CN113428862A - MXene/graphene oxide three-dimensional heterojunction aerogel and preparation method thereof - Google Patents
MXene/graphene oxide three-dimensional heterojunction aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to MXene/graphene oxide three-dimensional heterojunction aerogel and a preparation method thereof, wherein MXene and Graphene Oxide (GO) are combined according to a specific mass ratio, and a synthesis method of MXene/graphene oxide three-dimensional heterojunction aerogel material is formed by freeze drying.
Description
The technical field is as follows:
the invention relates to a preparation method of a three-dimensional material, in particular to a method for efficiently and stably preparing MXene/graphene oxide three-dimensional heterojunction aerogel by controlling the mass ratio of MXene to Graphene Oxide (GO), and belongs to the field of material preparation.
Background art:
MXene is a two-dimensional transition metal carbide or nitride, which is formed by HCl and LiFEtching agent for etching Ti3AlC2To obtain Ti3C2TxThis compares directly etching Ti with HF3AlC2Is safer and has simpler operation steps. The MXene material prepared by etching is composed of a single layer of Ti3C2TxStacked, the overall shape is kept the same as that of the raw material, and Ti in the particles3C2TxThe laminated layers are stacked in an accordion shape, the space between MXene material layers is usually 2.0-2.5nm, and the laminated layers can be peeled into a single piece by intercalation expanding the space between the layers or ultrasonic treatment. MXene is similar to graphene in electrochemical performance, has extremely high volume capacitance and reversibility, and is excellent in mechanical strength, oxidation resistance, hydrophilicity, chemical stability and the like due to special element composition and surface functional groups.
MXene and GO are both two-dimensional structures, and the three-dimensional structure aerogel has larger surface area and interlayer spacing because of more holes, and the mutual intercalation of MXene and GO can form a multilayer net structure to be beneficial to electron transfer, so the MXene has wider application, and in addition, functional groups such as-OH and the like exist on the surface of MXene, and the MXene is electronegative and has good reducibility.
The conductivity of the product of the three-dimensional GO assembly in the forming process can be improved, the characteristics of the GO assembly are combined with the structural characteristics of the GO assembly, the GO assembly has excellent performance in practical application, and the two-dimensional GO can become the three-dimensional GO assembly under corresponding conditions, so that the GO can be further developed in the application of the green energy field. Therefore, much attention has been paid to the study on the compounding of GO assemblies with other materials.
MXene and GO are compounded to form a three-dimensional heterojunction structure, the three-dimensional heterojunction structure has good performance in the electrocatalysis and adsorption processes, and the MXene/GO three-dimensional structure is constructed, so that the combination of the MXene and the GO gives the composite material more excellent performance. The three-dimensional MXene/GO takes GO as a carrier, and a typical graphene-like material MXene is loaded on the surface of the three-dimensional MXene/GO, so that the composite material has the excellent performances of both MXene and GO and is superior to the performances of pure MXene and GO.
The invention content is as follows:
the invention has considered the problems of complex preparation, low efficiency and the like in the prior art, and aims to provide a simple and effective preparation method of a three-dimensional heterojunction aerogel material, namely a method for preparing MXene/graphene oxide three-dimensional heterojunction aerogel by mutually doping MXene and GO according to a specific mass ratio.
The technical scheme adopted by the invention is that MXene and GO composite MXene/graphene oxide three-dimensional heterojunction aerogel materials with different proportions are obtained by mixing the prepared MXene solution and GO solution with known concentration according to specific mass ratios of 1:16, 1:8 and 1:4 and then freeze-drying.
Further, the preparation method of the MXene/graphene oxide three-dimensional heterojunction aerogel material comprises the following steps:
step 1, preparation of MXene suspension: preparing hydrochloric acid with a certain concentration, pouring the prepared hydrochloric acid solution into a polytetrafluoroethylene beaker, placing the beaker on a heating type magnetic stirrer for stirring, and weighing LiF and Ti with a certain mass ratio3AlC2And slowly adding the mixture into a polytetrafluoroethylene beaker, covering a preservative film, and starting heating and stirring. And after the reaction is finished, closing the instrument, naturally cooling the instrument to room temperature, then adding distilled water, transferring the diluted test solution into a beaker, standing for several hours, taking a clean centrifugal tube, pouring supernatant into the centrifugal tube, adding water into the precipitate again, performing ultrasonic treatment for half an hour, centrifuging the mixture to form uniform suspension, sucking the suspension out by using a pipette, putting the suspension into a clean centrifugal bottle, performing centrifugal washing on the suspension by using water, and measuring the pH of the solution by using a pH test paper until the solution is neutral.
And 2, carrying out ultrasonic treatment on the existing 2mg/mL graphene oxide aqueous solution.
Step 3, preparing MXene/graphene oxide three-dimensional heterojunction aerogel: taking a clean centrifugal tube for later use, diluting the prepared MXene suspension, and performing ultrasonic treatment to obtain a uniform MXene solution; mixing MXene and GO in a clean centrifugal tube according to a specific mass ratio, performing ultrasonic treatment to fully mix the MXene and GO, and freezing. And finally, putting the frozen MXene/GO mixed solution into a freeze dryer for freeze drying to obtain the MXene/graphene oxide three-dimensional heterojunction aerogel.
In the step 1: the heating temperature is 40 ℃, the reaction time is 12 hours, the rotating speed of a centrifugal machine is set to 4000r/min, the Ti is weighed after being washed for about 5 to 6 times3AlC2And LiF in a mass ratio of about 1:1.6 to 1: 2.
In the step 3: the freeze drying time is 24-30 h.
The invention has the beneficial effects that: the preparation process has good stability and repeatability, the prepared composite material has large specific surface area, the multi-layer net structure is also favorable for electron transfer, and the composite material also has good reducibility and has good application in the aspects of heat insulation, energy storage, heavy metal recycling and the like.
Description of the drawings:
fig. 1 is an SEM image of an MXene/graphene oxide three-dimensional heterojunction aerogel prepared when the mass ratio of MXene to GO is 1: 8.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the present invention more prominent, the present invention will be described in further detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
step 1, taking 7.5mL of 9mol/L hydrochloric acid, preparing 10mL of 6.75mol/L hydrochloric acid solution, pouring the prepared hydrochloric acid solution into a polytetrafluoroethylene beaker, putting the beaker on a heating type magnetic stirrer for stirring, weighing 0.8g of LiF and 0.5g of Ti3AlC2And slowly adding the mixture into a polytetrafluoroethylene beaker, covering a preservative film, and starting heating and stirring. After the reaction is completed, the instrument is closed and allowed to cool naturally to room temperature. Adding distilled water, transferring the diluted sample solution into a beaker, standing for several hours, taking a clean centrifuge tube, pouring supernatant into the centrifuge tube, adding water again into the precipitate, performing ultrasonic treatment for half an hour, centrifuging to obtain uniform suspension, sucking out the suspension by using a pipette, putting the suspension into a clean centrifuge bottle, performing centrifugal washing on the suspension by using water, and measuringIts pH until the suspension is neutral.
And 2, carrying out ultrasonic treatment on the existing 2mg/mL graphene oxide aqueous solution.
Step 3, preparing MXene/graphene oxide three-dimensional heterojunction aerogel with the MXene and GO mass ratio of 1: 16: taking a clean centrifuge tube for standby, and ultrasonically dispersing the prepared MXene suspension of 1.065mg/mL for 1h to obtain a uniform MXene solution. And mixing 8mL of the GO solution and 0.94mL of the MXene solution in a clean centrifuge tube, performing ultrasonic treatment, fully mixing the GO solution and the MXene solution, and freezing. And finally, putting the frozen MXene/GO mixed solution into a freeze dryer for freeze drying for 24-30h to obtain the MXene/graphene oxide three-dimensional heterojunction aerogel.
Example 2:
step 1, taking 7.8mL of 9mol/L hydrochloric acid, preparing 10mL of 7mol/L hydrochloric acid solution, pouring the prepared hydrochloric acid solution into a polytetrafluoroethylene beaker, placing the beaker on a heating type magnetic stirrer for stirring, and weighing 1.44g of LiF and 0.8g of Ti3AlC2And slowly adding the mixture into a polytetrafluoroethylene beaker, covering a preservative film, and starting heating and stirring. After the reaction is completed, the instrument is closed and allowed to cool naturally to room temperature. Then adding distilled water, transferring the diluted test solution into a beaker, standing for several hours, taking a clean centrifuge tube, pouring supernatant into the centrifuge tube, adding water into the precipitate again, performing ultrasonic treatment for half an hour, centrifuging to form uniform suspension, sucking the suspension by using a pipette, putting the suspension into a clean centrifuge bottle, performing centrifugal washing on the suspension by using water, and measuring the pH until the suspension is neutral.
And 2, carrying out ultrasonic treatment on the existing 2mg/mL graphene oxide aqueous solution.
Step 3, preparing MXene/graphene oxide three-dimensional heterojunction aerogel with the MXene and GO mass ratio of 1: 8: taking a clean centrifugal tube for later use, and ultrasonically dispersing the prepared MXene suspension liquid of 1.065mg/mL to obtain a uniform MXene solution; and mixing 8mL of the GO solution and 1.88mL of the MXene solution in a clean centrifuge tube, performing ultrasonic treatment, fully mixing the GO solution and the MXene solution, and freezing. And finally, putting the frozen MXene/GO mixed solution into a freeze dryer for freeze drying for 24-30h to obtain the MXene/graphene oxide three-dimensional heterojunction aerogel.
Example 3:
step 1, preparing 10mL of 7.5mol/L hydrochloric acid solution by taking 8.3mL of 9mol/L hydrochloric acid, pouring the prepared hydrochloric acid solution into a polytetrafluoroethylene beaker, putting the beaker on a heating type magnetic stirrer for stirring, and weighing 1.8g of LiF and 0.9g of Ti3AlC2And slowly adding the mixture into a polytetrafluoroethylene beaker, covering a preservative film, and starting heating and stirring. And after the reaction is finished, closing the instrument, naturally cooling the instrument to room temperature, adding distilled water into the instrument, transferring the diluted test solution into a beaker, standing for several hours, taking a clean centrifuge tube, pouring supernatant into the centrifuge tube, adding water into the precipitate again, performing centrifugation after half an hour of ultrasound to form uniform suspension, sucking the suspension out by using a pipette, putting the suspension into a clean centrifuge bottle, performing centrifugal washing on the suspension by using water, and measuring the pH of the suspension until the suspension is neutral.
And 2, carrying out ultrasonic treatment on the existing 2mg/mL graphene oxide aqueous solution.
Step 3, preparing MXene/graphene oxide three-dimensional heterojunction aerogel with the MXene and GO mass ratio of 1: 4: taking a clean centrifugal tube for later use, and ultrasonically dispersing the prepared MXene suspension liquid of 1.065mg/mL to obtain a uniform MXene solution; and mixing 8mL of the GO solution and 3.76mL of the MXene solution in a clean centrifuge tube, performing ultrasonic treatment, fully mixing the GO solution and the MXene solution, and freezing. And finally, putting the frozen MXene/GO mixed solution into a freeze dryer for freeze drying for 24-30h to obtain the MXene/graphene oxide three-dimensional heterojunction aerogel.
As can be seen from the attached figure 1, the stacking and the staggering of MXene flexible sheets in the assembly form a rich three-dimensional pore channel structure, the size distribution is in the range from micrometer to nanometer, and the assembly is similar to assemblies reported in other documents. The aerogel prepared according to the mass ratio is more delicate, the pore channels are smaller, the three-dimensional structure is favorable for increasing the specific surface area of the composite material, the mutual intercalation of MXene and GO in the MXene/graphene oxide three-dimensional heterojunction aerogel can form a multi-layer reticular structure which is favorable for electron transfer, and on the one hand, the required three-dimensional heterojunction aerogel material can be completely prepared by mixing according to the mass ratio.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (4)
1. An MXene/graphene oxide three-dimensional heterojunction aerogel is characterized in that: the three-dimensional heterojunction aerogel material is compounded by MXene and graphene oxide in the mass ratio of 1:16, 1:8 and 1: 4.
2. A preparation method of MXene/graphene oxide three-dimensional heterojunction aerogel is characterized by comprising the following steps:
step one, preparation of MXene suspension: preparing a hydrochloric acid solution with a certain concentration, pouring the prepared hydrochloric acid solution into a polytetrafluoroethylene beaker, placing the beaker on a heating type magnetic stirrer for stirring, and weighing LiF and Ti with a certain mass ratio3AlC2Slowly adding the mixture into a polytetrafluoroethylene beaker, covering a preservative film, and starting heating and stirring; after the reaction is finished, closing the instrument, and naturally cooling the instrument to room temperature; then adding distilled water, transferring the diluted test solution into a beaker, standing for several hours, taking a clean centrifuge tube, pouring supernatant into the centrifuge tube, adding water again into the precipitate, performing ultrasonic treatment for half an hour, centrifuging to form uniform suspension, sucking out the suspension by using a pipette, putting the suspension into a clean centrifuge bottle, performing centrifugal washing on the suspension by using water, and measuring the pH of the solution by using a pH test paper until the solution is neutral;
step two, carrying out ultrasonic treatment on the existing 2mg/mL graphene oxide aqueous solution;
step three, preparing MXene/graphene oxide three-dimensional heterojunction aerogel: taking a clean centrifugal tube for later use, diluting the prepared MXene suspension, and performing ultrasonic treatment to obtain a uniform MXene solution; mixing MXene and graphene oxide in a clean centrifugal tube according to a specific mass ratio, performing ultrasonic treatment to fully mix the MXene and the graphene oxide, and freezing; and finally, putting the frozen MXene/graphene oxide mixed solution into a freeze dryer for freeze drying to obtain the MXene/graphene oxide three-dimensional heterojunction aerogel.
3. The preparation method of MXene/graphene oxide three-dimensional heterojunction aerogel according to claim 2, wherein the preparation method comprises the following steps: in the first step, the heating temperature is 40 ℃, the reaction time is 12 hours, the rotating speed of a centrifugal machine is set to 4000r/min, the Ti is weighed after being washed for about 5-6 times3AlC2And LiF in a mass ratio of 1:1.6 to 1: 2.
4. The preparation method of MXene/graphene oxide three-dimensional heterojunction aerogel according to claim 2, wherein the preparation method comprises the following steps: in the third step, the freeze drying time is 24-30 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731380A (en) * | 2021-09-27 | 2021-12-03 | 烟台大学 | MXene/graphene/polyethyleneimine composite aerogel and preparation method and application thereof |
| CN113979438A (en) * | 2021-12-23 | 2022-01-28 | 中博龙辉装备集团股份有限公司 | Graphene titanium carbide composite porous gel film and preparation method and application thereof |
| CN116216718A (en) * | 2023-01-13 | 2023-06-06 | 青岛理工大学 | graphene/MXene composite aerogel material and preparation method thereof |
-
2021
- 2021-07-15 CN CN202110802426.9A patent/CN113428862A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 原因: "轻质石墨烯与MXene气凝胶的制备及其电磁屏蔽性能", 《中国优秀硕士论文数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113731380A (en) * | 2021-09-27 | 2021-12-03 | 烟台大学 | MXene/graphene/polyethyleneimine composite aerogel and preparation method and application thereof |
| CN113731380B (en) * | 2021-09-27 | 2023-07-25 | 烟台大学 | MXene/graphene/polyethyleneimine composite aerogel and preparation method and application thereof |
| CN113979438A (en) * | 2021-12-23 | 2022-01-28 | 中博龙辉装备集团股份有限公司 | Graphene titanium carbide composite porous gel film and preparation method and application thereof |
| CN116216718A (en) * | 2023-01-13 | 2023-06-06 | 青岛理工大学 | graphene/MXene composite aerogel material and preparation method thereof |
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