CN103121672B - 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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- CN103121672B CN103121672B CN201310090294.7A CN201310090294A CN103121672B CN 103121672 B CN103121672 B CN 103121672B CN 201310090294 A CN201310090294 A CN 201310090294A CN 103121672 B CN103121672 B CN 103121672B
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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, single-layer graphene (Science has successfully prepared by microcomputer stripping method in the Geim seminar of Britain graceful Chester university, 2004,306,666-669), studies show that, Graphene is comprised of the tightly packed flat monolayer carbon atom forming of bi-dimensional cellular shape lattice, between its each carbon atom and three carbon atoms close with it, by σ key, be connected, form sp
2hybrid structure; Each carbon atom also has a 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 the experimental studies such as Graphene and derivative preparation, character and application.
At present, people mainly concentrate on two-dimensional material self-assembly aspect for the research of Graphene, a remarkable defect of this structure is to exist between graphene sheet layer strong interaction, thereby be easily superimposed with each other, cannot make Graphene there is higher specific surface area, the advantageous characteristic of performance nanoscale twins, the application in some fields is restricted.
Summary of the invention
One of object of the present invention is to propose a kind of graphene oxide microballoon with three-dimensional porous structure, with it, overcomes deficiency of the prior art.
Two of object of the present invention is to provide a kind of Graphene microballoon.
Three of object of the present invention be to provide a kind of have simple to operate, cost is low, production efficiency high, and the preparation method of the graphene oxide microballoon that can accomplish scale production and Graphene microballoon.
Four of object 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 graphene oxide microballoon, comprises the three-dimensional porous structure mainly being formed by graphene oxide sheet assembling, and described three-dimensional porous structure comprises class red blood cell structure.
A Graphene microballoon, comprises the three-dimensional porous structure mainly being formed by the graphene oxide sheet assembling of reducing, and described three-dimensional porous structure comprises 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 edge is thicker, and middle hollow, external diameter is adjustable within the scope of 10-50 μ m at 70-300 μ m, internal diameter.
A preparation method for graphene oxide microballoon, comprising:
(1) electrostatic spray: precursor solution is processed and formed microspheroidal drop through electrostatic spray;
(2) wet method is collected: by described microspheroidal drop input solidification liquid, make graphene oxide microballoon;
Wherein, described precursor solution comprises graphene oxide suspension;
The solution of the solution that described solidification liquid comprises cats product or polycation solution material;
Described graphene oxide microballoon comprises the three-dimensional porous structure mainly being formed by 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 with the speed of injecting of setting, make precursor solution from the ejection of conduction syringe needle, form 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 by described microspheroidal drop input solidification liquid, make 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 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 within the scope of 20-300 μ m.
Compared with prior art, the present invention at least tool have the following advantages:
(1) the present invention adopts electrostatic spray-wet method to collect and forms graphene oxide microballoon, and injection stream, in arriving the process of solidification liquid, is accompanied by the volatilization of solvent, forms vesicular structure; Graphene oxide drop arrives after solidification liquid, functional component in solidification liquid (as, cats product) in and graphene oxide lamella surface charge, form fold, graphene oxide lamella bending, folding, graphene oxide microballoon is had compared with 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, be raw materials usedly easy to get, production cost is lower, efficiency is high, can realize preparation in enormous quantities.
Accompanying drawing explanation
Fig. 1 is the structural representation of electrostatic spray-wet method collection device in the present invention's one better embodiment;
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 forming, 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 of preparing aforementioned graphene oxide microballoon and Graphene microballoon, its have simple to operate, cost is low, production efficiency is high, the feature 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 Fig. 1 apparatus shown, and can comprise the steps:
(1) electrostatic spray: with set the speed pushing belt of injecting have metal needle in have the plastic injector of graphene oxide suspension, metal needle connects positive high voltage equipment, under DC Electric Field, graphene oxide suspension sprays in the mode of microballoon.
(2) wet method collection: with the CTAB(cetyl trimethylammonium bromide of setting stirring velocity) aqueous solution is done solidification liquid and is collected graphene oxide microballoon, microballoon arrives after solidification liquid, in solidification liquid in solution and graphene oxide water solvent through a double diffusion process, finally reach the state of a balance, now graphene oxide microballoon size is fixed.
Further, for obtaining Graphene microballoon, aforementioned preparation method also can further comprise following steps:
(3) reduction: hydrazine hydrate reduction graphene oxide microballoon obtains Graphene microballoon.
The voltage of the extra electric field of abovementioned steps in (1) can be 0-30 KV, to form electrostatic field.Graphene oxide suspension drop is subject to self surface tension effects and keeps crescent at syringe needle nozzle exit, after applying high pressure, under the induction 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 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 continues to increase, when the electrostatic force of charge generation is enough to overcome its surface tension, just ejection from " taylor cone " of drop, is broken into many graphene oxide small dropletss.Along with the increase of voltage, droplet dia reduces, and when increasing to a certain degree, occurs bead phenomenon, and diameter increases.
The inject speed of abovementioned steps in (1) can be 0.001-90 mm/min, and along with reducing of the speed of injecting, graphene oxide microballoon presents and reduces trend.
The graphene oxide strength of solution of abovementioned steps in (1) 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 increases, diameter also increases thereupon.
The graphene oxide dispersion liquid of abovementioned steps in (1) can be graphite (Graphite) the graphene oxide single or multiple lift dispersion liquid that oxidation obtains through 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.
The stirring velocity of abovementioned steps in (2) can be 0-1500 rpm, and along with the increase of stirring velocity, double diffusion speed is accelerated, and graphene oxide microsphere diameter reduces.
The CTAB(cetyl trimethylammonium bromide of abovementioned steps in (2)) 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 graphene oxide tiny balloon; When CTAB concentration increases gradually, graphene oxide class red blood cell structure is more and more, and while increasing to 0.75 mg/ml, 90 % are graphene oxide class red blood cell structure.
Abovementioned steps (2) described in solidification liquid 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.
The hydrazine hydrate reduction of abovementioned steps in (3) can be other reductive agents, as sodium borohydride, hydroiodic acid HI, xitix etc.
The diameter that aforementioned preparation method obtains graphene oxide microballoon can regulate and control between 20-300 μ m.
The present invention has utilized electrostatic spray technology first to control the diameter of graphene oxide drop, to the graphene oxide suspension flowing out with the speed of necessarily injecting, apply high pressure, graphene oxide suspension drop is subject to the surface tension of self and the electrical forces effect contrary 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, in arriving the process of receptor, is accompanied by the volatilization of solvent, has certain vesicular structure to form.
Recycling wet method receives, when graphene oxide small droplets arrives after CTAB solidification liquid, electronegative being neutralized of drop outer ring graphene oxide, graphene oxide bending tablet, folding, solidifies curingly, between drop internal solvent water and the solidification liquid CTAB aqueous solution, forms double diffusion, water is toward external diffusion time, transporting graphene oxide lamella constantly to diffuse interface motion, the CTAB aqueous solution, constantly to drop internal divergence, also solidifies its internal oxidation graphene sheet layer.
Because graphene oxide drop itself is ejection spherical in shape, along with the carrying out of double diffusion effect, internal oxidation graphene sheet layer moves to interface, forms tiny balloon; When the CTAB aqueous solution is very fast to graphene oxide microballoon inner diffusing rate, when not arriving interface completely, 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.After reduction, obtain Graphene microballoon.
The present invention obtains 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, there is broad prospect of application, 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.
Below in conjunction with some preferred embodiments, the technical solution of the present invention is further explained.
It should be noted that, the experimental technique using in following embodiment if no special instructions, is ordinary method, 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 used Milli-Q high purity water (18.2 Μ Ω) that is in experimentation.
Postscript, wherein graphene oxide can be standby by hummers legal system.
embodiment 1:
12.5 mg/ml graphene oxide suspension are carried out to EFI and stir and receive with the 0.35 mg/ml CTAB aqueous solution.Electrostatic spray-wet method collection device as shown in Figure 1, comprises puopulsion unit, electrostatic generator and receiving trap.In 2 ml plastic injectors, suck a certain amount of graphene oxide suspension, needle point internal diameter 0.50 mm.The positive pole of high-voltage power supply is connected on needle point to receiving trap solidification liquid ground connection.In the speed of injecting, be 0.05 mm/min, impressed voltage is to form and stablize injection stream under the condition of 9 KV, low whipping speed is 2, CTAB concentration receives graphene oxide microballoon while being 0.35 mg/ml, obtain graphene oxide tiny balloon, by Powerful Light Microscope and scanning electronic microscope, observe.
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, by Fig. 3 a, can find out that prepared graphene oxide has micro-sphere structure, and its diameter is about 104 μ m; Under Fig. 3 b of high magnification more, observe, 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 to EFI and stir and receive with the 0.55 mg/ml CTAB aqueous solution.In 2 ml plastic injectors, suck a certain amount of graphene oxide suspension, needle point internal diameter 0.50 mm.The positive pole of high-voltage power supply is connected on needle point to receiving trap solidification liquid ground connection.In the speed of injecting, be 0.05 mm/min, impressed voltage is to form and stablize injection stream under the condition of 9 KV, low whipping speed is 2, CTAB concentration receives graphene oxide microballoon while being 0.55 mg/ml, obtain graphene oxide tiny balloon, part for graphene oxide class red blood cell structure, by Powerful Light Microscope and scanning electronic microscope, observe.
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, by Fig. 5 a, can find out that prepared graphene oxide has micro-sphere structure, and its diameter is about 81 μ m; Under Fig. 5 b of high magnification more, observe, 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 to EFI and stir and receive with the 0.75 mg/ml CTAB aqueous solution.In 2 ml plastic injectors, suck a certain amount of graphene oxide suspension, needle point internal diameter 0.50 mm.The positive pole of high-voltage power supply is connected on needle point to receiving trap solidification liquid ground connection.In the speed of injecting, be 0.05 mm/min, impressed voltage is to form and stablize injection stream under the condition of 9 KV, low whipping speed is 2, CTAB concentration receives graphene oxide microballoon while being 0.75 mg/ml, obtain graphene oxide class red blood cell structure, at 80 ℃, hydrazine hydrate reduction obtains Graphene class red blood cell structure.By Powerful Light Microscope and scanning electronic microscope, observe.
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, mean outside diameter approximately 89 μ m, internal diameter approximately 34 μ m.Fig. 7 a-7b is the electron scanning micrograph of graphene oxide class red blood cell structure, by Fig. 7 a, can find out prepared graphene oxide class red blood cell structure, its external diameter approximately 90.4 μ m, internal diameter approximately 16 μ m; Under Fig. 7 b of high magnification more, observe, 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, by Fig. 8 a, can find out that 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 people was easy to know by inference, all do not depart from patent right scope of the present invention.
Claims (10)
1. a graphene oxide microballoon, comprises the three-dimensional porous structure mainly being formed by graphene oxide sheet assembling, it is characterized in that, described three-dimensional porous structure comprises class red blood cell structure.
2. a Graphene microballoon, is characterized in that, comprises the three-dimensional porous structure mainly being formed by the graphene oxide sheet assembling of reducing, and described three-dimensional porous structure comprises class red blood cell structure.
3. a preparation method for graphene oxide microballoon, is characterized in that, comprising:
(1) electrostatic spray: precursor solution is processed and formed microspheroidal drop through electrostatic spray;
(2) wet method is collected: by described microspheroidal drop input solidification liquid, make graphene oxide microballoon;
Wherein, described precursor solution comprises graphene oxide suspension;
The solution that described solidification liquid comprises cats product;
Described graphene oxide microballoon comprises the three-dimensional porous structure mainly being formed by graphene oxide sheet assembling, and described three-dimensional porous structure comprises spherical hollow structure, class red blood cell structure or bagel 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 with the speed of injecting of setting, make precursor solution from the ejection of conduction syringe needle, form microspheroidal drop.
5. according to the preparation method of the graphene oxide microballoon described in claim 3 or 4, 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 0-30KV, and the setting speed of injecting is 0.001-90mm/min, and the concentration of described graphene oxide solution is 0.02-20mg/ml.
8. the preparation method of graphene oxide microballoon according to claim 3, it is characterized in that, step (2) comprising: the speed with 0-1500rpm stirs solidification liquid, and by described microspheroidal drop input solidification liquid, make graphene oxide microballoon, wherein, described solidification liquid comprises the cetyl trimethylammonium bromide aqueous solution that concentration is 0.1mg/ml-2mg/ml.
9. the preparation method of a Graphene microballoon, it is characterized in that, comprise: get the prepared graphene oxide microballoon of any one method in graphene oxide microballoon described in claim 1 or claim 3-8 and make 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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| CN108314029B (en) * | 2018-01-18 | 2019-03-12 | 东莞理工学院 | Hollow bowl-shape graphene oxide micro motor and preparation method thereof |
| CN110364682B (en) * | 2018-04-11 | 2022-06-24 | 广州墨羲科技有限公司 | Three-dimensional graphene microsphere composite material, and manufacturing method and application thereof |
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