CN115784212A - Hollow graphene capsule and solvent-induced self-curling preparation method thereof - Google Patents
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- 239000002775 capsule Substances 0.000 title claims abstract description 29
- 239000002904 solvent Substances 0.000 title claims abstract description 28
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Abstract
The invention discloses a hollow graphene capsule and a solvent-induced self-curling preparation method thereof. The hollow graphene capsule is formed by self-curling of graphene-based nanosheets into a hollow closed structure, and the closed structure has reversibility; the thickness of the hollow graphene capsule is the same as that of the graphene-based nanosheet; the particle size of the hollow graphene capsule is 30-90 nm. Dispersing the graphene-based nanosheets into deionized water, and performing ultrasonic treatment to form uniformly dispersed graphene-based nano dispersion liquid; and adding a nonpolar solvent into the graphene-based nano dispersion liquid to obtain the self-curled hollow graphene capsule. According to the invention, the graphene-based nanomaterial with a novel structure is synthesized by regulating the concentration of the graphene-based nanosheets in water, ultrasonic treatment and the size of the graphene-based nanosheets and adopting solvent induction, so that a structure regulation foundation is provided for the novel graphene nanomaterial.
Description
Technical Field
The invention relates to the technical field of nano-coils, in particular to a solvent-induced self-curling method for preparing a hollow graphene capsule.
Background
Graphene-based nanomaterials are one of the most pyrogenic materials studied in recent years, attracting the research interest of a large number of scientists. Graphene-based nanomaterials are two-dimensional materials composed of carbon atom skeletons and exfoliated from graphite, and are widely researched due to unique structures and properties of the two-dimensional materials, including Graphene (G) nanomaterials, graphene Oxide (GO) nanomaterials, reduced Graphene oxide (r-GO) nanomaterials, nitrogen and phosphorus element doped Graphene (Nitrogen doped Graphene, phosphorus doped Graphene, N-G, P-G), nitrogen and phosphorus element doped Graphene oxide (N-GO, P-GO) nanomaterials. At present, the research on graphene is mainly on the research on the properties of graphene, such as how to improve the electrochemical properties of graphene through element doping and how to change the photo-thermal properties of graphene through element regulation, and the regulation and control research on the structure of graphene is less. The carbon nanotube is a circular tubular structure composed of carbon atoms, and the football alkene C60 is a spherical structure molecule composed of 60 carbon atoms, so that the two-dimensional structure of the carbon nanotube can be regulated by regulating the structural form of graphene, carbon substances with various novel structural shapes can be synthesized, and the carbon nanotube has new properties different from graphene. By designing the novel structure of the graphene-based nano material, the function and property regulation of the novel graphene-based carbon material can be realized, and the application is wider.
The graphene-based nanomaterial is of a two-dimensional structure which is formed by a hexagonal structure formed by nonpolar carbon, a multi-wall carbon nanotube structure can be formed by curling graphene nanosheets, and after a functionalized material is loaded on the surface of graphene, the functionalized material structure wrapped by the carbon nanotube is realized, and the promotion of properties such as a gas sensor, energy storage and a lubricating material is realized. At present, a plurality of graphene nano rolls or carbon nano rolls are prepared, for example, a patent with the application number of 201410243627.X discloses a preparation method of a carbon nano roll material, graphene is dissolved in an organic solvent, a certain amount of ferrocene formaldehyde is added, and the carbon nano roll material is synthesized by an ultrasonic method. Patent application No. 202210257545.5 discloses a preparation method of a graphene oxide nano roll, which is prepared by taking a graphene oxide aqueous solution as a solvent and a carrier, adding silver nitrate, trisodium citrate and N, N-dimethylethanolamine into the solvent and the carrier, stirring at a constant speed at normal temperature, ultrasonically dispersing, centrifugally cleaning and removing impurities. The patent with application number 202010560973.6 discloses carbon nanocolloid and a preparation method and application thereof, wherein carbon nanodots are subjected to solvothermal reaction in a polar aprotic solvent to form the carbon nanocolloid. Although the organic solvent is added in the above preparation methods, the preparation methods do not use the solvent polarity to control the graphene material to prepare the nano-coil. At present, few researches are carried out on methods for regulating and controlling the structure of the graphene-based nano material according to the polarity of a solvent.
Disclosure of Invention
In view of the above prior art, the present invention aims to provide a solvent-induced self-crimping method for preparing hollow graphene capsules. According to the invention, the graphene-based nano material with a novel structure is synthesized by a solvent-induced self-curling method, a structure regulation and control foundation is provided for the novel graphene nano material, and a novel functional property regulation and control strategy is also provided for the novel graphene-based structure nano material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a hollow graphene capsule is provided, wherein the hollow graphene capsule is formed by self-curling of graphene-based nanosheets into a hollow closed structure, and the closed structure has reversibility; the thickness of the hollow graphene capsule is the same as that of the graphene-based nanosheet; the particle size of the hollow graphene capsule is 30-90 nm.
Preferably, the hollow graphene capsule is dispersed in water, and the two-dimensional structure of the graphene-based nanosheet can be restored within 1-24 h.
In a second aspect of the present invention, there is provided a solvent-induced self-crimping method for preparing a hollow graphene capsule, comprising the steps of:
(1) Dispersing graphene-based nanosheets into deionized water, and performing ultrasonic treatment to form uniformly dispersed graphene-based nano dispersion liquid;
(2) And adding a nonpolar solvent into the graphene-based nano dispersion liquid to obtain the self-curled hollow graphene capsule.
Preferably, in step (1), the graphene-based nanosheets are selected from graphene nanosheets, graphene oxide nanosheets, nitrogen-doped graphene nanosheets or reduced graphene oxide nanosheets.
Preferably, in the step (1), the concentration of the graphene-based nano dispersion liquid is 1-2.5mg/mL.
Preferably, in the step (1), the power of the ultrasonic treatment is 42kHz, the frequency is 100W, and the time is 6-8 h; the temperature of the ultrasonic treatment is 30-40 ℃.
Preferably, in the step (1), the size of the graphene-based nanoplatelets in the graphene-based nanodispersion is 150-300nm.
Preferably, in the step (2), the volume ratio of the nonpolar solvent to the deionized water is (1-10): 1.
preferably, in the step (2), the nonpolar solvent is a nonpolar organic solvent, and the nonpolar organic solvent is at least one selected from ethanol, acetone, ethyl acetate, tetrahydrofuran, diethyl ether, N-hexane and N, N-dimethylformamide.
The invention has the beneficial effects that:
(1) The invention discloses a method for preparing a hollow graphene capsule by a solvent-induced self-curling method for the first time, which utilizes the solvent-induced self-curling method to regulate and control the polarity of a solvent by adding an organic solvent with a certain proportion into an aqueous solution, thereby regulating and controlling the dispersion state and morphological structure of graphene-based nanosheets in the solution. The method has the advantages of simple synthesis method, easy operation, batch synthesis, strong controllability and the like, and can promote the synthesis and application of the novel graphene-based nano material.
(2) The invention prepares the hollow graphene-based nanocapsules by a solvent-induced self-curling method, wherein the hollow graphene-based nanocapsules comprise graphene oxide hollow nanocapsules, graphene hollow nanocapsules and the like. And the nanocapsules can restore the two-dimensional nanosheet structure after being fully dispersed in the aqueous solution. Compared with a common graphene-based two-dimensional structure, the novel hollow graphene-based nanocapsule structure is synthesized, and a research basis is provided for the property research of the novel structural material.
(3) The hollow nanocapsule prepared by the invention can be used in the research fields of drug delivery, tissue engineering and the like due to the unique hollow structure, and the graphene-based nanocapsule synthesized by the invention is easy to produce in large scale and simple to operate, so that the hollow nanocapsule can be widely applied in the fields of biology, energy storage, lubrication and the like.
(4) The method of the invention adopts a solvent induction regulation strategy, is easy to realize batch production, and does not need expensive instruments and equipment. And the synthesized hollow nano structure has strong innovation, can be used for drug carriers, energy storage materials and the like, can easily realize industrialization, and has wide application prospect.
Drawings
FIG. 1: the a picture is a Transmission Electron Microscope (TEM) picture of Graphene Oxide (GO) nanosheets, and the b picture is a TEM picture of graphene (G).
FIG. 2 is a schematic diagram: fig. a and b are TEM and high-resolution transmission electron microscope images of solvent-induced self-curled Graphene Oxide (GO) hollow nanocapsules, respectively. And c and d are respectively a TEM image and a high-resolution transmission electron microscope image of the solvent-induced self-curled graphene (G) hollow nanocapsule.
FIG. 3: the images a and b are TEM images of 1h and 12h after the hollow graphene oxide nanocapsule is redispersed in the aqueous solution respectively. And c and d are TEM images of 1h and 12h after the hollow graphene nano capsule is re-dispersed in the aqueous solution respectively.
FIG. 4 is a schematic view of: and a picture a and a picture b are transmission electron microscope pictures of the solid graphene nano-material prepared in the comparative example 1 under different scales.
FIG. 5 is a schematic view of: and the a picture and the b picture are transmission electron microscope pictures of the solid graphene nano material prepared in the comparative example 2 under different scales.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As introduced in the background section, the prior art for preparing nano-coil by using graphene two-dimensional structure has no related report of regulating structural change according to solvent polarity. Rolling up of graphene oxide sheets through solution-induced self-assembly in dispersions (Bo Tang et al, nanoscale,2018, 10, 4113) although it is disclosed that graphene oxide sheets roll up in graphene oxide solutions to gradually form nanoscrolls as the DMF content increases. However, the nano-coil is not an integrally closed capsule structure but an open similar tubular structure, the nano-coil cannot realize the encapsulation of substances, the application field is limited, and the nano-capsule can realize the research of drug delivery and the like.
Based on this, the object of the present invention is to provide a solvent-induced self-crimping method for preparing hollow graphene capsules. According to the method, the graphene or graphene oxide nano material is ultrasonically oxidized in the aqueous solution to form a nano material solution with a uniformly dispersed water phase, and then a nonpolar solvent is added into the nano material solution to realize the structural regulation and control of the graphene or graphene oxide nano material. After the non-polar organic solvent is added into the graphene-based nanosheets, the graphene-based nanosheets exhibit solvent-induced self-curling properties, and the two-dimensional nanosheets self-curl to form hollow nanocapsules. The nanocapsules are capable of re-unfolding into a two-dimensional nanosheet structure after re-dispersing the aqueous solution.
According to research, the graphene-based nanosheets are subjected to ultrasonic treatment at certain ultrasonic power, frequency, ultrasonic temperature and time to obtain a dispersion liquid with the concentration of 1-2.5 mg/mL; and controlling the size of the graphene-based nanosheets in the graphene-based nanodispersion. Under the premise, the polarity of the solvent is changed, and the dispersion state of the two-dimensional nano material in the solution is further changed, so that the two-dimensional nano structure shrinks to reduce the surface energy, and a self-curling phenomenon is generated to form a hollow nano capsule structure. Therefore, the structural state of the graphene-based nano material is changed by changing the polarity of the solvent, and a brand-new novel structure of the graphene-based hollow nano capsule with a closed structure is synthesized by a solvent-induced self-curling method, so that a structural design basis is provided for further researching the performance of the graphene-based hollow nano capsule.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention were all conventional in the art and commercially available.
Example 1
(1) Weighing graphene nanosheets, dispersing the graphene nanosheets into deionized water, and uniformly stirring to form nanosheet dispersion liquid of 2 mg/mL. The dispersion was then placed in an ultrasonic cleaner for 6h to form a uniformly dispersed nanoplate dispersion of 200nm size.
(2) Adding absolute ethyl alcohol into the graphene nanosheet dispersion liquid, and adding ethanol to water in a volume ratio of 5. And (3) centrifuging the mixed dispersion liquid at a high speed, collecting the nanocapsules, and dispersing the collected product in absolute ethyl alcohol again. In order to observe the recovery properties of the nanocapsules, the nanocapsules obtained by centrifugation were redispersed in an aqueous solution and observed by transmission electron microscopy after 1 and 12 hours of dispersion in the aqueous solution. After 1h, part of the nanocapsules recover the original two-dimensional sheet structure; and observing after 12h, and recovering all the nanocapsules to the original two-dimensional sheet structure.
(3) Preparing samples of the graphene nanocapsules dispersed in the organic solution and the recovered nanocapsules, and feeding the prepared samples into a transmission electron microscope for observation.
Under the above conditions, the two-dimensional graphene-based nanosheet material shown in fig. 1b is synthesized into the hollow nanocapsule by using the two-dimensional graphene-based nanomaterial through a solvent induction method, and as a result, the synthesized hollow nanocapsule has a uniform size and presents a multi-layer wrapped and curled hollow capsule structure as shown in cd of fig. 2. And as shown in cd of fig. 3, after the nanocapsule is redispersed in the aqueous solution, the original two-dimensional spreading form can be restored, and therefore the form regulation is reversible.
Example 2
1) Weighing graphene oxide nanosheets, dispersing the graphene oxide nanosheets into deionized water, and uniformly stirring to form 1mg/mL nanosheet dispersion liquid. And then placing the dispersion liquid into an ultrasonic cleaning machine for ultrasonic treatment for 8 hours to form the uniformly dispersed nano-sheet dispersion liquid with the size of 150 nm.
(2) Adding acetone into the graphene oxide nanosheet dispersion liquid, wherein the proportion of acetone to water is 8. And (4) centrifuging the mixed dispersion liquid at a high speed, collecting the nanocapsules, and re-dispersing the collected product in acetone. In order to observe the recovery properties of the nanocapsules, the nanocapsules obtained by centrifugation were redispersed in an aqueous solution and observed by transmission electron microscopy after 1 and 12 hours of dispersion in the aqueous solution. After 1h, most of the nanocapsules recover the original two-dimensional sheet structure; and observing after 12h, and recovering all the nanocapsules to the original two-dimensional sheet structure.
(3) Preparing samples of the graphene oxide nanocapsules dispersed in the acetone solution and the recovered nanocapsules, and feeding the prepared samples into a transmission electron microscope for observation.
Under the above conditions, the two-dimensional graphene oxide-based nanosheet material shown in fig. 1a is synthesized into the hollow nanocapsule by using the two-dimensional graphene oxide-based nanomaterial through a solvent induction method, and as a result, the synthesized hollow nanocapsule has a uniform size and presents a multi-layer wrapped and curled hollow capsule structure as shown in fig. 2 ab. And as shown in fig. 3ab, after the nanocapsules are redispersed in the aqueous solution, the original two-dimensional spreading form can be recovered, so that the form regulation is reversible.
Comparative example 1
The difference from example 1 is that: the ultrasonic temperature is 50 ℃, and the ultrasonic time is 12h, so that the uniformly dispersed nanosheet dispersion with the size of 50nm is formed.
As can be seen from the transmission electron micrograph of FIG. 4, a solid structure was produced, not a hollow structure.
Comparative example 2
The difference from example 1 is that: 4mg/mL of the nanosheet dispersion was formed.
As can be seen from the transmission electron micrograph of FIG. 5, the prepared structure is also a solid structure, not a hollow structure.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. A hollow graphene capsule is characterized in that the hollow graphene capsule is formed by self-curling of graphene-based nano sheets to form a hollow closed structure, and the closed structure has reversibility; the thickness of the hollow graphene capsule is the same as that of the graphene-based nanosheet; the particle size of the hollow graphene capsule is 30-90 nm.
2. The hollow graphene capsule according to claim 1, wherein the two-dimensional structure of the graphene-based nanosheets can be restored within 1-24h by dispersing the hollow graphene capsule in water.
3. A solvent-induced self-crimping method for preparing the hollow graphene capsule of claim 1 or 2, comprising the steps of:
(1) Dispersing graphene-based nanosheets into deionized water, and performing ultrasonic treatment to form uniformly dispersed graphene-based nano dispersion liquid;
(2) And adding a nonpolar solvent into the graphene-based nano dispersion liquid to obtain the self-curled hollow graphene capsule.
4. The production method according to claim 3, wherein in step (1), the graphene-based nanoplatelets are selected from graphene nanoplatelets, graphene oxide nanoplatelets, nitrogen-doped graphene nanoplatelets or reduced graphene oxide nanoplatelets.
5. The preparation method according to claim 3, wherein in the step (1), the concentration of the graphene-based nanodispersion is 1-2.5mg/mL.
6. The preparation method according to claim 3, wherein in the step (1), the power of the ultrasonic treatment is 42kHz, the frequency is 100W, and the time is 6-8 h; the temperature of the ultrasonic treatment is 30-40 ℃.
7. The preparation method according to claim 3, wherein in the step (1), the size of the graphene-based nanoplatelets in the graphene-based nanodispersion is 150-300nm.
8. The preparation method according to claim 3, wherein in the step (2), the volume ratio of the nonpolar solvent to the deionized water is (1-10): 1.
9. the method according to claim 3, wherein in the step (2), the nonpolar solvent is a nonpolar organic solvent selected from at least one of ethanol, acetone, ethyl acetate, tetrahydrofuran, diethyl ether, N-hexane, and N, N-dimethylformamide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20170088747A (en) * | 2014-12-23 | 2017-08-02 | 유씨엘 비즈니스 피엘씨 | Method for producing dispersions of nanosheets |
| US20180028715A1 (en) * | 2016-07-27 | 2018-02-01 | Contraline, Inc. | Carbon-based compositions useful for occlusive medical devices and methods of making and using them |
| CN113023713A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Preparation method of red phosphorus/graphene composite roll |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170088747A (en) * | 2014-12-23 | 2017-08-02 | 유씨엘 비즈니스 피엘씨 | Method for producing dispersions of nanosheets |
| US20180028715A1 (en) * | 2016-07-27 | 2018-02-01 | Contraline, Inc. | Carbon-based compositions useful for occlusive medical devices and methods of making and using them |
| CN113023713A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Preparation method of red phosphorus/graphene composite roll |
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