CN115215334B - Preparation method of graphene oxide aerogel hollow microspheres - Google Patents
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Abstract
The invention discloses a preparation method of graphene oxide aerogel hollow microspheres, which comprises the following steps: preparing graphene oxide solution, and regulating the pH value of the graphene oxide solution by using dilute hydrochloric acid solution; mixing graphene oxide with a regulated pH value with an oil phase, performing ultrasonic treatment, and then vigorously shaking to obtain stable and rich emulsion, adding a salt solution of metal ions, sufficiently shaking to uniformly mix the solution, and standing until the reaction is complete; washing the obtained emulsion with deionized water, centrifuging, obtaining emulsion balls on the upper layer, and drying to remove the internal oil phase. The preparation method of the graphene oxide aerogel hollow microspheres solves the problems that the existing preparation method of the graphene oxide aerogel hollow microspheres needs high temperature and high pressure, the cost is increased, the template is modified or functionalized by adding an additional surfactant, the preparation process is complex, the hard template is not environment-friendly by using harmful substances to dissolve, and the like.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method of graphene oxide aerogel hollow microspheres.
Background
Graphene Oxide (GO) has been attracting attention as a precursor of conductive materials due to its antibacterial properties, mechanical strength, air resistance properties. Graphene oxide is a material prepared from sp 2 And sp (sp) 3 The planar surface of the sheet-like structure composed of hybridized carbon atoms has a plurality of oxygen-containing functional groups (namely hydroxyl, epoxy, carboxyl and the like). According to the current model, the graphene oxide sheets have hydrophilic carboxyl groups on the periphery and hydrophobic carbon planes on the basal plane. The carboxyl functionality at the GO edge can be deprotonated to generate charged groups, in considerable polarity contrast to the widely hydrophobic "surface" of the sheet. The amphipathy explains the tendency of graphene oxide on the interface to a great extent, and can be used as a surfactant to stabilize Pickering type emulsion. According to microscopic mechanism analysis, hydroxyl, carboxyl, carbonyl and other groups on the graphene oxide sheets can coordinate with metal ions, so that chemical crosslinking is generated between the graphene oxide sheets to form covalent chemical bonds, and the interactions play a key role in self-assembling the GO sheets into a three-dimensional structure, so that the two-dimensional graphene oxide nano sheets are self-assembled into a three-dimensional spherical structure, and the firmness and stability of the sphere are improved.
The current situation of preparing graphene oxide aerogel hollow microspheres mainly comprises the following steps: the most common method for synthesizing graphene oxide aerogel hollow microspheres generally adopts a hydrothermal method and a template method for synthesis. Freeze-drying a dispersion containing a reducing agent, graphene oxide, and water in san, cui Xinan, et al to form an aerogel sample having a fixed shape; and then carrying out hydrothermal reduction reaction on the aerogel sample at 50-200 ℃ for 0.5-24 hours to obtain a graphene oxide aerogel finished product. (patent number CN 112299398A). However, this method is accompanied by high temperature, which inevitably increases the cost and limits the practical use in industrial life. Therefore, the main research is focused on the template method, such as Li Heran, li Qing, and the like, for preparing hollow graphene oxide microspheres by a hard template method (silicon template method). The preparation method comprises the steps of carrying out spray drying on aqueous dispersion liquid containing amination nanometer silicon dioxide particles and graphene oxide to obtain composite particles of graphene oxide coated amination nanometer silicon dioxide; and (3) etching the composite particles of the graphene oxide coated amino nano silicon dioxide obtained in the previous step by using acid, and removing the amino nano silicon dioxide particles in the composite particles to obtain the hollow sphere graphene oxide carrier. (patent number CN110354835 a). Huang et al coated GO on colloidal Polystyrene (PS) particles using aerosol spray pyrolysis (polymer templating), and then removed the PS core under thermal conditions. The template method generally needs to use expensive surfactant to functionalize/modify the template due to incompatibility of the template surface and the shell material, so that the preparation process is complex and the cost is high.
In view of the above, it is necessary to design a preparation method of graphene oxide aerogel hollow microspheres.
Disclosure of Invention
The invention aims to provide a preparation method of graphene oxide aerogel hollow microspheres, which solves the problems that the existing preparation method of graphene oxide aerogel hollow microspheres needs high temperature and high pressure, increases cost, needs to add additional surfactant to modify or functionalize a template, causes complex preparation process, uses harmful substances to dissolve the hard template, is not green and environment-friendly, and the like.
In order to achieve the above purpose, the invention provides a preparation method of graphene oxide aerogel hollow microspheres, which comprises the following steps:
s1, preparing graphene oxide solution, and regulating the pH value of the graphene oxide solution by using dilute hydrochloric acid solution;
s2, mixing graphene oxide with a regulated pH value with an oil phase, performing ultrasonic treatment, and then vigorously shaking to obtain stable and rich emulsion, adding a salt solution of metal ions, sufficiently shaking to uniformly mix the solution, and standing until the reaction is complete;
s3, washing the obtained emulsion with deionized water, centrifuging, obtaining emulsion balls on the upper layer, and drying to remove an internal oil phase.
Preferably, the pH value of the graphene oxide solution in step S1 is 2.0-3.0.
Preferably, the oil phase in the step S2 is toluene or n-hexane.
Preferably, in the step S2, the purity of the graphene oxide is greater than 99%, the thickness is 0.5-1.2nm, the number of layers is 1-2, the transverse dimension is 2-8 μm, the carbon-oxygen ratio is 2-4, and the concentration of the graphene oxide is 0.5mg/mL-5mg/mL.
Preferably, the ultrasonic time in the step S2 is 1min-5min.
Preferably, the metal ion in the step S2 is one of a transition metal, an alkali metal or a main group metal.
Preferably, the mass ratio of the metal ion to the graphene oxide in the step S2 is 0.2-1.
Preferably, the reaction time in the step S2 is 6h-12h.
Preferably, the centrifugal speed in the step S3 is 1500-2000 rpm for 5min.
Preferably, the drying temperature in the step S3 is 40-100 ℃ and the drying time is 24-36h.
The preparation method of the graphene oxide aerogel hollow microsphere is simple, a hard template is not needed, the size of the sphere is controllable, and the shell is loose and porous. The invention selects a simple and easy method for preparing the crosslinked graphene oxide microsphere, and the method takes graphene oxide as a surfactant in Pickering type emulsion, and can regulate and control the size of the microsphere by changing the concentration of the graphene oxide, so that stable microsphere with controllable size is formed with different oil phases. And then, metal cations are added to react with carboxyl groups at the edges of graphene oxide sheets to generate chemical crosslinking among the graphene oxide sheets to form covalent chemical bonds, so that the firmness and stability of the sphere are improved. And because the stacking of the sheets is not performed, the cross-linking of the edges of the sheets is performed, the surface area of the hollow spherical shell is greatly increased, active sites are increased, and a plurality of channels are formed for the shell due to the precipitation of the oil phase in the process of removing the internal oil phase in a drying manner, so that the finally formed hollow spherical shell has a loose and porous structure. The microsphere prepared by bonding metal cations and GO edge carboxyl groups provides more possibilities for application.
Therefore, the preparation method of the graphene oxide aerogel hollow microspheres has the following beneficial effects:
(1) The preparation method of the graphene oxide hollow microsphere is simple, does not contain toxic reagents, is environment-friendly, is easy to separate, has low cost and high yield, does not need high temperature and high pressure, and the prepared graphene oxide hollow microsphere has good mechanical strength (i.e. firmness) and rich shell pore channels.
(2) The preparation method solves the problems that the prior graphene oxide hollow microsphere is difficult to dissolve and release due to the additional addition of a surfactant and an internal template, and the shell is easy to collapse and deform.
(3) The size of the microsphere can be regulated by changing the concentration of the graphene oxide, so that the microsphere which meets the production requirement is prepared, the particle size of the graphene oxide hollow microsphere is in the micron level, the mechanical strength is high, the shell channels are rich, and the graphene oxide hollow microsphere can be widely applied to more fields.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is an optical microscope image of emulsion spheres under different conditions according to example 1 of the present invention, wherein a is emulsion sphere before calcium ion addition and b is emulsion sphere after calcium ion addition;
FIG. 2 is an optical microscope image of emulsion balls under different conditions according to example 2 of the present invention, wherein a is emulsion balls before calcium ion addition, and b is emulsion balls after calcium ion addition;
FIG. 3 is an optical microscope image of emulsion spheres under different conditions according to example 3 of the present invention, wherein a is emulsion sphere before calcium ion addition and b is emulsion sphere after calcium ion addition;
FIG. 4 is an optical microscope image of emulsion balls under different conditions according to example 4 of the present invention, wherein a is emulsion balls before adding copper ions, and b is emulsion balls after adding copper ions;
fig. 5 is an optical microscope picture of a hollow graphene oxide microsphere prepared in the embodiment of the present invention, wherein a is the hollow graphene oxide microsphere in embodiment 1, b is the hollow graphene oxide microsphere in embodiment 2, c is the hollow graphene oxide microsphere in embodiment 3, and d is the hollow graphene oxide microsphere in embodiment 4;
FIG. 6 is a graph showing the centrifugation of emulsions with and without metal ions under different conditions according to the examples of the present invention.
Fig. 7 is an infrared diagram of a hollow graphene oxide microsphere prepared in an embodiment of the present invention.
Detailed Description
The invention provides a preparation method of graphene oxide aerogel hollow microspheres, which comprises the following steps:
s1, preparing graphene oxide solution, and regulating the pH value of the graphene oxide solution to 2.0-3.0 by using dilute hydrochloric acid solution.
S2, mixing graphene oxide with a regulated pH value with an oil phase, carrying out ultrasonic treatment for 1min-5min, then shaking vigorously to obtain stable and rich emulsion, adding a salt solution of metal ions, fully shaking to uniformly mix the metal ions and the graphene oxide, and standing until the reaction is complete, wherein the reaction time is 6-12 h; the oil phase is toluene or n-hexane, the purity of graphene oxide is greater than 99%, the thickness is 0.5-1.2nm, the number of layers is 1-2, the transverse dimension is 2-8 mu m, the carbon-oxygen ratio is 2-4, and the concentration of graphene oxide is 0.5mg/mL-5mg/mL.
S3, washing the obtained emulsion with deionized water, centrifuging at 1500-2000 rpm for 5min, drying the upper layer to remove the internal oil phase, wherein the drying temperature is 40-100 ℃ and the drying time is 24-36h.
The metal ion is one of transition metal, alkali metal or main group metal.
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Example 1
The preparation method of the graphene oxide aerogel hollow microspheres comprises the following steps:
s1, preparing 50mL of graphene oxide solution with the concentration of 1mg/mL, and regulating the pH value of the graphene oxide solution to 2.5 by using dilute hydrochloric acid solution with the concentration of 1 mol/L.
S2, mixing the GO with the adjusted pH value and toluene in a volume ratio of 1:1, carrying out ultrasonic treatment for 5min, shaking vigorously by hands to form stable and rich emulsion, adding 2mL of 5mg/mL calcium chloride solution, shaking sufficiently to uniformly mix, and standing for 12h for reaction.
S3, washing the obtained emulsion balls with deionized water, centrifuging at 2000 rpm, and removing redundant calcium ions adsorbed on the surfaces of the microspheres and complexes of graphene oxide and calcium ions among the microspheres. Pouring out the upper microsphere, and drying at 45deg.C under vacuum (-0.1 MPa) for 24 hr.
The emulsion balls before and after calcium ion addition were observed under an optical microscope to obtain an observation chart as shown in fig. 1. As can be seen from the graph, the average particle size of the emulsion balls before the calcium ion is not added for crosslinking is about 600 microns, and the average particle size of the emulsion balls after the calcium ion is added for crosslinking is about 300 microns. And the amount of emulsion balls is more abundant after calcium ions are added for crosslinking, and the stacking is more compact. Thus, after calcium ions are added, the particle size of emulsion balls is reduced, and the ball amount is increased.
The picture under an optical microscope of the dried graphene oxide hollow microspheres is shown as a in fig. 5, a clear spherical structure can be obviously observed, and the particle size is about 300 microns.
The infrared diagram of the dried graphene oxide hollow microspheres is shown in fig. 7, and as can be seen from fig. 7, the infrared spectrogram of the graphene oxide hollow microspheres is 3430cm -1 Peaks appear at the left and right sides, which are stretching vibration peaks of water molecules-OH between graphene oxide layers. At 1613cm -1 And 1726cm -1 There is a carboxyl extension vibration peak, which indicates that not all carboxyl groups coordinate with calcium ions. In addition at 1382cm -1 The part is calcium oxideStretching vibration peak, the carboxyl and calcium ion are proved to crosslink.
Example 2
The preparation method of the graphene oxide aerogel hollow microspheres comprises the following steps:
s1, preparing 50mL of graphene oxide solution with the concentration of 2mg/mL, and regulating the pH value of the graphene oxide solution to 2.5 by using 1mol/L dilute hydrochloric acid solution.
S2, mixing the GO with the pH value regulated and toluene in a volume ratio of 1:1, performing ultrasonic treatment for 5min, and vigorously shaking by hands to form stable and rich emulsion. Then, 2mL of 50mg/mL calcium chloride solution is added, the mixture is fully shaken to be uniformly mixed, and the mixture is left to stand for reaction for 12h.
S3, washing the obtained emulsion ball with deionized water, centrifuging at 2000 rpm, and removing superfluous calcium ions attached to the surface of the microsphere and complexes of graphene oxide and calcium ions among the microspheres. Pouring out the upper microsphere. Drying at 45deg.C under vacuum (-0.1 MPa) for 24 hr.
The emulsion balls before and after calcium ion addition were observed under an optical microscope to obtain an observation chart as shown in fig. 2. As can be seen from the graph, the average particle size of the emulsion balls before the calcium ion is not added for crosslinking is about 500 microns, and the average particle size of the emulsion balls after the calcium ion is added for crosslinking is about 200 microns. Compared with the former group, the concentration of graphene oxide is increased, and the particle size of the spheres is reduced.
The picture under an optical microscope of the dried graphene oxide hollow microspheres is shown as b in fig. 5, so that clear spherical structures can be obviously observed, and the particle size is about 200 microns.
Example 3
The preparation method of the graphene oxide aerogel hollow microspheres comprises the following steps:
s1, preparing 50mL of graphene oxide solution with the concentration of 2mg/mL, and regulating the pH value of the graphene oxide solution to 2.5 by using 1mol/L dilute hydrochloric acid solution.
S2, mixing the GO with the pH value regulated and the n-hexane in a volume ratio of 1:1, performing ultrasonic treatment for 5min, and vigorously shaking by hands to form stable and rich emulsion. Then, 2mL of 50mg/mL calcium chloride solution is added, the mixture is fully shaken to be uniformly mixed, and the mixture is left to stand for reaction for 12h.
S3, washing the obtained emulsion ball with deionized water, centrifuging at 2000 rpm, and removing superfluous calcium ions attached to the surface of the microsphere and complexes of graphene oxide and calcium ions among the microspheres. Pouring out the upper microsphere. Drying at 30℃for 36h.
The emulsion balls before and after calcium ion addition were observed under an optical microscope to obtain an observation chart as shown in fig. 3. As can be seen from the graph, the average particle size of the emulsion balls before the calcium ion is not added for crosslinking is about 300 microns, and the average particle size of the emulsion balls after the calcium ion is added for crosslinking is about 200 microns.
The image of the dried graphene oxide hollow microspheres under an optical microscope is shown as c in fig. 5, a clear spherical structure can be obviously observed, and the particle size is about 50 microns. In addition to this, there is a small amount of collapsed, collapsed balls, taking into account that the balls collapse due to insufficient supporting forces on the ball surface, possibly when drying to remove the internal oil phase. Such collapsed balls may also prove that the ball is hollow in structure.
Example 4
The preparation method of the graphene oxide aerogel hollow microspheres comprises the following steps:
s1, preparing 50mL of graphene oxide solution with the concentration of 2mg/mL, and regulating the pH value of the graphene oxide solution to 2.5 by using 1mol/L dilute hydrochloric acid solution.
S2, mixing the GO with the pH value regulated and the n-hexane in a volume ratio of 1:1, performing ultrasonic treatment for 5min, and vigorously shaking by hands to form stable and rich emulsion. Then, 2mL of 50mg/mL copper chloride solution is added, and the mixture is fully shaken to be uniformly mixed, and the mixture is left to stand for reaction for 12 hours.
And S3, washing the obtained emulsion ball with deionized water, centrifuging at 2000 revolutions, and removing redundant copper ions attached to the surface of the microsphere and complexes of graphene oxide and copper ions among the microsphere. Pouring out the upper microsphere. Drying at 30℃for 36h.
The emulsion balls before and after adding copper ions were observed under an optical microscope to obtain an observation chart as shown in fig. 4. As can be seen from the graph, the average particle size of the emulsion balls before the copper ion crosslinking is not added is about 300 microns, and the average particle size of the emulsion balls after the copper ion crosslinking is added is about 200 microns.
The image of the dried graphene oxide hollow microspheres under an optical microscope is shown as d in fig. 5, a clear spherical structure can be obviously observed, and the particle size is about 40 microns. The amount of balls is smaller than in the previous group, considering that it may be the reason that the copper ion coordination ability is weaker than the calcium ion coordination ability.
Fig. 6 is a graph of the above 8 groups of samples 2000 after centrifugation for 5 minutes, and it can be seen from the graph that each group of balls without metal ion crosslinking has a disintegrated after centrifugation, the balls after metal ion crosslinking are added, the structure of the balls is still maintained after centrifugation, and precipitates are all generated, which are the crosslinked product of the excessive graphene oxide and the metal ions. Thus, the reaction of the metal ions and the graphene oxide can also be verified.
Therefore, the preparation method of the graphene oxide aerogel hollow microspheres solves the problems that the existing preparation method of the graphene oxide aerogel hollow microspheres needs high temperature and high pressure, increases cost, needs additional surfactant to modify or functionalize a template, causes complex preparation process, uses harmful substances to dissolve a hard template, is not environment-friendly and the like.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (8)
1. The preparation method of the graphene oxide aerogel hollow microspheres is characterized by comprising the following steps of:
s1, preparing graphene oxide solution, and regulating the pH value of the graphene oxide solution by using dilute hydrochloric acid solution;
s2, mixing graphene oxide with a regulated pH value with an oil phase, performing ultrasonic treatment, and then vigorously shaking to obtain stable and rich emulsion, adding a salt solution of metal ions, sufficiently shaking to uniformly mix the solution, and standing until the reaction is complete;
s3, washing the obtained emulsion with deionized water, centrifuging, obtaining emulsion balls on the upper layer, and drying to remove an internal oil phase;
the oil phase in the step S2 is toluene or n-hexane;
the metal ion in the step S2 is one of transition metal or main group metal.
2. The method for preparing graphene oxide aerogel hollow microspheres according to claim 1, wherein the method comprises the following steps: the pH value of the graphene oxide solution in the step S1 is 2.0-3.0.
3. The method for preparing graphene oxide aerogel hollow microspheres according to claim 1, wherein the method comprises the following steps: the purity of the graphene oxide in the step S2 is greater than 99%, the thickness is 0.5-1.2nm, the number of layers is 1-2, the transverse dimension is 2-8 mu m, the carbon-oxygen ratio is 2-4, and the concentration of the graphene oxide is 0.5mg/mL-5mg/mL.
4. The method for preparing graphene oxide aerogel hollow microspheres according to claim 1, wherein the method comprises the following steps: the ultrasonic time in the step S2 is 1min-5min.
5. The method for preparing graphene oxide aerogel hollow microspheres according to claim 1, wherein the method comprises the following steps: the mass ratio of the metal ions to the graphene oxide in the step S2 is 0.2-1.
6. The method for preparing graphene oxide aerogel hollow microspheres according to claim 1, wherein the method comprises the following steps: the reaction time in the step S2 is 6-12 h.
7. The method for preparing graphene oxide aerogel hollow microspheres according to claim 1, wherein the method comprises the following steps: and the centrifugal rotating speed in the step S3 is 1500-2000 revolutions for 5min.
8. The method for preparing graphene oxide aerogel hollow microspheres according to claim 1, wherein the method comprises the following steps: the drying temperature in the step S3 is 40-100 ℃ and the drying time is 24-36h.
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| JP2014240330A (en) * | 2013-05-16 | 2014-12-25 | 独立行政法人物質・材料研究機構 | Method for preparing graphene spherical hollow body, graphene spherical hollow body, graphene spherical hollow body integrated electrode, and graphene spherical hollow body integrated capacitor |
| CN105565394A (en) * | 2015-12-14 | 2016-05-11 | 大连理工大学 | Preparation method of graphene hollow microspheres loaded with magnetic nanoparticles |
| KR20200010274A (en) * | 2017-04-28 | 2020-01-30 | 항저우 고우시 테크놀로지 컴퍼니 리미티드 | Paper Ball Graphene Microspheres, Composites and Manufacturing Method Thereof |
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| CN105131596B (en) * | 2015-09-14 | 2017-10-24 | 江南大学 | A kind of preparation method of graphene/polyaniline compound hollow microballoon |
| CN107226464B (en) * | 2017-07-24 | 2019-06-14 | 中国石油大学(华东) | The preparation method of graphene aerogel based on emulsion method |
| CN109054975A (en) * | 2018-07-23 | 2018-12-21 | 中国科学院上海高等研究院 | A kind of graphite oxide alkenyl Pickering lotion and its preparation method and application |
| CN110203909A (en) * | 2019-06-27 | 2019-09-06 | 中素新科技有限公司 | Graphene aerogel microballoon and preparation method thereof |
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| JP2014240330A (en) * | 2013-05-16 | 2014-12-25 | 独立行政法人物質・材料研究機構 | Method for preparing graphene spherical hollow body, graphene spherical hollow body, graphene spherical hollow body integrated electrode, and graphene spherical hollow body integrated capacitor |
| CN105565394A (en) * | 2015-12-14 | 2016-05-11 | 大连理工大学 | Preparation method of graphene hollow microspheres loaded with magnetic nanoparticles |
| KR20200010274A (en) * | 2017-04-28 | 2020-01-30 | 항저우 고우시 테크놀로지 컴퍼니 리미티드 | Paper Ball Graphene Microspheres, Composites and Manufacturing Method Thereof |
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