CN112473630A - Composite graphene chitosan aerogel and preparation method and application thereof - Google Patents
Composite graphene chitosan aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of aerogel adsorption materials, in particular to a composite graphene chitosan aerogel and a preparation method and application thereof. The composite graphene chitosan aerogel is prepared by mixing and crosslinking chitosan aerogel, graphene and KH 560; the mass ratio of the chitosan aerogel to the graphene to the KH560 is 1: 0.08-0.3: 0.05-0.3. The composite graphene chitosan aerogel disclosed by the invention has good mechanical strength and acid resistance, is easy to recover and can be repeatedly used; the invention also provides a preparation method and application thereof, which are used for adsorbing hexavalent chromium ions in wastewater, the maximum adsorption capacity reaches 166mg/g, the selectivity is extremely high, and when other metal ions coexist, the maximum adsorption capacity reaches 150 mg/g.
Description
Technical Field
The invention relates to the technical field of aerogel adsorption materials, in particular to a composite graphene chitosan aerogel and a preparation method and application thereof.
Background
As a heavy metal pollutant, metal chromium ions receive more and more attention in the field of environmental protection in recent years. Especially hexavalent chromium cr (vi), is easily dissolved in water, has very high toxicity, and causes great damage to the human body, such as lung cancer, impaired renal function, liver function, and the like. Chemical precipitation, membrane separation, electrolytic separation, adsorption and the like are respectively used for removing Cr (VI) in the wastewater, wherein the adsorption method is a widely applied and efficient method. The commonly used adsorbents mainly include activated carbon, magnetic particles, organic polymers, etc., which are mainly in the form of powder and fine particles, and have weak adsorption capacity and are not easy to separate and regenerate, thus increasing the cost of water treatment.
The aerogel has rich pore structure and is easy to separate from water, so the aerogel has good adsorption application prospect, can be biodegraded and regenerated, and is a sustainable development biomaterial. Wherein chitosan aerogel is the biomass aerogel that high efficiency adsorbed metal ion, but chitosan aerogel has two shortcomings: the mechanical strength is relatively low and easily decomposed in an acidic environment.
Cr (vi) is an acidic ion, and therefore requires good adsorption performance of the adsorbent under low pH conditions. The ability to enhance the acid environment resistance of chitosan aerogels by cross-linking them is an effective way to improve their performance. The conventional crosslinking agent is seriously polluted and can destroy the porous structure of the aerogel, and the application is limited.
Patent CN201811032482.3 discloses a nano-cellulose crosslinked graphene/chitosan aerogel, which is prepared by mixing and crosslinking dialdehyde nano-cellulose, amino modified graphene oxide and chitosan, and has the advantages of excellent adsorption performance of graphene and chitosan, and the use of toxic crosslinking agents is avoided, so that the nano-cellulose aerogel has the advantage of large specific surface area, is easy to separate from a water body, does not cause secondary pollution, and is an environment-friendly novel adsorption material. However, the nano-cellulose crosslinked graphene/chitosan aerogel is mainly used for removing organic dyes in wastewater, has a good adsorption effect on Congo red and amino black, has a removal rate of more than 92%, is poor in acid resistance, and is poor in adsorption effect when applied to a low pH condition.
Patent CN201811337239.2 discloses a preparation method of cellulose-graphene oxide-chitosan ternary composite aerogel, which comprises dissolving cellulose by using a low-temperature alkaline-urea circulating freeze thawing method, obtaining cellulose-graphene oxide composite gel by using a sol-gel method, oxidizing hydroxyl in cellulose into aldehyde groups by using sodium periodate as an oxidant, further reacting with a chitosan solution to obtain cellulose-graphene oxide-chitosan ternary composite gel, and obtaining the ternary composite aerogel by combining a freeze drying technology. The addition of chitosan and graphene oxide not only enhances the mechanical properties of the material, but also improves the specific surface area and porosity of the aerogel material, but also has poor acid resistance and poor adsorption effect when applied to a low pH condition.
Disclosure of Invention
The invention aims to provide the composite graphene chitosan aerogel which has good mechanical strength and acid resistance, is easy to recover and can be repeatedly used; the invention also provides a preparation method and application thereof, which are used for adsorbing hexavalent chromium ions in wastewater, the maximum adsorption capacity reaches 166mg/g, the selectivity is extremely high, and when other metal ions coexist, the maximum adsorption capacity reaches 150 mg/g.
The composite graphene chitosan aerogel is prepared by mixing and crosslinking chitosan aerogel, graphene and KH 560.
The mass ratio of the chitosan aerogel to the graphene to the KH560 is 1: 0.08-0.3: 0.05-0.3.
The KH560 with too little dosage can cause insufficient crosslinking, reduce the adsorption capacity of the aerogel and reduce the service life; excessive usage can block the pore channels of the aerogel and cover the adsorption sites.
The graphene consumption is too small, the prepared composite graphene aerogel is insufficient in mechanical strength, weak in adsorption capacity and short in service life; too much graphene can cause that much graphene has no aerogel distribution, and the adsorption capacity is not improved.
The preparation method of the composite graphene chitosan aerogel comprises the following steps:
(1) dispersing chitosan aerogel powder in an acid solution, and fully stirring to obtain a dispersion liquid A;
(2) adding graphene into the dispersion liquid A, and performing ultrasonic dispersion to obtain a dispersion liquid B;
(3) adding KH560 into the dispersion liquid B, and heating to 50-100 ℃ for reaction to obtain composite hydrogel;
(4) and cooling the composite hydrogel at room temperature, and then putting the cooled composite hydrogel into a freeze drying box for freeze drying to obtain the composite graphene chitosan aerogel.
In the step (1), the acid solution is nitric acid or hydrochloric acid, the pH value is 1-6, and the temperature is 20-30 ℃; the mass ratio of the chitosan aerogel powder to the acid solution is 1: 100-200.
In the step (2), the ultrasonic time is 1-5 h.
In the step (3), the reaction time is 5-10 h, and the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the surface of the graphene are realized.
In the step (4), the freeze drying time is 5-10 h, and the temperature is-30 to-50 ℃.
The composite graphene chitosan aerogel disclosed by the invention is mainly used for adsorbing hexavalent chromium ions in wastewater.
According to the invention, gamma- (2, 3-glycidoxy) -propyl trimethoxy silane (KH560) is used as a cross-linking agent, KH560 has the advantages of environmental protection, and meanwhile, the pore structure of the aerogel can be maintained, so that the acid resistance of the chitosan aerogel can be effectively improved, the stability of the chitosan aerogel in an acid environment can be enhanced, and the chitosan aerogel can be prevented from being hydrolyzed.
In addition, the mechanical strength of chitosan is lower, the mechanical strength of the chitosan is improved by adding graphene, the graphene has rich specific surface and high mechanical strength, rich functional groups are ideal materials for preparing the composite chitosan aerogel, but the graphene is well dispersed in water and is not easy to recover.
Compared with the prior art, the invention has the following beneficial effects:
(1) aiming at the defects of the chitosan aerogel, the stability of the chitosan aerogel in an acid environment is improved through KH560 crosslinking, the mechanical strength of the chitosan aerogel is improved through self-assembled graphene, and a macroporous structure can be provided, the prepared graphene chitosan aerogel takes the chitosan aerogel as a main material, the graphene is taken as a supporting material, and KH560 is taken as a crosslinking agent, so that the chitosan aerogel is green and environment-friendly, has good mechanical strength and acid resistance, is easy to recover, and can be repeatedly used;
(2) the preparation method is simple, the chitosan aerogel and KH560 are subjected to a crosslinking reaction on the surface of the graphene, and a condensation reaction with the graphene, and then the composite graphene chitosan aerogel can be obtained through simple freeze drying and self-assembly, so that the large-scale production is facilitated;
(3) the composite graphene chitosan aerogel prepared by the invention is used for adsorbing hexavalent chromium ions in wastewater, has excellent performance, has extremely high selectivity, and can still reach 150mg/g when other metal ions coexist, and the maximum adsorption capacity can reach 166 mg/g.
Drawings
Fig. 1 is a scanning electron microscope image of the composite graphene chitosan aerogel prepared in example 1;
fig. 2 is an infrared spectrum of the composite graphene Chitosan Aerogel (CA) and Graphene (GO), chitosan aerogel (CS) prepared in example 1.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The composite graphene chitosan aerogel is prepared by the following method:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.2g of KH560, adding into the dispersion liquid B, heating to 50 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
Example 2
The composite graphene chitosan aerogel is prepared by the following method:
(1) dispersing 1.5g of chitosan aerogel powder in hydrochloric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.2g of KH560, adding into the dispersion liquid B, heating to 50 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
Example 3
The composite graphene chitosan aerogel is prepared by the following method:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 4, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.2g of KH560, adding into the dispersion liquid B, heating to 50 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
Example 4
The composite graphene chitosan aerogel is prepared by the following method:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.1g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.2g of KH560, adding into the dispersion liquid B, heating to 50 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
Example 5
The composite graphene chitosan aerogel is prepared by the following method:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.1g of KH560, adding into the dispersion liquid B, heating to 50 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
Example 6
The composite graphene chitosan aerogel is prepared by the following method:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.2g of KH560, adding into the dispersion liquid B, heating to 100 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
Example 7
The composite graphene chitosan aerogel is prepared by the following method:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.2g of KH560, adding into the dispersion liquid B, heating to 50 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of-30 ℃ to obtain the composite graphene Chitosan Aerogel (CA).
Comparative example 1
Compared with the embodiment 1, the method for preparing the composite chitosan aerogel without adding graphene comprises the following steps:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.2g of KH560, adding into the dispersion A, heating to 50 ℃, and reacting for 10h to realize the crosslinking reaction of the KH560 and the chitosan aerogel, so as to obtain the composite hydrogel;
(3) and (3) cooling the composite hydrogel for 3 hours at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5 hours at the temperature of 50 ℃ below zero to obtain the composite chitosan aerogel.
Comparative example 2
Compared with the example 1, the preparation method of the composite graphene chitosan aerogel without adding KH560 comprises the following steps:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) heating the dispersion liquid B to 50 ℃, and reacting for 10 hours to obtain composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3 hours at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5 hours at the temperature of 50 ℃ below zero to obtain the composite graphene chitosan aerogel.
Comparative example 3
In this comparative example, compared to example 1, using cellulose as a cross-linking agent instead of KH560, a composite chitosan aerogel was prepared as follows:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100mL) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3)0.2g of microcrystalline cellulose, 0.5g of potassium hydroxide and 1g of urea were added to 10ml of deionized water, and stirred at room temperature for 1 hour to obtain solution C.
(4) Mixing the dispersion liquid B and the solution C, heating to 50 ℃, and reacting for 10 hours to realize the cross-linking reaction of KH560 and the chitosan aerogel and the condensation reaction on the surface of GO to obtain composite hydrogel;
(5) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
Comparative example 4
Compared with the embodiment 1, the method for preparing the composite graphene chitosan aerogel by increasing the dosage of KH560 comprises the following steps:
(1) dispersing 1.5g of chitosan aerogel powder in a nitric acid solution (100ml) with the pH value of 2, and fully dispersing the chitosan aerogel powder by stirring and ultrasound to obtain a dispersion liquid A;
(2) weighing 0.3g of graphene, adding the graphene into the dispersion liquid A, and carrying out ultrasonic stirring for 3 hours to completely disperse the graphene in the dispersion liquid A to obtain a dispersion liquid B;
(3) weighing 0.7g of KH560, adding into the dispersion liquid B, heating to 50 ℃, and reacting for 10h to realize the cross-linking reaction of the KH560 and the chitosan aerogel and the condensation reaction on the GO surface to obtain the composite hydrogel;
(4) and (3) cooling the composite hydrogel for 3h at room temperature, then transferring the composite hydrogel into a freeze dryer, and freeze-drying the composite hydrogel for 5h at the temperature of 50 ℃ below zero to obtain the composite graphene Chitosan Aerogel (CA).
The composite aerogels prepared in examples 1 to 7 and comparative examples 1 to 4 were subjected to a hexavalent chromium metal ion adsorption test by the following method:
dispersing 100mg of composite aerogel in 200mL of hexavalent chromium metal ion aqueous solution (the initial concentration of hexavalent chromium is 200mg/L), adsorbing for 3h at the temperature of 30 ℃, regulating and controlling the pH value of the solution by using dilute hydrochloric acid, and inspecting the adsorption performance of the composite aerogel on hexavalent chromium metal ions under different pH conditions.
In addition, is arranged atAdding other metal ions (Cu) into hexavalent chromium metal ion aqueous solution (hexavalent chromium initial concentration is 200mg/L)2+、Cd2+、Cr3+At a concentration of 200mg/L) and an anion (PO 4)3-、SO42-) And adsorbing for 3h at the temperature of 30 ℃ to investigate the adsorption performance of the composite aerogel on hexavalent chromium metal ions when other metal ions exist.
Regenerating the used Composite Aerogel (CA), and inspecting the adsorption performance of the regenerated Composite Aerogel (CA), wherein the method specifically comprises the following steps: the used CA was added to 100mL of 0.1M NaOH solution, stirred for 20min, dried, and the above procedure was repeated until no hexavalent chromium ions were detected in the solution. Each sample was used repeatedly 6 times to examine its adsorption performance.
The concentration of the remaining hexavalent chromium metal ions in the aqueous solution was detected by an ultraviolet spectrophotometer, and the adsorption amount of the composite aerogel was obtained by calculation, with the results shown in table 1.
TABLE 1 results of adsorption property test of composite aerogels prepared in examples 1 to 7 and comparative examples 1 to 4
Claims (10)
1. The invention discloses a composite graphene chitosan aerogel, which is characterized in that: is prepared by mixing and crosslinking chitosan aerogel, graphene and KH 560.
2. The composite graphene chitosan aerogel of claim 1, wherein: the mass ratio of the chitosan aerogel to the graphene to the KH560 is 1: 0.08-0.3: 0.05-0.3.
3. A method for preparing the composite graphene chitosan aerogel according to any one of claims 1 to 2, which is characterized in that: the method comprises the following steps:
(1) dispersing chitosan aerogel powder in an acid solution, and fully stirring to obtain a dispersion liquid A;
(2) adding graphene into the dispersion liquid A, and performing ultrasonic dispersion to obtain a dispersion liquid B;
(3) adding KH560 into the dispersion liquid B, and heating to 50-100 ℃ for reaction to obtain composite hydrogel;
(4) and cooling the composite hydrogel at room temperature, and then putting the cooled composite hydrogel into a freeze drying box for freeze drying to obtain the composite graphene chitosan aerogel.
4. The preparation method of the composite graphene chitosan aerogel according to claim 3, characterized in that: in the step (1), the acid solution is nitric acid or hydrochloric acid, and the pH value is 1-6.
5. The preparation method of the composite graphene chitosan aerogel according to claim 3, characterized in that: in the step (1), the mass ratio of the chitosan aerogel powder to the acid solution is 1: 100-200.
6. The preparation method of the composite graphene chitosan aerogel according to claim 3, characterized in that: in the step (1), the temperature of the acid solution is 20-30 ℃.
7. The preparation method of the composite graphene chitosan aerogel according to claim 3, characterized in that: in the step (2), the ultrasonic time is 1-5 h.
8. The preparation method of the composite graphene chitosan aerogel according to claim 3, characterized in that: in the step (3), the reaction time is 5-10 h.
9. The preparation method of the composite graphene chitosan aerogel according to claim 3, characterized in that: in the step (4), the freeze drying time is 5-10 h, and the temperature is-30 to-50 ℃.
10. Use of the composite graphene chitosan aerogel according to any one of claims 1-2, wherein: used for absorbing hexavalent chromium ions in the wastewater.
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