CN103121672A - Graphene oxide microsphere and graphene microsphere and preparation methods thereof - Google Patents
Graphene oxide microsphere and graphene microsphere and preparation methods thereof Download PDFInfo
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Abstract
The invention discloses a graphene oxide microsphere and a graphene microsphere and preparation methods thereof. The graphene oxide microsphere and the graphene microsphere respectively comprise a three-dimensional porous structure mainly formed by assembling graphene oxide slices or reduced graphene oxide slices, wherein the three-dimensional porous structure comprises a simulated erythrocyte structure. The preparation method of the graphene oxide microsphere comprises the following steps: (1) electrostatic spraying: carrying out electrostatic spraying treatment on a precursor solution, so that a microsphere-shaped liquid drop is formed; and (2) wet collection: injecting a solidification liquid into the microsphere-shaped liquid drop, so that the graphene oxide microsphere is prepared. The preparation method of the graphene microsphere comprises the following step: preparing the graphene oxide microsphere into the graphene microsphere by utilizing a chemical reduction method. The preparation methods are simple to operate and convenient to regulate and control. The prepared graphene microsphere is high in purity, and the raw materials are obtained easily, so that the production cost is low and the production efficiency is high. Therefore, the graphene microsphere can be prepared in batches.
Description
Technical field
The present invention relates to a kind of novel graphite alkene material and preparation technology thereof, relate in particular to a kind of graphene oxide microballoon, Graphene microballoon and preparation method thereof, belong to material science, particularly nano material or inorganic functional material field.
Background technology
2004, the Geim seminar of Britain graceful Chester university has successfully prepared single-layer graphene (Science by the microcomputer stripping method, 2004,306,666-669), studies show that, Graphene is comprised of the tightly packed flat monolayer carbon atom that forms of bi-dimensional cellular shape lattice, be connected by the σ key between its each carbon atom and three carbon atoms close with it, form sp
2Hybrid structure; Each carbon atom also has the not π-electron of Cheng Jian simultaneously, and this residue π-electron can move freely in crystal.The theoretic throat of Graphene is only 0.34 nm, is considered to the basic structural unit of other each dimension Carbon Materials, and it can be overmolding to the soccerballene of zero dimension, is curled into the nanotube of one dimension, is piled into three-dimensional graphite.Compare with other Carbon Materials, Graphene has good electroconductibility, high mechanical property, stable chemical, the huge more excellent character such as specific surface area, thus the New Times of having opened Graphene and the experimental studies such as derivative preparation, character and application thereof.
At present, people mainly concentrate on two-dimensional material self-assembly aspect for the research of Graphene, a remarkable defective of this structure is to exist between graphene sheet layer strong interaction, thereby easily be superimposed with each other, can't make Graphene have higher specific surface area, the advantageous characteristic of performance nanoscale twins, the application in some fields is restricted.
Summary of the invention
One of purpose of the present invention is to propose a kind of graphene oxide microballoon with three-dimensional porous structure, overcomes deficiency of the prior art with it.
Two of purpose of the present invention is to provide a kind of Graphene microballoon.
Three of purpose of the present invention be to provide a kind of have simple to operate, cost is low, the production efficiency high, and the preparation method of the graphene oxide microballoon that can accomplish scale production and Graphene microballoon.
Four of purpose of the present invention is to provide the application of aforementioned Graphene microballoon in fields such as environmental improvement, sensing, medical treatment, the energy.
For realizing aforementioned goal of the invention, the present invention has adopted following technical scheme:
A kind of graphene oxide microballoon comprises the three-dimensional porous structure that is mainly formed by the graphene oxide sheet assembling, and described three-dimensional porous structure comprises the class red blood cell structure.
A kind of Graphene microballoon comprises mainly and assembles by the graphene oxide sheet of reduction the three-dimensional porous structure that forms that described three-dimensional porous structure comprises the class red blood cell structure.
Described class red blood cell structure is for being similar to erythrocytic structure, and particularly, it is the round pie structure of two sides indent, and the edge is thicker, and middle hollow, external diameter is adjustable in 10-50 μ m scope at 70-300 μ m, internal diameter.
A kind of preparation method of graphene oxide microballoon comprises:
(1) electrostatic spray: precursor solution is processed through electrostatic spray formed the microspheroidal drop;
(2) wet method is collected: with described microspheroidal drop input solidification liquid, make the graphene oxide microballoon;
Wherein, described precursor solution comprises graphene oxide suspension;
Described solidification liquid comprises the solution of cats product or the solution of polycation solution material;
Described graphene oxide microballoon comprises the three-dimensional porous structure that is mainly formed by the graphene oxide sheet assembling, and described three-dimensional porous structure comprises spherical hollow structure, class red blood cell structure, bagel structure, class tadpole structure, jellyfish structure or nucleocapsid structure.
As one of comparatively preferred embodiment, described electrostatic spray is processed and is comprised: precursor solution is placed in jet apparatus, and apply setting voltage on the conduction syringe needle of described jet apparatus, then make precursor solution from the ejection of conduction syringe needle with the speed of injecting of setting, form the microspheroidal drop.
As one of comparatively preferred embodiment, described precursor solution also comprises the functional materials compound with graphene oxide suspension, described functional materials comprises metal and/or nonmetal nano material, functional high molecule material, biomolecules material or organic small molecule material, but is not limited to this.
As one of comparatively preferred embodiment, described solidification liquid comprises the aqueous solution of cats product, and described cats product comprises cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride, but is not limited to this.
As one of comparatively preferred embodiment, the condition that described electrostatic spray is processed comprises: setting voltage is 0-30 KV, and setting the speed of injecting is 0.001-90 mm/min, and the concentration of described graphene oxide solution is 0.02-20 mg/ml.
As one of comparatively preferred embodiment, step (2) comprising: the speed with 0-1500 rpm stirs solidification liquid, and with described microspheroidal drop input solidification liquid, make the graphene oxide microballoon, wherein, described solidification liquid comprises the cetyl trimethylammonium bromide aqueous solution that concentration is 0.1 mg/ml-2 mg/ml.
A kind of preparation method of Graphene microballoon, it is characterized in that, comprise: get the prepared graphene oxide microballoon of above-mentioned graphene oxide microballoon or aforesaid method and make the Graphene microballoon through chemical reduction method, described chemical reduction method comprises the methods such as chemical reduction, photoreduction or thermochemistry reduction based on reductive agent, and described reductive agent comprises hydrazine hydrate, sodium borohydride, hydroiodic acid HI or xitix.
Further, the diameter of described Graphene microballoon is adjustable in 20-300 μ m scope.
Compared with prior art, the present invention has following advantage at least:
(1) the present invention adopts electrostatic spray-wet method to collect and forms the graphene oxide microballoon, and injection stream is accompanied by the volatilization of solvent in the process that arrives solidification liquid, form vesicular structure; After the graphene oxide drop arrives solidification liquid, functional component in solidification liquid (as, cats product) in and graphene oxide lamella surface charge, form fold, graphene oxide lamella bending, folding, make the graphene oxide microballoon have than bigger serface, aqueous solvent and the CTAB aqueous solution carry out double diffusion, form vesicular structure, and this graphene oxide microballoon is expected to have broad application prospects at aspects such as absorption, sensing, lithium electricity and Chu Qing.
(2) relatively simple, the conveniently regulating and controlling of technological operation of the present invention, can prepare high purity oxygen functionalized graphene microballoon, raw materials usedly be easy to get, production cost is lower, efficient is high, can realize preparation in enormous quantities.
Description of drawings
Fig. 1 is the structural representation of electrostatic spray in the present invention's one better embodiment-wet method collection device;
Fig. 2 is the optical microscope photograph of the embodiment 1 graphene oxide tiny balloon that obtains;
Fig. 3 a and Fig. 3 b are the electron scanning micrograph of the embodiment 1 graphene oxide tiny balloon that obtains;
Fig. 4 is the optical microscope photograph of the embodiment 2 graphene oxide microballoon that obtains;
Fig. 5 a-Fig. 5 b is the electron scanning micrograph of the embodiment 2 graphene oxide microballoon that obtains;
Fig. 6 is the optical microscope photograph of the embodiment 3 graphite oxide class red blood cell structure microballoon that obtains;
Fig. 7 a-Fig. 7 b is the electron scanning micrograph of the embodiment 3 graphene oxide class red blood cell structure microballoon that obtains;
Fig. 8 a-Fig. 8 b is the electron scanning micrograph of the embodiment 3 Graphene class red blood cell structure microballoon that obtains.
Embodiment
One aspect of the present invention aims to provide a kind of novel material based on Graphene, particularly a kind of graphene oxide microballoon and Graphene microballoon, it has mainly assembles by graphene oxide sheet or through the graphene oxide sheet of reduction the three-dimensional porous structure that forms, and described three-dimensional porous structure comprises spherical hollow structure, class red blood cell structure, bagel structure, class tadpole structure, jellyfish structure or nucleocapsid structure etc.Particularly, wherein-class red blood cell structure microballoon Graphene has significant porous, pleated structure.
Another aspect of the present invention aims to provide a kind of method for preparing aforementioned graphene oxide microballoon and Graphene microballoon, its have simple to operate, cost is low, production efficiency is high, the characteristics such as can large batch ofly prepare, and, the method can by regulate the regulation and control of different experiment parameter the radius of the graphene oxide microballoon that obtains or Graphene microballoon.
In of the present invention one comparatively preferred concrete application examples, the preparation technology of this graphene oxide microballoon can implement by equipment shown in Figure 1, and can comprise the steps:
⑴ electrostatic spray: with setting inject the speed pushing belt have metal needle in the plastic injector of graphene oxide suspension is arranged, metal needle connects positive high voltage equipment, under DC Electric Field, graphene oxide suspension sprays in the mode of microballoon.
⑵ wet method collection: with the CTAB(cetyl trimethylammonium bromide of setting stirring velocity) aqueous solution is done solidification liquid and is collected the graphene oxide microballoon, after microballoon arrives solidification liquid, in solidification liquid in solution and graphene oxide water solvent through a double diffusion process, finally reach the state of a balance, this moment, graphene oxide microballoon size was fixed.
Further, for obtaining the Graphene microballoon, aforementioned preparation method also can further comprise following steps:
⑶ reduction: hydrazine hydrate reduction graphene oxide microballoon obtains the Graphene microballoon.
The voltage of the extra electric field in abovementioned steps ⑴ can be 0-30 KV, to form electrostatic field.The graphene oxide suspension drop is subject to self surface tension effects and keeps crescent at the syringe needle nozzle exit, after applying high pressure, under the inducing of electrical forces, make that graphene oxide suspension is inner assembles a large amount of electric charges, drop is subject to an electrical forces with the surface tension opposite direction.Along with strength of electric field increases gradually, the drop at nozzle place is taper by spherical elongation, is referred to as taylor cone.When strength of electric field continuation increase, when the electrostatic force of charge generation was enough to overcome its surface tension, just ejection from " taylor cone " of drop was broken into many graphene oxide small dropletss.Along with the increase of voltage, droplet dia reduces, and when increasing to a certain degree, the bead phenomenon occurs, and diameter increases.
The speed of injecting in abovementioned steps ⑴ can be 0.001-90 mm/min, and along with reducing of the speed of injecting, the graphene oxide microballoon presents and reduces trend.
Graphene oxide strength of solution in abovementioned steps ⑴ can be 0.02-20 mg/ml, also can adopt common ultrasonic, cytoclasis is ultrasonic etc., and different modes is peeled off.When graphene oxide concentration hour, essentially no graphene oxide microballoon forms, after concentration increased, diameter also increased thereupon.
Graphene oxide dispersion liquid in abovementioned steps ⑴ can be graphite (Graphite) the graphene oxide single or multiple lift dispersion liquid that oxidation obtains through the HUMMMERS method, further compound other functional materials also comprises nanostructure, DNA biomolecules, medicine organic molecule, the functional high molecule materials etc. such as carbon nanotube, metal, nonmetal, metal oxide, sulfide.
Stirring velocity in abovementioned steps ⑵ can be 0-1500 rpm, and along with the increase of stirring velocity, double diffusion speed is accelerated, and the graphene oxide microsphere diameter reduces.
CTAB(cetyl trimethylammonium bromide in abovementioned steps ⑵) concentration of aqueous solution can be 0.1-2 mg/ml.CTAB concentration has the greatest impact to graphene oxide microballoon pattern.In CTAB concentration hour, 90 % are the graphene oxide tiny balloon; When CTAB concentration increased gradually, graphene oxide class red blood cell structure was more and more, and when increasing to 0.75 mg/ml, 90 % are graphene oxide class red blood cell structure.
Solidification liquid described in abovementioned steps ⑵ can be other solution, as polycation solution material of other cats product palmityl trimethyl ammonium chlorides, natural and synthetic etc.
Abovementioned steps (3) also can adopt the treatment processs such as photoreduction, thermochemistry reduction.
Hydrazine hydrate reduction in abovementioned steps ⑶ can be other reductive agents, as sodium borohydride, hydroiodic acid HI, xitix etc.
The diameter that aforementioned preparation method obtains the graphene oxide microballoon can regulate and control between 20-300 μ m.
The present invention has utilized the electrostatic spray technology first to control the diameter of graphene oxide drop, apply high pressure to the graphene oxide suspension that flows out with the speed of necessarily injecting, the graphene oxide suspension drop is subject to the surface tension of self and the electrical forces effect opposite with it.Along with strength of electric field increases gradually, form taylor cone.When strength of electric field reaches a threshold value, just ejection from " taylor cone " of drop is broken into many graphene oxide small dropletss.Injection stream is accompanied by the volatilization of solvent in the process that arrives receptor, have certain vesicular structure to form.
The recycling wet method receives, after the graphene oxide small droplets arrives the CTAB solidification liquid, electronegative being neutralized of drop outer ring graphene oxide, graphene oxide bending tablet, folding solidifies curing, forms double diffusion between drop internal solvent water and the solidification liquid CTAB aqueous solution, in the time of the past external diffusion of water, transporting the graphene oxide lamella constantly to the diffuse interface motion, the CTAB aqueous solution also solidifies its internal oxidation graphene sheet layer constantly to the drop internal divergence.
Because the graphene oxide drop itself is ejection spherical in shape, along with the carrying out of double diffusion effect, the internal oxidation graphene sheet layer forms tiny balloon to motion at the interface; When the CTAB aqueous solution is very fast to graphene oxide microballoon inner diffusing rate, when arriving at the interface fully, the internal oxidation graphene sheet layer in solidified inside, do not obtain a kind of graphene oxide of new pattern---class red blood cell structure microballoon graphene oxide.Obtain the Graphene microballoon after reduction.
The present invention obtains the Graphene microballoon and can present by macroscopical forms such as dispersion liquid, powder, film, fibrous reticulum, ball float and blocks.
Graphene microballoon of the present invention, in fields such as environmental improvement, sensing, medical treatment, the energy, broad prospect of application is arranged, as: the electrochemical energy storages such as absorption, oily water separation, ultracapacitor, lithium ion battery, fuel cell, medicine controlled release carrier, electrochemical sensing electrode etc.
The technical solution of the present invention is further explained below in conjunction with some preferred embodiments.
Need to prove, the experimental technique that uses in following embodiment is ordinary method if no special instructions, and material, reagent and instrument used wherein if no special instructions, all can be bought by commercial sources.Agents useful for same is analytical pure.The Milli-Q high purity water (18.2 Μ Ω) that is used in experimentation.
Postscript, wherein graphene oxide can be standby by the hummers legal system.
Embodiment 1:
12.5 mg/ml graphene oxide suspension are carried out EFI and stir with the 0.35 mg/ml CTAB aqueous solution receive.Electrostatic spray-wet method collection device comprises puopulsion unit, electrostatic generator and receiving trap as shown in Figure 1.Suck a certain amount of graphene oxide suspension, needle point internal diameter 0.50 mm in 2 ml plastic injectors.The positive pole of high-voltage power supply is connected on needle point receiving trap solidification liquid ground connection.Be 0.05 mm/min in the speed of injecting, impressed voltage is to form under the condition of 9 KV to stablize injection stream, low whipping speed is 2, reception graphene oxide microballoon when CTAB concentration is 0.35 mg/ml, obtain the graphene oxide tiny balloon, observe by Powerful Light Microscope and scanning electronic microscope.
Fig. 2 is the optical microscope photograph of above-mentioned graphene oxide tiny balloon, as can be seen from the figure its size homogeneous comparatively, and diameter is in 90 μ m left and right.Fig. 3 a-3b is the electron scanning micrograph of graphene oxide tiny balloon, can find out that by Fig. 3 a prepared graphene oxide has micro-sphere structure, and its diameter is about 104 μ m; Observe under Fig. 3 b of high magnification more, can find out that the lamella of graphene oxide microsphere surface has obvious fold.
Embodiment 2:
12.5 mg/ml graphene oxide suspension are carried out EFI and stir with the 0.55 mg/ml CTAB aqueous solution receive.Suck a certain amount of graphene oxide suspension, needle point internal diameter 0.50 mm in 2 ml plastic injectors.The positive pole of high-voltage power supply is connected on needle point receiving trap solidification liquid ground connection.Be 0.05 mm/min in the speed of injecting, impressed voltage is to form under the condition of 9 KV to stablize injection stream, low whipping speed is 2, reception graphene oxide microballoon when CTAB concentration is 0.55 mg/ml, obtain graphene oxide tiny balloon, part for graphene oxide class red blood cell structure, observe by Powerful Light Microscope and scanning electronic microscope.
Fig. 4 is the optical microscope photograph of above-mentioned graphene oxide microballoon, as can be seen from the figure its size homogeneous comparatively, and diameter is in 99 μ m left and right.Fig. 5 a-5b is the electron scanning micrograph of graphene oxide microballoon, can find out that by Fig. 5 a prepared graphene oxide has micro-sphere structure, and its diameter is about 81 μ m; Observe under Fig. 5 b of high magnification more, can find out that graphene oxide microballoon external and internal compositions is variant.
Embodiment 3:
12.5 mg/ml graphene oxide suspension are carried out EFI and stir with the 0.75 mg/ml CTAB aqueous solution receive.Suck a certain amount of graphene oxide suspension, needle point internal diameter 0.50 mm in 2 ml plastic injectors.The positive pole of high-voltage power supply is connected on needle point receiving trap solidification liquid ground connection.Be 0.05 mm/min in the speed of injecting, impressed voltage is to form under the condition of 9 KV to stablize injection stream, low whipping speed is 2, reception graphene oxide microballoon when CTAB concentration is 0.75 mg/ml, obtain graphene oxide class red blood cell structure, under 80 ℃, hydrazine hydrate reduction obtains Graphene class red blood cell structure.Observe by Powerful Light Microscope and scanning electronic microscope.
Fig. 6 is the optical microscope photograph of above-mentioned graphene oxide class red blood cell structure, as can be seen from the figure its size homogeneous comparatively, and mean outside diameter is 89 μ m approximately, and internal diameter is 34 μ m approximately.Fig. 7 a-7b is the electron scanning micrograph of graphene oxide class red blood cell structure, can find out prepared graphene oxide class red blood cell structure by Fig. 7 a, and its external diameter is 90.4 μ m approximately, and internal diameter is 16 μ m approximately; Observe under Fig. 7 b of high magnification more, can find out obvious fold.Fig. 8 a-8b is the electron scanning micrograph of the Graphene class red blood cell structure of hydrazine hydrate reduction, can find out that by Fig. 8 a Graphene class red blood cell structure is very fluffy, porous; Fig. 8 b can find out the many folds of Graphene class red blood cell structure, loose porous.
It is pointed out that disclosed is one or more of preferred embodiment, the change of every part or modification and come from technological thought of the present invention and be have the knack of this technology the people was easy to know by inference, all do not break away from patent right scope of the present invention.
Claims (10)
1. a graphene oxide microballoon, comprise the three-dimensional porous structure that is mainly formed by the graphene oxide sheet assembling, it is characterized in that, described three-dimensional porous structure comprises the class red blood cell structure.
2. a Graphene microballoon, is characterized in that, comprises mainly assembling by the graphene oxide sheet of reduction the three-dimensional porous structure that forms, and described three-dimensional porous structure comprises the class red blood cell structure.
3. the preparation method of a graphene oxide microballoon, is characterized in that, comprising:
(1) electrostatic spray: precursor solution is processed through electrostatic spray formed the microspheroidal drop;
(2) wet method is collected: with described microspheroidal drop input solidification liquid, make the graphene oxide microballoon;
Wherein, described precursor solution comprises graphene oxide suspension;
Described solidification liquid comprises the solution of cats product or the solution of polycation solution material;
Described graphene oxide microballoon comprises the three-dimensional porous structure that is mainly formed by the graphene oxide sheet assembling, and described three-dimensional porous structure comprises spherical hollow structure, class red blood cell structure, bagel structure, class tadpole structure, jellyfish structure or nucleocapsid structure.
4. the preparation method of graphene oxide microballoon according to claim 3, it is characterized in that, described electrostatic spray is processed and is comprised: precursor solution is placed in jet apparatus, and apply setting voltage on the conduction syringe needle of described jet apparatus, then make precursor solution from the ejection of conduction syringe needle with the speed of injecting of setting, form the microspheroidal drop.
5. the preparation method of according to claim 3 or 4 described graphene oxide microballoons, it is characterized in that, described precursor solution also comprises the functional materials compound with graphene oxide suspension, and described functional materials comprises metal and/or nonmetal nano material, functional high molecule material, biomolecules material or organic small molecule material.
6. the preparation method of graphene oxide microballoon according to claim 3, it is characterized in that, described solidification liquid comprises the aqueous solution of cats product, and described cats product comprises cetyl trimethylammonium bromide or palmityl trimethyl ammonium chloride.
7. the preparation method of graphene oxide microballoon according to claim 4, it is characterized in that, the condition that described electrostatic spray is processed comprises: setting voltage is 0-30 KV, and setting the speed of injecting is 0.001-90 mm/min, and the concentration of described graphene oxide solution is 0.02-20 mg/ml.
8. the preparation method of graphene oxide microballoon according to claim 3, it is characterized in that, step (2) comprising: the speed with 0-1500 rpm stirs solidification liquid, and with described microspheroidal drop input solidification liquid, make the graphene oxide microballoon, wherein, described solidification liquid comprises the cetyl trimethylammonium bromide aqueous solution that concentration is 0.1 mg/ml-2 mg/ml.
9. the preparation method of a Graphene microballoon, it is characterized in that, comprise: get that in graphene oxide microballoon claimed in claim 1 or claim 3-8, the prepared graphene oxide microballoon of any one method makes the Graphene microballoon through chemical reduction method, described chemical reduction method comprises chemical reduction, photoreduction or the thermochemistry reduction method based on reductive agent, and described reductive agent comprises hydrazine hydrate, sodium borohydride, hydroiodic acid HI or xitix.
10. the preparation method of Graphene microballoon according to claim 9, is characterized in that, the diameter of described Graphene microballoon is 20-300 μ m.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837972A (en) * | 2010-05-28 | 2010-09-22 | 南京邮电大学 | Graphene three-dimensional structure and preparation method thereof |
| CN101982408A (en) * | 2010-10-20 | 2011-03-02 | 天津大学 | Graphene three-dimensional material as well as preparation method and application thereof |
| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
-
2013
- 2013-03-20 CN CN201310090294.7A patent/CN103121672B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837972A (en) * | 2010-05-28 | 2010-09-22 | 南京邮电大学 | Graphene three-dimensional structure and preparation method thereof |
| CN101982408A (en) * | 2010-10-20 | 2011-03-02 | 天津大学 | Graphene three-dimensional material as well as preparation method and application thereof |
| CN102923698A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Preparation method for three-dimensional porous graphene for supercapacitor |
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| CN104495830A (en) * | 2015-01-04 | 2015-04-08 | 黑龙江大学 | Preparation method of porous graphene microbeads |
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