethyleneimine modified graphene oxide; the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide to the chitosan is 1:1: 0.5.
The preparation method of the nanocellulose crosslinked graphene/chitosan aerogel comprises the following steps:
1) dissolving 2.0g of sodium periodate in 40mL of distilled water, adding 1M sulfuric acid to adjust the pH value to 4, then adding 1.0g of nano-cellulose to react for 16h at 40 ℃ in a dark place, filtering, washing, and removing the unreacted sodium periodate to obtain dialdehyde nano-cellulose;
2) mixing 2.0g of polyethyleneimine and 1.0g of graphene oxide, heating at 85 ℃ for 5 hours for reaction, filtering with a membrane, and removing unreacted polyethyleneimine to obtain polyethyleneimine-modified graphene oxide;
3) dispersing dialdehyde nano-cellulose in distilled water to prepare dialdehyde nano-cellulose solution with the mass fraction of 4%;
dispersing polyethyleneimine modified graphene oxide in distilled water to prepare an amino modified graphene oxide solution with the mass fraction of 4%;
mixing a dialdehyde nano cellulose solution and an amino modified graphene oxide solution according to the mass ratio of 1:1 of dialdehyde nano cellulose to polyethyleneimine modified graphene oxide, and performing ultrasonic treatment to obtain a uniform composite solution;
4) weighing 0.5g of chitosan, adding the chitosan into 19.4g of 2% acetic acid solution, and heating at 50 ℃ to completely dissolve the chitosan to obtain chitosan solution;
dropwise adding the composite solution obtained in the step 3) into a chitosan solution according to the mass ratio of 1:1:0.5 of the dialdehyde nano-cellulose, the amino modified graphene oxide and the chitosan, and uniformly stirring and mixing to obtain a dialdehyde nano-cellulose/amino modified graphene oxide/chitosan mixed solution;
5) and (3) filling the dialdehyde nanocellulose/amino modified graphene oxide/chitosan mixed solution into a mold, performing crosslinking reaction for 5 hours at room temperature, and then freeze-drying for 30 hours to obtain the dialdehyde nanocellulose crosslinked graphene/chitosan composite aerogel.
Examples of the experiments
The experimental example detects the adsorption performance of the nano-cellulose cross-linked graphene/chitosan aerogel obtained in examples 1-6 on organic dyes. The detection method comprises the following steps: accurately weighing 5mg of sample, adding into 10mL of Congo red solution of 100mg/mL, and placing into a water bath constant temperature oscillator (30 deg.C, 100 r.min)-1) After the solution was oscillated and the adsorption equilibrium was reached, the absorbance of the dye solution was measured at a wavelength of 497nm by an ultraviolet spectrophotometer, the amount of adsorbed congo red was determined by calculating the dye concentration, and the congo red removal rate was calculated, and the results are shown in table 1.
Table 1 results of detecting adsorption properties of cellulose crosslinked graphene oxide/chitosan aerogels obtained in examples 1 to 6
As can be seen from table 1, the nanocellulose crosslinked graphene/chitosan composite aerogel has a good adsorption effect on congo red. The removal rate of Congo red in the experimental examples 1-6 is more than 92%. Experimental results show that the nano-cellulose crosslinked graphene/chitosan composite aerogel obtained by the invention has a good adsorption effect on Congo red dye, and has a wide application prospect in the field of printing and dyeing wastewater adsorbents.
Claims (6)
1. A nanometer cellulose crosslinked graphene/chitosan aerogel for removing organic dyes in wastewater is characterized in that: prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan;
the mass ratio of the dialdehyde nano-cellulose to the amino modified graphene oxide is 1: 0.25-3;
the mass ratio of the dialdehyde nano cellulose to the chitosan is 1: 0.5-3;
the amino modified graphene oxide is polyethyleneimine modified graphene oxide;
the amino modified graphene oxide is prepared by adopting a method comprising the following steps: mixing polyethyleneimine and graphene oxide according to the mass ratio of 2-5.5: 1;
the preparation method of the nano-cellulose crosslinked graphene/chitosan aerogel comprises the following steps: reacting and drying a mixed solution of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan in a mold to obtain the modified graphene oxide chitosan nano-composite material;
the mixed solution is prepared by adopting a method comprising the following steps: providing a composite solution of dialdehyde nano-cellulose and amino modified graphene oxide; and adding the composite solution into a chitosan solution, and uniformly mixing to obtain the chitosan/chitosan composite material.
2. The nanocellulose-crosslinked graphene/chitosan aerogel for the removal of organic dyes from wastewater as claimed in claim 1, characterized in that: the dialdehyde nano-crystalline cellulose is dialdehyde nano-crystalline cellulose.
3. The nanocellulose-crosslinked graphene/chitosan aerogel for the removal of organic dyes from wastewater as claimed in claim 1, characterized in that: the temperature of the mixed crosslinking is 15-40 ℃.
4. A method for preparing nano-cellulose cross-linked graphene/chitosan aerogel as claimed in claim 1, wherein: the method comprises the following steps: reacting and drying a mixed solution of dialdehyde nano-cellulose, amino modified graphene oxide and chitosan in a mold to obtain the modified graphene oxide chitosan nano-composite material;
the mixed solution is prepared by adopting a method comprising the following steps: providing a composite solution of dialdehyde nano-cellulose and amino modified graphene oxide; and adding the composite solution into a chitosan solution, and uniformly mixing to obtain the chitosan/chitosan composite material.
5. The preparation method of the nano-cellulose crosslinked graphene/chitosan aerogel according to claim 4, characterized in that: the mass fraction of chitosan in the chitosan solution is 0.02-3%.
6. Use of the nanocellulose-crosslinked graphene/chitosan aerogel of claim 1 for the removal of organic dyes from wastewater.
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Application publication date: 20190111 Assignee: Henan Pengxi Technology Co.,Ltd. Assignor: HENAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2022980028227 Denomination of invention: A nano cellulose cross-linked graphene/chitosan aerogel and its preparation method and application Granted publication date: 20210716 License type: Exclusive License Record date: 20230111 |