CN113731380B - MXene/graphene/polyethyleneimine composite aerogel and preparation method and application thereof - Google Patents
MXene/graphene/polyethyleneimine composite aerogel and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of adsorption materials, and provides a preparation method of MXene/graphene/polyethyleneimine composite aerogel. The invention adopts MXene to improve the mechanical strength of the gel, and utilizes graphene oxide to be reduced into graphene in the hydrothermal reaction to promote the formation of gel materials, thereby improving the specific surface area of the aerogel. In addition, as the MXene and the graphene are both in a layered two-dimensional structure, the aerogel has the characteristic of large specific surface area, and the specific surface area of the aerogel is further improved. The composite aerogel prepared by the method has high specific surface area, and the adsorption performance of the aerogel on uranyl ions and heavy metal ions is further improved by the active sites provided by MXene and graphene.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to an MXene/graphene/polyethyleneimine composite aerogel and a preparation method and application thereof.
Background
With the rapid development of the global nuclear power industry, a large amount of uranium-containing wastewater such as uranium mining wastewater, uranium refining and nuclear fuel manufacturing wastewater, reactor operation wastewater, post-treatment wastewater of reactor fuel, wastewater generated by radioisotope production, and wastewater generated by factories and research departments using radioisotope, etc. is discharged in various major production links of the nuclear power industry and in the application of radioisotope. In addition, the salt is sunk in the sea water, the sea water desalinization can generate waste water rich in uranyl ions, and other industrial waste water also contains heavy metal ions. In the prior art, adsorption materials are generally adopted to treat and recycle uranium-rich wastewater or other industrial wastewater to extract uranium elements or heavy metal ions, so that the problems of scarcity of uranyl resources and water pollution caused by uranyl ions and heavy metal ions are solved. Among the adsorbent materials, porous materials are a very effective type of adsorbent, and therefore, development of porous materials having excellent adsorption properties is important.
Polyethyleneimine aerogel is a porous solid material with a three-dimensional network structure, has many excellent physicochemical properties, such as higher specific surface area, large pore volume, low density and the like, but the specific surface area of the polyethyleneimine aerogel is still limited for the adsorption of uranyl ions and heavy metal ions, and the specific surface area of the polyethyleneimine aerogel needs to be further increased.
Disclosure of Invention
In view of the above, the invention provides an MXene/graphene/polyethyleneimine composite aerogel, and a preparation method and application thereof. The composite aerogel provided by the invention has a high specific surface area, is in a porous structure, and has large adsorption capacity on uranyl ions and heavy metal ions.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the MXene/graphene/polyethyleneimine composite aerogel is characterized by comprising the following steps of:
mixing an MXene material and water, and sequentially carrying out ultrasonic treatment and centrifugation to obtain an MXene suspension;
mixing the MXene suspension, graphene oxide and polyethyleneimine for hydrothermal reaction to obtain an MXene/graphene/polyethyleneimine composite hydrogel;
and drying the MXene/graphene/polyethyleneimine composite hydrogel to obtain the MXene/graphene/polyethyleneimine composite aerogel.
Preferably, the MXene material is Ti 3 C 2 T x 、Ti 2 CT x 、Nb 2 CT x 、V 2 CT x And Cr (V) 2 CT x One or more of them, wherein T x is-OH and-F.
Preferably, the concentration of the MXene suspension is 10-50 mg/mL; the mass ratio of the MXene, the graphene oxide and the polyethyleneimine in the MXene suspension is 1:1:0.2 to 1.
Preferably, the preparation method of the MXene material comprises the following steps: and mixing MAX phase ceramic powder and lithium fluoride-hydrochloric acid mixed solution for reaction to obtain the MXene material.
Preferably, the material of the MAX phase ceramic powder is Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC and Cr 2 One or more of AlC; the concentration of lithium fluoride in the lithium fluoride-hydrochloric acid mixed solution is 12mol/L; the concentration of hydrochloric acid in the lithium fluoride-hydrochloric acid mixed solution is 9mol/L; the mass ratio of the MAX phase ceramic powder to the lithium fluoride is 0.5-2: 1.
preferably, the temperature of the hydrothermal reaction is 100-200 ℃, and the time of the hydrothermal reaction is 1-12 h.
Preferably, the rotational speed of the centrifugation is 2000-6000 rpm, and the time of the centrifugation is 5-10 min.
Preferably, the drying comprises prefreezing and freeze-drying which are performed sequentially; the pre-freezing temperature is-20 ℃ to-196 ℃, and the pre-freezing time is 0.5 to 6 hours; the temperature of the freeze drying is-45 ℃ to 40 ℃, and the pressure of the freeze drying is 2 Pa to 50Pa; the freeze drying time is 6-48 h.
The invention provides the MXene/graphene/polyethyleneimine composite aerogel obtained by the preparation method, and the density of the MXene/graphene/polyethyleneimine composite aerogel is 0.05-0.5 g/cm 3 The specific surface area of the MXene/graphene/polyethyleneimine composite aerogel is 100-1600 m 2 /g。
The invention provides an MXene/graphene/polyethyleneimine composite aerogel prepared by the preparation method or application of the MXene/graphene/polyethyleneimine composite aerogel in the field of uranyl ion and heavy metal ion adsorption.
The invention provides a preparation method of MXene/graphene/polyethyleneimine composite aerogel, which comprises the following steps: mixing an MXene material and water, and sequentially carrying out ultrasonic treatment and centrifugation to obtain an MXene suspension; mixing the MXene suspension, graphene oxide and polyethyleneimine for hydrothermal reaction to obtain an MXene/graphene/polyethyleneimine composite hydrogel; and drying the MXene/graphene/polyethyleneimine composite hydrogel to obtain the MXene/graphene/polyethyleneimine composite aerogel. The invention adopts MXene to improve the mechanical strength of gel, and uses graphene oxide to be reduced into graphene in hydrothermal reaction to promote the formation of gel materials, and as the graphene oxide contains a large amount of oxygen-containing functional groups, the oxygen-containing functional groups are reduced after the reduction in the hydrothermal reaction, the hydrophilicity of graphene oxide sheets is weakened, so that the sheets are mutually close to each other for crosslinking, and finally the material is gelled, thereby improving the specific surface area of aerogel. In addition, as the MXene and the graphene are both in a layered two-dimensional structure, the aerogel has the characteristic of large specific surface area, and the specific surface area of the aerogel is further improved.
The composite aerogel with high specific surface area is prepared by mixing MXene, graphene and polyethyleneimine for reaction. Meanwhile, the active sites provided by the MXene and the graphene further improve the adsorption performance of the aerogel on uranyl ions and heavy metal ions. The results of the examples show that the prepared composite aerogel is in a porous state and has a specific surface area of 1600m at most 2 And/g, the adsorption quantity of uranyl ions is 220mg/g, and the adsorption performance is excellent.
Drawings
FIG. 1 shows the Ti as obtained in example 1 3 C 2 T x Scanning electron microscope pictures of the graphene/polyethyleneimine composite aerogel;
FIG. 2 shows the Ti obtained in example 1 3 C 2 T x Graphene/polyethyleneScanning electron microscope pictures (a) of the alkene imine composite aerogel and a titanium element distribution diagram (b) corresponding to the scanning electron microscope pictures;
FIG. 3 shows the Ti as obtained in example 1 3 C 2 T x The adsorption quantity of the graphene/polyethyleneimine composite aerogel to uranyl ions and heavy metal ions;
FIG. 4 shows Nb obtained in example 2 2 CT x Scanning electron microscope pictures of the graphene/polyethyleneimine composite aerogel;
FIG. 5 is a diagram of Nb obtained in example 2 2 CT x The adsorption quantity of the graphene/polyethyleneimine composite aerogel to uranyl ions and heavy metal ions;
FIG. 6 is V obtained in example 3 2 CT x Scanning electron microscope pictures of the graphene/polyethyleneimine composite aerogel;
FIG. 7 is V obtained in example 3 2 CT x Nitrogen adsorption and desorption curves of the graphene/polyethyleneimine composite aerogel;
FIG. 8 is a drawing of Cr obtained in example 4 2 CT x Scanning electron microscope pictures of the graphene/polyethyleneimine composite aerogel;
FIG. 9 is a drawing of Cr obtained in example 4 2 CT x Adsorption quantity of uranyl ions and heavy metal ions by the graphene/polyethyleneimine composite aerogel.
Detailed Description
The invention provides a preparation method of MXene/graphene/polyethyleneimine composite aerogel, which comprises the following steps:
mixing an MXene material and water, and sequentially carrying out ultrasonic treatment and centrifugation to obtain an MXene suspension;
mixing the MXene suspension, graphene oxide and polyethyleneimine for hydrothermal reaction to obtain an MXene/graphene/polyethyleneimine composite hydrogel;
and drying the MXene/graphene/polyethyleneimine composite hydrogel to obtain the MXene/graphene/polyethyleneimine composite aerogel.
The preparation raw materials used in the invention are all commercially available unless otherwise specified.
In the present invention, the MXene material may be used as a commercially available product or prepared by itself. The invention preferably adopts a self-preparation mode to obtain the MXene material. In the present invention, the preparation method of the MXene material preferably includes: and mixing MAX phase ceramic powder and lithium fluoride-hydrochloric acid mixed solution for reaction to obtain the MXene material. In the present invention, the material of the MAX phase ceramic powder is preferably Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC and Cr 2 One or more of AlC, more preferably Ti 3 AlC 2 、Ti 2 AlC and V 2 AlC. The MAX phase ceramic selected by the invention is low in price, and the prepared MXene has larger specific surface area, thereby being beneficial to improving the adsorption performance of the composite aerogel.
In the invention, the concentration of lithium fluoride in the lithium fluoride-hydrochloric acid mixed solution is preferably 12mol/L; the concentration of hydrochloric acid in the lithium fluoride-hydrochloric acid mixed solution is preferably 9mol/L; the mass ratio of the MAX phase ceramic powder to the lithium fluoride is preferably 0.5-2: 1, more preferably 1 to 2:1, most preferably 1:1. the mass ratio of the MAX phase ceramic powder to the lithium fluoride is limited in the range, which is favorable for the full etching of the MAX phase, and the MXene with larger specific surface area is obtained, so that the adsorption performance of the composite aerogel is improved. In the present invention, the reaction is preferably carried out under magnetic stirring, the temperature of the reaction is preferably 30 to 50 ℃, more preferably 40 ℃, and the time of the reaction is preferably 6 to 48 hours, more preferably 24 hours.
After the reaction is finished, the invention preferably carries out centrifugal separation and washing on the obtained product feed liquid in sequence to obtain an MXene material; the washing detergent is preferably deionized water, and the MXene material is obtained after washing until supernatant is nearly neutral.
In the present invention, the MXene material is preferably Ti 3 C 2 T x 、Ti 2 CT x 、Nb 2 CT x 、V 2 CT x And Cr (V) 2 CT x One or more of them, more preferably Ti 3 C 2 T x 、Ti 2 CT x And V 2 CT x Wherein T is x is-OH and-F. Compared with similar products sold in the market, the MXene material prepared by the method has lower cost and better dispersibility.
The MXene material and water are mixed and then sequentially subjected to ultrasonic treatment and centrifugation to obtain the MXene suspension. The invention adopts an ultrasonic mode to peel the MXene material, and adopts a centrifugal mode to separate the unpeeled MXene material. In the present invention, the number of layers of the MXene in the MXene suspension is preferably not higher than 5, more preferably not higher than 3, and most preferably 1. In the present invention, the rotational speed of the centrifugation is preferably 2000 to 6000rpm, more preferably 5000rpm, and the time of the centrifugation is preferably 5 to 10min, more preferably 10min. In the present invention, after the MXene suspension is obtained, the concentration of the MXene suspension is preferably adjusted to 10 to 50mg/mL, more preferably to 10 to 30mg/mL, and even more preferably to 10 to 20mg/mL by using deionized water. The concentration of the MXene suspension is preferably limited in the above range, which is beneficial to preparing high-quality composite aerogel materials. If the concentration of the MXene suspension is too low, the solids content is too small, which is insufficient to form a gel; if the concentration of the MXene suspension is too high, the MXene dispersibility becomes poor, the suspension stability becomes poor, and the gel formation is also adversely affected.
After the MXene suspension is obtained, the MXene suspension, graphene oxide and polyethyleneimine are mixed for hydrothermal reaction, so that the MXene/graphene/polyethyleneimine composite hydrogel is obtained. The invention preferably mixes the MXene suspension, graphene oxide and polyethylenimine by ultrasonic agitation. In the present invention, the mass ratio of the MXene, graphene oxide and polyethyleneimine in the MXene suspension is preferably 1:1:0.2 to 1, more preferably 1:1:0.5 to 1, more preferably 1:1:0.6 to 1, most preferably 1:1:0.8. in the invention, the mass ratio of the MXene, the graphene oxide and the polyethyleneimine is preferably limited in the range, which is favorable for improving the specific surface area of the composite aerogel and the adsorption performance of the composite aerogel on uranyl ions and heavy metal ions. Meanwhile, the self-assembly effect of the graphene oxide in the hydrothermal process promotes the formation of a gel material, and in the process, the graphene oxide is reduced to graphene.
In the present invention, the hydrothermal reaction is preferably performed in a hydrothermal kettle; the temperature of the hydrothermal reaction is preferably 100 to 200 ℃, more preferably 120 to 180 ℃, and even more preferably 130 to 150 ℃; the hydrothermal reaction time is 1 to 12 hours, more preferably 2 to 10 hours, still more preferably 8 to 10 hours. The hydrothermal reaction conditions are preferably limited in the above range, which is beneficial to the dispersion of MXene and graphene in the gel material and the formation of the gel material with high specific surface area, and is beneficial to the safe performance of the reaction.
After the MXene/graphene/polyethyleneimine composite hydrogel is obtained, the MXene/graphene/polyethyleneimine composite hydrogel is dried to obtain the MXene/graphene/polyethyleneimine composite aerogel. In the present invention, the drying preferably includes prefreezing and freeze-drying performed sequentially; the pre-freezing temperature is preferably-20 ℃ to-196 ℃, more preferably-50 ℃ to-196 ℃, and even more preferably-100 ℃ to-196 ℃. The pre-freezing time is preferably 0.5 to 6 hours, more preferably 1 to 4 hours, and even more preferably 1 to 2 hours; the temperature of the freeze drying is preferably-45-40 ℃, more preferably-45-0 ℃, and even more preferably-45-35 ℃; the pressure of the freeze-drying is preferably 2 to 50Pa, more preferably 2 to 10Pa, and still more preferably 2 to 5Pa; the time for the freeze-drying is preferably 6 to 48 hours, more preferably 6 to 24 hours, and still more preferably 12 to 16 hours. The invention adopts a pre-freeze drying mode to reduce the sheet stacking of MXene and graphene in the drying process, and can better maintain the porous form of gel, thereby further improving the adsorption performance of the composite aerogel.
The invention also provides the MXene/graphene/polyethyleneimine composite aerogel prepared by the technical scheme. In the invention, the density of the MXene/graphene/polyethyleneimine composite aerogel is preferably 0.05-0.5 g/cm 3 More preferably 0.05 to 0.1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The specific surface area of the MXene/graphene/polyethyleneimine composite aerogel is preferably 100-1600 m 2 Preferably 500 to 1000m 2 /g。
The invention also provides application of the MXene/graphene/polyethyleneimine composite aerogel obtained by the technical scheme in the fields of uranyl ion and heavy metal ion adsorption. In the present invention, the aerogel powder is preferably added to the wastewater solution for adsorption. In the invention, the feed liquid ratio of the powder to the wastewater is preferably 1mg/30mL, the wastewater is preferably the wastewater containing uranyl ions and/or heavy metal ions, and the heavy metal ions are preferably one or more of mercury ions, lead ions and copper ions; the concentration of uranyl ions and heavy metal ions in the wastewater solution is preferably 10-200 mg/L, more preferably 50-100 mg/L; the time of the adsorption is preferably 3 to 12 hours, more preferably 6 to 9 hours; the adsorption is preferably carried out under shaking conditions.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention.
Example 1
1.6g of lamellar MAX phase Ti 3 AlC 2 Adding ceramic powder into 20.0mL hydrochloric acid (9.0M) solution with 2.0g lithium fluoride dissolved therein, magnetically stirring at 35deg.C for reaction for 24 hr, and washing the reaction product until the supernatant is nearly neutral to obtain Ti 3 C 2 T x (T x are-OH and-F) materials. The obtained Ti 3 C 2 T x Dispersing the material in deionized water, ultrasonic stripping, centrifuging at 6000rpm for 10min, and removing Ti not stripped at the bottom 3 C 2 T x Nano-sheet to obtain Ti 3 C 2 T x The nanoplatelets stabilize the suspension.
Regulation of Ti 3 C 2 T x The concentration of the stable suspension of the nano-sheets is 20mg/mL, and the concentration is 10mLTi 3 C 2 T x 200mg of graphene oxide and 200mg of polyethyleneimine are added into the stable nanosheet suspension, and then the mixture is subjected to ultrasonic treatment and stirring to be fully mixed, so that a mixed solution is obtained. Placing the mixed solution in a hydrothermal kettle, and performing hydrothermal reaction at 120 ℃ for 12 hours to form Ti 3 C 2 T x Graphene/polyethyleneimine composite hydrogel. Pre-freezing the obtained composite hydrogel for 0.5h at the liquid nitrogen temperature of minus 196 ℃,then vacuum freeze drying at 25deg.C under 10Pa for 48 hr to obtain Ti 3 C 2 T x Graphene/polyethyleneimine composite aerogel.
X-ray photoelectron spectrometer (Thermo ESCALAB 250 XI) Ti of Siemens technology company of America 3 C 2 T x (T x The content of-OH and-F) in the-OH and-F) materials was measured to be 0.5% by weight and 1.2% by weight, respectively.
Mass-volume method is adopted for Ti 3 C 2 T x The density of the graphene/polyethyleneimine composite aerogel is measured to be 0.05g/cm 3 . Adopts nitrogen adsorption and desorption method to absorb Ti 3 C 2 T x Specific surface area of graphene/polyethyleneimine composite aerogel is measured and is 1600m 2 /g。
FIG. 1 shows the Ti as obtained in example 1 3 C 2 Scanning electron micrographs of Tx/graphene/polyethyleneimine composite aerogel materials, as can be seen in FIG. 1, ti 3 C 2 Tx/graphene/polyethyleneimine composite aerogel has a rich porous structure.
FIG. 2 shows the Ti obtained in example 1 3 C 2 T x Scanning electron microscope photo (a) of graphene/polyethyleneimine composite aerogel and corresponding titanium element distribution diagram (b), wherein titanium element is uniformly distributed in the aerogel, which shows that Ti 3 C 2 T x The nano-sheets are uniformly distributed in the composite gel.
FIG. 3 shows the Ti as obtained in example 1 3 C 2 T x Adsorption quantity of uranyl ions and heavy metal ions by the graphene/polyethyleneimine composite aerogel. The adsorption experiment comprises the following specific steps: 50mL of the wastewater solution in which the uranyl ion, mercury ion, lead ion and copper ion concentrations were 50mg/L was accurately measured in a 150mL Erlenmeyer flask, 5mg of aerogel powder was added to the wastewater solution, and then the Erlenmeyer flask was placed in an oscillator and oscillated at room temperature for 6 hours. After the oscillation is finished, measuring uranyl ions, mercury ions and lead in the adsorbed wastewater by utilizing an inductively coupled plasma spectrumThe concentrations of the ions and copper ions were calculated from the difference in the concentrations of the ions and the mass of the aerogel powder, and the adsorption amount of each ion by the aerogel was calculated. As can be seen from FIG. 3, ti 3 C 2 The adsorption capacity of the Tx/graphene/polyethyleneimine composite aerogel for uranyl ions is 220mg/g, and the adsorption capacity for heavy metal ions such as mercury ions, lead ions and copper ions is 150mg/g, 130mg/g and 80mg/g respectively, so that the composite aerogel has good adsorption performance.
Example 2
The MAX phase is Nb 2 AlC. The other reaction conditions were the same as in example 1, and Nb was finally obtained 2 CT x (T x is-OH and-F)/graphene/polyethyleneimine composite aerogel.
Measurement of Nb using X-ray photoelectron spectrometer (model Thermo ESCALAB 250 XI) from Siemens technology Co 2 CT x (T x The content of-OH and-F) in the-OH and-F) materials was measured to be 0.8% by weight and 1.5% by weight, respectively.
Mass-to-volume method for Nb 2 CT x The density of the graphene/polyethyleneimine composite aerogel is measured and is 0.12g/cm 3 . Nb is adsorbed and desorbed by adopting a nitrogen adsorption and desorption method 2 CT x Specific surface area of graphene/polyethyleneimine composite aerogel is measured, and the specific surface area is 940m 2 /g。
FIG. 4 is Nb obtained in example 2 2 CT x Scanning electron micrographs of graphene/polyethyleneimine composite aerogel, as can be seen from FIG. 4, nb 2 CT x The graphene/polyethyleneimine composite aerogel has a rich porous structure.
The Nb obtained in example 2 was obtained in the same manner as in example 1 2 CT x The adsorption performance of the graphene/polyethyleneimine composite aerogel was tested, and the results are shown in FIG. 5, and FIG. 5 is Nb obtained in example 2 2 The adsorption amount of the CTx/graphene/polyethyleneimine composite aerogel to uranyl ions and heavy metal ions can be seen from FIG. 5, nb 2 The adsorption capacity of CTx/graphene/polyethyleneimine composite aerogel to uranyl ions is 208mg +.g, the adsorption amounts of the mercury ions, lead ions, copper ions and other heavy metal ions are 133mg/g, 114mg/g and 56mg/g respectively, and the adsorption performance is good.
Example 3
The MAX phase is V 2 AlC. The other reaction conditions were the same as in example 1, and V was finally obtained 2 CT x (T x is-OH and-F)/graphene/polyethyleneimine composite aerogel.
Measurement of Nb using X-ray photoelectron spectrometer (model Thermo ESCALAB 250 XI) from Siemens technology Co 2 CT x (T x The content of-OH and-F) in the-OH and-F) materials was measured to be 0.6% by weight and 1.4% by weight, respectively.
The density of the composite aerogel obtained in example 3 was measured by the mass-volume method and was 0.5g/cm 3 . The specific surface area of the composite aerogel obtained in example 3 was measured by a nitrogen adsorption/desorption method, and found to be 770m 2 /g。
FIG. 6 is V obtained in example 3 2 CT x (T x Scanning electron micrographs of-OH and-F)/graphene/polyethyleneimine composite aerogel, as can be seen in FIG. 6, V 2 CT x The graphene/polyethyleneimine composite aerogel has a rich porous structure.
FIG. 7 is V obtained in example 3 2 CT x The nitrogen adsorption and desorption curve of the graphene/polyethyleneimine composite aerogel can be calculated according to the nitrogen adsorption isotherm, and V 2 CT x The specific surface area of the graphene/polyethyleneimine composite aerogel is 770m 2 /g。
Example 4
The MAX phase is Cr 2 AlC. The other reaction conditions were the same as in example 1, and Cr was finally obtained 2 CT x (T x is-OH and-F)/graphene/polyethyleneimine composite aerogel.
Measurement of Nb using X-ray photoelectron spectrometer (model Thermo ESCALAB 250 XI) from Siemens technology Co 2 CT x (T x of-OH and-F) materialsF content, measured as 0.7% and 1.2% by weight, respectively.
The density of the composite aerogel obtained in example 4 was measured by the mass-volume method and was 0.28g/cm 3 . The specific surface area of the composite aerogel obtained in example 4 was measured by a nitrogen adsorption/desorption method, and found to be 100m 2 /g。
FIG. 8 is a drawing of Cr obtained in example 4 2 CT x (T x Scanning electron micrographs of-OH and-F)/graphene/polyethyleneimine composite aerogel, as can be seen in FIG. 8, cr 2 CT x (T x is-OH and-F / The graphene/polyethyleneimine composite aerogel has a rich porous structure.
Cr was obtained in example 4 by the method of example 1 2 CT x (T x The adsorption performance of the-OH and-F)/graphene/polyethyleneimine composite aerogel was tested, and the results are shown in FIG. 9, and FIG. 9 is Cr obtained in example 4 2 CT x /(T x Adsorption amount of uranyl ion and heavy metal ion by-OH and-F) graphene/polyethyleneimine composite aerogel, as can be seen from FIG. 9, the obtained Cr 2 CT x The adsorption capacity of the graphene/polyethyleneimine composite aerogel for uranyl ions is 188mg/g respectively, and the adsorption capacity of the graphene/polyethyleneimine composite aerogel for heavy metal ions such as mercury ions, lead ions and copper ions is 113mg/g, 108mg/g and 66mg/g respectively, so that the graphene/polyethyleneimine composite aerogel has good adsorption performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the MXene/graphene/polyethyleneimine composite aerogel is characterized by comprising the following steps of:
mixing an MXene material and water, and sequentially carrying out ultrasonic treatment and centrifugation to obtain an MXene suspension;
mixing the MXene suspension, graphene oxide and polyethyleneimine for hydrothermal reaction to obtain an MXene/graphene/polyethyleneimine composite hydrogel;
drying the MXene/graphene/polyethyleneimine composite hydrogel to obtain MXene/graphene/polyethyleneimine composite aerogel;
the concentration of the MXene suspension is 10-50 mg/mL; the mass ratio of the MXene, the graphene oxide and the polyethyleneimine in the MXene suspension is 1:1: 0.2-1;
the temperature of the hydrothermal reaction is 100-200 ℃, and the time of the hydrothermal reaction is 1-12 h;
the drying comprises pre-freezing and freeze-drying which are sequentially carried out; the pre-freezing temperature is-20 to-196 ℃, and the pre-freezing time is 0.5 to 6 hours; the temperature of the freeze drying is-45-40 ℃, and the pressure of the freeze drying is 2-50 Pa; and the freeze drying time is 6-48 h.
2. The method according to claim 1, wherein the MXene material is Ti 3 C 2 T x 、Ti 2 CT x 、Nb 2 CT x 、V 2 CT x And Cr (V) 2 CT x One or more of them, wherein T x is-OH and-F.
3. The method of manufacturing according to claim 1, wherein the method of manufacturing the MXene material comprises the steps of: and mixing MAX phase ceramic powder and lithium fluoride-hydrochloric acid mixed solution for reaction to obtain the MXene material.
4. The method according to claim 3, wherein the MAX-phase ceramic powder is made of Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC and Cr 2 One or more of AlC; the concentration of lithium fluoride in the lithium fluoride-hydrochloric acid mixed solution is 12mol/L; the concentration of hydrochloric acid in the lithium fluoride-hydrochloric acid mixed solution is 9mol/L; the MAX phase ceramic powder and the fluorinationThe mass ratio of lithium is 0.5-2: 1.
5. the preparation method according to claim 1, wherein the rotational speed of the centrifugation is 2000-6000 rpm, and the centrifugation time is 5-10 min.
6. The MXene/graphene/polyethyleneimine composite aerogel obtained by the preparation method according to any one of claims 1 to 5, wherein the density of the MXene/graphene/polyethyleneimine composite aerogel is 0.05 to 0.5g/cm 3 The specific surface area of the MXene/graphene/polyethyleneimine composite aerogel is 100-160 m 2 /g。
7. The application of the MXene/graphene/polyethyleneimine composite aerogel in the field of uranyl ion and heavy metal ion adsorption in claim 6.
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