CN110642246A - Preparation method of graphene microspheres - Google Patents
Preparation method of graphene microspheres Download PDFInfo
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- CN110642246A CN110642246A CN201810672649.6A CN201810672649A CN110642246A CN 110642246 A CN110642246 A CN 110642246A CN 201810672649 A CN201810672649 A CN 201810672649A CN 110642246 A CN110642246 A CN 110642246A
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- graphene
- oil phase
- graphene oxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012071 phase Substances 0.000 claims abstract description 76
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 42
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- 238000003756 stirring Methods 0.000 claims abstract description 37
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- 150000001875 compounds Chemical class 0.000 claims abstract description 18
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- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 35
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- 239000002002 slurry Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
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- 239000000463 material Substances 0.000 description 10
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/40—
-
- B01J35/51—
-
- B01J35/615—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses a preparation method of graphene microspheres, which comprises the following steps: 1) adjusting the pH value of an aqueous phase system of the aqueous solution of the graphene oxide to 9-11 by using an alkaline compound; 2) preparing a composite oil phase system of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 6: 1-15: 1; 3) adding a surfactant into the composite oil phase system, then adding the water phase system in the step 1), wherein the volume ratio of the oil phase to the water phase is 2:1-8:1, then adding a diamino compound, and stirring and reacting for 3-8 hours at 40-100 ℃ to obtain the graphene oxide microspheres. According to the invention, graphene is assembled together by hydrogen bonds or van der Waals force under the action of a diamine compound in a reverse emulsion system containing a composite oil phase, so that the graphene has uniform controllable size distribution, sufficient strength and a porous structure, a high-strength porous spherical shape is formed and maintained, and the application range of the graphene in a catalyst carrier is expanded.
Description
Technical Field
The invention relates to a preparation method of spherical graphene, in particular to a method for preparing graphene microspheres by an inverse emulsion method.
Background
Graphene (Graphene) is oneThe new material with single-layer sheet structure formed from carbon atoms is a planar film which is hexagonal and honeycomb-shaped, and is formed from carbon atoms by using sp2 hybridized orbitals, and has the thickness of only one carbon atom (0.334 nm). Graphene is the thinnest one of known materials, the theoretical specific surface area of the graphene reaches 2630m2/g, 1.0g of graphene can be paved on the whole football field, and the graphene also has very high mechanical property, and the theoretical strength reaches 130 GPa; when the graphene is used as a raw material to prepare the polyolefin catalyst carrier, the carrier material has very good mechanical strength, the mechanical strength of the carrier material during polymerization reaction is effectively ensured, the carrier material has a very large specific surface area, the number of active points of the carrier material during catalyst loading can be increased, and the catalyst has higher catalytic efficiency. In addition, graphene also possesses great electron mobility (15000 cm)2/(v s)) and thermal conductivity (5000W/(m K)). The speed of transferring electrons at room temperature is higher than that of the known conductor, the graphene is very similar to a carbon nano tube in chemical property and similar to layered clay in structure, and the structural characteristic enables the graphene to have great potential in improving the performance of the polymer, so that not only is the mechanical performance improved, but also the electrical and thermal functional properties of the polymer can be changed. Therefore, graphene has become a leading technology of current interest in the material science and catalytic science.
At present, there are roughly four methods for obtaining a graphene sheet material; firstly, adopt the mechanical stripping method, peel off graphite with the graphite flake at first, glue the two sides of graphite flake on a special sticky tape then, tear the sticky tape and part the graphite flake simultaneously, this method is easy to operate, but the graphite alkene size that obtains of preparation is limited to the number of piles of uncontrollable graphite alkene. The other is a Chemical Vapor Deposition (CVD) method, which can prepare large-area high-quality graphene through a CVD method, but the method still has some problems to be solved. And thirdly, an epitaxial growth method, namely, large-area single crystal SiC is heated at high temperature to grow the graphene on the single crystal SiC, Si is removed under ultra-vacuum or normal pressure to leave C, and then a graphene thin layer with the area similar to that of the original SiC is obtained, but the graphene prepared by the method still cannot reach uniform thickness, and different used substrate materials also have different influences on the growth of the graphene, so that the graphene is not easy to separate from the substrate materials. Fourthly, a Graphene Oxide (GO) reduction method, and a chemical oxidation-reduction method is the most common way for preparing graphene on a large scale. Particularly, GO is used as an important precursor for preparing graphene, and the surface of the GO has a certain amount of carboxyl, hydroxyl and epoxy functional groups, so that a good structural basis is provided for the functionalized graphene composite material.
Theoretically, thermodynamically stable spheres formed by staggered stacking of GO sheets have larger pore volume, porosity and specific surface area, and have better application prospects in the fields of biomedicine, catalysis, extraction separation, energy storage and the like. The GO prepared by the chemical oxidation method is still in a flat-layer structure generally, a three-dimensional structure is difficult to directly form, and secondary forming is needed to obtain the three-dimensional GO, namely, the GO with a lamellar structure is prepared firstly, and then the GO with the three-dimensional structure is induced by a physical or chemical means. However, GO has poor solubility and poor dispersibility in a reaction system, and cannot exist in a single-layer form due to agglomeration dispersion, which seriously affects the performance and the applicability of GO, so how to prevent the overlapping of GO sheets and form a spherical or more complex polyhedral structure by disordered stacking of single-layer graphene fragments which are originally easy to form layered stacks is a hotspot and difficulty in the current graphene research field.
At present, there are patent reports on the preparation of graphene materials with microsphere/sphere/spherical shell structures, such as: CN201210310685.0, CN201510995764.3, CN201510904410.3, CN201610566864.9, CN201611150811.5, CN201610056421.5, CN201610017335.3, CN201310090294.7, CN201510960743.8, CN201510708931.1, and the like.
WO2010/128650a2 discloses a method for preparing spherical graphene flowers by a CVD method. Dispersing graphene in water or alcohol, and performing ultrasonic treatment or ball milling, granulating and drying to obtain the spherical graphene. The methods all adopt self-assembly chemical reaction to form the three-dimensional material of the graphene. Because the flake graphene is combined by chemical bonds, in practical application, even if the graphene flower can be well dispersed in a medium, the graphene flower is dispersed in a spherical mode, and the graphene spheres or the graphene flower are difficult to be re-dispersed into the monomer graphene with the flake structure, so that the excellent performance of the graphene two-dimensional lamellar structure is greatly reduced or even can not be embodied, the application range is limited, and particularly the form of the graphene flake structure dispersion required in the field of polymer composite materials is limited.
The method for preparing the spherical graphene by adopting a physical method such as that provided by CN201110439517.7 comprises the steps of dispersing graphene in water or alcohol, carrying out ultrasonic treatment or ball milling, and then carrying out granulation and drying to obtain the spherical graphene; or stirring and dispersing the graphene powder in water, and then granulating and drying to obtain the spherical graphene. The granulation drying adopts equipment such as pyrolysis granulation drying equipment, freezing granulation drying equipment, and fluidization spray granulation equipment. The obtained spherical graphene can be applied to catalyst carriers, drug transportation, lithium ion batteries and super capacitors. But the sphericity is very poor, the morphology is extremely irregular, no porous structure exists, and the active sites cannot be uniformly distributed after the catalyst is finally loaded when the catalyst is used as a carrier.
The chemical method is more common to obtain the graphene microspheres. CN201110438815.4 reports a preparation method of graphene conversion porous carbon microspheres, graphite oxide is added into deionized water and subjected to ultrasonic stripping for 30-300 min to obtain graphene oxide dispersion liquid, an acid or alkali initiator is added and mixed uniformly, the concentration of the initiator in the graphite oxide dispersion liquid is 0.01-5 mol/L, and after a sealing reaction, hydrothermal treatment is carried out for 2-40 h at 100-250 ℃ to prepare the porous carbon microspheres, wherein the porous carbon microspheres can be applied to the field of supercapacitors. The acid in the initiator is protonic acid or Lewis acid. Protonic acids such as HCl, HBr, H2SO4、HClO4Or H3PO4Etc., Lewis acids, e.g. BF3、AlCl3、AlBr3、TiCl4、SnCl4、SbCl4、PCl5、ZnCl2Isometal halides or POCl3、CrO2Cl、SOCl2、VOCl3And the like. The alkali in the initiator is ammonia water, NaOH or KOH.
CN201110355267.9 also discloses a preparation method of graphene hollow microspheres for anisotropic conductive material, comprising: (1) dispersing graphite oxide in water, performing ultrasonic treatment, centrifuging, and drying in vacuum to obtain graphene oxide powder; (2) dispersing the graphene oxide in an alkaline solution with the pH value of 10-12 according to the mass-to-volume ratio of 0.1-0.5 g: 20ml, and stirring for 10-120 minutes at the temperature of 20-50 ℃ to obtain a graphene oxide suspension; (3) pouring the graphene oxide suspension into vegetable oil at the temperature of 80-90 ℃, stirring, and emulsifying for 10-120 minutes; heating the system to 95 ℃, stirring for 10-120 minutes, discharging water in the system, centrifugally separating out vegetable oil and graphene oxide hollow microspheres, washing with petroleum ether, and drying in vacuum to obtain graphene oxide hollow microspheres; (4) and dispersing the graphene oxide hollow microspheres in a reducing agent according to the mass ratio of 1: 100-100: 1, and reacting at 20-100 ℃ for 10-120 minutes to obtain the graphene hollow microspheres. The vegetable oil used in the patent is specifically defined as one of olive oil, castor oil, palm oil, linseed oil, camellia oil, safflower seed oil, peanut oil and rapeseed oil. The obtained product is a hollow microsphere, the internal pore diameter of the sphere is larger, and the hydrazine hydrate in the preparation method can not enable the sphere to have a more stable chemical structure after being reduced, but the spherical structure can be influenced due to the falling of functional groups, so that the application of the sphere in a specific field is limited.
CN201610187114.0 discloses a graphene aerogel ball with a honeycomb structure and a preparation method thereof. The method comprises the following steps: 1) uniformly stirring graphene oxide, water and an alkaline substance (sodium hydroxide, potassium hydroxide or 25% ammonia water by mass) to obtain slurry; 2) extruding the slurry into a coagulating bath through a needle head to obtain a graphene oxide hydrogel ball; 3) soaking the graphene oxide hydrogel spheres in water, adding a reducing agent, and heating for reaction for 10 hours to obtain reduced graphene oxide hydrogel spheres; 4) placing the reduced graphene oxide gel spheres in a low-temperature environment, freezing for 1-2 hours, and then unfreezing at room temperature; 5) soaking and washing the graphene oxide aerogel in a solvent, and drying the graphene oxide aerogel in an oven at 60 ℃ to obtain reduced graphene oxide aerogel balls; 6) and (3) carrying out high-temperature treatment on the reduced graphene oxide aerogel balls under the protection of argon to obtain the graphene aerogel balls. The aerogel spheres have a honeycomb structure, the pore size of the aerogel is 5-200 microns, the thickness of the pore wall is 10-300 nanometers, and the pore wall contains mesopores with the pore diameter of 1-5 nanometers.
CN201610055019.5 discloses a preparation method of graphene/hollow carbon nanospheres. Mixing ammonia water, water and ethanol to obtain a solution A, and mixing tetraethoxysilane and ethanol to obtain a solution B. Dropwise adding the solution B into the solution A under stirring to obtain a mixed solution, adding a silane coupling agent KH-550, stirring for 10-12 h, washing the obtained product, and drying in vacuum to obtain KH-550 modified SiO2Nanospheres. Dispersing the nanospheres in water, adding a graphene oxide solution, stirring, filtering, washing and drying to obtain SiO2Nanospheres/graphene oxide. Ammonia water, ethanol and SiO2Ultrasonically mixing nanospheres/graphene oxide, adding resorcinol and formaldehyde solution, stirring for 24h, carrying out hydrothermal treatment for 24h, and drying the obtained product to obtain the SiO-containing material2Nanosphere/graphene oxide polymer nanospheres. After drying the polymer nanospheres, carbonizing in nitrogen atmosphere, and removing SiO in the product by NaOH solution2And obtaining the graphene/hollow carbon nanosphere. The graphene/hollow carbon nanospheres obtained by the invention are used for electrode materials of super capacitors.
CN201410844167.6 specifically discloses a method for preparing graphene oxide nano gel spheres by an inverse miniemulsion method, which comprises the following steps: (1) respectively mixing 1mg/mL, 3mg/mL, 5mg/mL, 7mg/mL, 9mg/mL, 11mg/mL, 13mg/mL and 15mg/mL graphene oxide solutions with a surfactant, a cosurfactant and an organic solvent, and performing ultrasonic emulsification to obtain uniform and stable emulsion; (2) heating the emulsion obtained in the step (1) in a water bath until water in liquid drops is removed to obtain gel particles, and then cleaning the gel particles with absolute ethyl alcohol to obtain monodisperse graphene oxide gel; (3) and (3) adding N, N-dimethylformamide into a closed container, dispersing the graphene oxide gel obtained in the step (2) into the N, N-dimethylformamide, adding a reducing agent, and heating and reducing to obtain the target product. The surfactant is any one of Span80, Tween80 and TritonX-100. The cosurfactant is n-butyl alcohol. The organic solvent is cyclohexane. The reducing agent is any one of hydrazine hydrate, sodium borohydride and vitamin C. The diameter of the obtained graphene nanosphere is 30-300nm, and the graphene nanosphere can be widely applied to the aspects of high-adsorbability materials, drug transportation, catalyst carriers, lithium ion battery cathode materials, super capacitors and the like.
In summary, although various methods in the prior art can obtain spherical graphene, the preparation method is mostly a physical condensation process, and because intermolecular force formed by liquid surface tension is weak, the mechanical strength of the obtained graphene spheres is generally low, and the application of the graphene spheres in many fields, particularly in the field of catalyst carriers, is limited.
Disclosure of Invention
The invention aims to provide a preparation method of graphene microspheres.
The preparation method of the graphene microspheres is obtained by taking single-layer graphene oxide as a raw material through a reverse emulsion method, and comprises the following steps:
1) adjusting the pH value of an aqueous phase system of the aqueous solution of the graphene oxide to 9-11 by using an alkaline compound;
2) preparing a composite oil phase system of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 6: 1-15: 1;
3) adding a surfactant into the composite oil phase system, then adding the water phase system in the step 1), wherein the volume ratio of the oil phase to the water phase is 2:1-8:1, then adding a diamino compound, and stirring and reacting for 3-8 hours at 40-100 ℃ to obtain the graphene oxide microspheres.
More specifically, the preparation method of the graphene microsphere comprises the following steps:
1) preparation of Graphene Oxide (GO) slurry
Deionized water is used as a dispersing solvent to prepare GO slurry, the concentration of the GO slurry is controlled to be 0.5-20 mg/mL, ultrasonic treatment is carried out for 10-60 min, an alkaline compound is added until the pH value of a water phase is 9-11, preferably, the concentration of GO is 2-15 mg/mL, and ultrasonic treatment is carried out for 20-40 min;
2) preparation of composite oil phase
Preparing a composite oil phase of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 6: 1-15: 1, preferably 8: 1-10: 1, and adding a surfactant, wherein the addition amount of the surfactant accounts for 0.5-5% of the total volume of the water phase and the oil phase;
3) mixing of aqueous phase and oil phase
Mixing the composite oil phase and the GO slurry, stirring for 0.1-2 hours at 10-100 ℃, and forming an emulsion system at a stirring speed of 2000-5000R/min, wherein the volume ratio of the composite oil phase to the GO slurry is 2-8, and preferably 3-5;
4) formation of crosslinked microspheres
Adding a diamino compound into the emulsion system, wherein the content of the diamino compound accounts for 10-50% of the amount of the graphene oxide, reacting for 3-8 hours at 40-100 ℃ under the stirring of 500-1000R/min, and washing and drying to obtain the graphene microspheres.
In the present invention, the basic compound is capable of ionizing OH in an aqueous solution-The various types of basic compounds of (1).
The alkaline compound is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium hydroxide or ammonia water, preferably ammonia water.
The surfactant is selected from anionic surfactant, cationic surfactant or high molecular surfactant.
The surfactant is preferably a high molecular surfactant.
Among the high molecular surfactants, C is more preferable12-C28The long-chain oleic acid ester polymer surfactant is preferably (Z) -mono-9-octadecenoic acid sorbitan ester or polyoxyethylene sorbitan monooleate.
The diamine compound is selected from C2-C25Diamine compound of (1), preferably C2-C12Diamine compounds.
The diamine compound is selected from ethylenediamine, propylenediamine, hexamethylenediamine or p-phenylenediamine.
Preferably, the content of the diamine compound accounts for 10% -50% of the content of the graphene oxide.
The technical effects of the invention are as follows:
oxygen-containing functional groups (hydroxyl and carboxyl) on the surface of graphene oxide are utilized to be acted in an inverse emulsion system containing a composite oil phase through diamine compounds, so that the graphene is assembled together by hydrogen bonds or van der Waals force, and the sheets are connected, so that the graphene has uniform and controllable size distribution, sufficient strength and a porous structure. Form and maintain high-strength porous spheres, so that the spheres still keep better spherical degree and pore structure in later washing and other using processes, and the application of graphene in a catalyst carrier is expanded. And the method has short flow, low cost and good application prospect.
Drawings
Fig. 1 example 1 AFM photograph of homemade graphene oxide.
Fig. 2 SEM photograph of the graphene microsphere obtained in example 2.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Performance testing and experimental conditions:
testing the appearance of the microspheres: according to GB/T16594-1996, GB/T16594-2008 (scanning electron microscope measuring method for micrometer length)
Testing the specific surface area of the microspheres: according to GB/T7702.20-2008
Testing of graphene oxide sheet diameter size and sheet thickness: according to GB/T27760-
In the examples, except that the graphene oxide was a self-made product, the other raw materials were all commercial raw materials.
Example 1 preparation of graphene oxide
Adding 23mL of 98 wt% concentrated sulfuric acid into a dry beaker, cooling to about 0 ℃ in an ice bath, adding a solid mixture of 1g of graphite powder and 0.5g of sodium nitrate, stirring, slowly adding 3g of potassium permanganate, and stirring at a temperature of not more than 20 ℃ for reaction for 2 hours to obtain a first mixed solution, wherein the solution is viscous greenish black;
heating the first mixed solution to about 35 ℃, and continuously stirring and reacting for 30min to obtain a second mixed solution, wherein the mixed solution is changed from dark green to brown;
continuously and slowly dripping 46mL of deionized water into the second mixed solution, controlling the temperature to be about 100 ℃, continuing stirring for 20min, stopping stirring, and then adding 3mL of 30 wt% H2O2Reducing the residual oxidant to obtain a suspension, wherein the solution turns bright yellow;
filtering the suspension while the suspension is hot, washing the filtrate with a dilute hydrochloric acid solution with the concentration of 5 wt% until no sulfate radical is detected in the filtrate, then placing the filtrate in a drying oven at 60 ℃ for full drying until the color of the filtrate is changed from golden yellow to black, and then crushing and sieving the filtrate by using a crusher to obtain the graphene oxide. As shown in figure 1-GO graphene oxide AFM photographs (in the figure, the left ordinate is the two-dimensional radial value in microns; the right scale is the scale of lamella thickness). The obtained graphene oxide has the lamella size distribution of 2-5 mu m and is high-quality graphene oxide with a single lamella (about 1 nm).
Example 2
Preparing 50mL of 12mg/mL GO concentrated solution by using the GO in the embodiment 1, and slowly dropwise adding ammonia water until the pH value of the solution is 10 after carrying out ultrasonic treatment for 30 min;
preparing a composite oil phase of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 8:1, and the volume of the oil phase is 4.5 times that of GO;
adding a certain amount of (Z) -mono-9-octadecenoic acid sorbitan ester into the prepared oil phase, wherein the addition amount accounts for 5 percent of the total volume of the water phase and the oil phase;
mixing the oil phase and the water phase, stirring at 3000R/min by a homogenizer, adding into a three-necked bottle, mechanically stirring for 30min, adding hexamethylene diamine after the emulsion is stable, wherein the mass of the hexamethylene diamine accounts for 35% of the solid content of GO, and reacting for 5 hours at 80 ℃ and 600R/min;
after the reaction is finished, washing and drying the graphene oxide microspheres by using petroleum ether, n-hexane and ethanol in sequence to obtain the graphene oxide microspheres.
Tests show that the average particle size is 70 mu m, the particle size distribution is narrow, and the spherical regularity is highHigh, 250m specific surface area by BET test2(ii) in terms of/g. The SEM photograph of the graphene oxide microspheres is shown in fig. 2.
As can be seen from the pictures, the graphene oxide with a lamellar structure has been obviously processed into a microspherical structure with a dense surface.
Example 3
Preparing a 12mg/mL GO concentrated solution by using GO in example 1, carrying out ultrasonic treatment for 30min, and slowly dropwise adding ammonia water until the pH value of the solution is 9.
Preparing a composite oil phase of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 10:1, and the volume of the oil phase is prepared according to 3 times of the volume of GO;
adding a certain amount of polyoxyethylene sorbitan monooleate into the prepared oil phase, wherein the addition amount accounts for 3 percent of the total volume of the water phase and the oil phase;
mixing the oil phase and the water phase, stirring at 3500R/min by a homogenizer, adding into a three-necked bottle, mechanically stirring for 30min, adding phenylenediamine after the emulsion is stable, wherein the phenylenediamine accounts for 20% of the solid content of GO, reacting at 55 ℃ for 5 hours, and stirring at 800R/min during the reaction;
after the reaction is finished, washing and drying the graphene microspheres by using petroleum ether, n-hexane and ethanol in sequence to obtain the graphene microspheres.
The tested microspheres have the average particle size of 60 mu m and the specific surface area of 290m2/g。
Example 4
Preparing a 12mg/mL GO concentrated solution by using GO in example 1, carrying out ultrasonic treatment for 30min, and slowly dropwise adding ammonia water until the pH value of the solution is 11.
Preparing a composite oil phase of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 10:1, and the volume of the oil phase is prepared according to 5 times of the volume of GO;
adding a certain amount of polyoxyethylene sorbitan monooleate into the prepared oil phase, wherein the addition amount accounts for 2 percent of the total volume of the water phase and the oil phase;
mixing the oil phase and the water phase, stirring at 5000R/min by a homogenizer, adding into a three-necked bottle, mechanically stirring for 30min, adding pentamethylene diamine after the emulsion is stabilized, wherein the mass of the pentamethylene diamine accounts for 15% of the solid content of GO, and reacting for 5 hours at 90 ℃ under the condition of 500R/min;
after the reaction is finished, washing and drying the graphene microspheres by using petroleum ether, n-hexane and ethanol in sequence to obtain the graphene microspheres.
The average particle diameter is 85 μm and the specific surface area is 230m2/g。
Comparative example 1
Preparing 50mL of 12mg/mL GO concentrated solution by using the GO in the embodiment 1, and slowly dropwise adding ammonia water until the pH value of the solution is 10 after carrying out ultrasonic treatment for 30 min;
preparing a liquid carbon tetrachloride oil phase, wherein the volume of the oil phase is 3.0 times that of GO;
adding (Z) -mono-9-octadecenoic acid sorbitan ester into the oil phase, wherein the addition amount accounts for 5% of the total volume of the water phase and the oil phase;
mixing the oil phase and the water phase, stirring at 5000R/min by a homogenizer, adding into a three-necked bottle, mechanically stirring for 30min, adding hexamethylene diamine after the emulsion is stable, wherein the mass of the hexamethylene diamine accounts for 30% of the solid content of GO, and reacting at 60 ℃ and 600R/min for 5 hours;
after the reaction is finished, washing and drying the graphene oxide microspheres by using petroleum ether, n-hexane and ethanol in sequence to obtain the graphene oxide microspheres.
Tests show that the average particle size is 40 micrometers, the range of partial particle sizes is wide, the spherical regularity is poor, part of microspheres have a fracture phenomenon, and the specific surface area is 80m through a BET test2/g。
Comparative example 2
And (3) preparing a 12mg/mL GO concentrated solution by using the GO in the example 1, carrying out ultrasonic treatment for 30min, and slowly dropwise adding ammonia water until the pH value of the solution is 9.
Preparing a composite oil phase of liquid paraffin and carbon tetrachloride; wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 10:1, and the volume of the oil phase is prepared according to 2.5 times of the volume of GO;
adding a certain amount of surfactant, namely Sodium Dodecyl Sulfate (SDS), into the prepared oil phase; wherein the addition amount accounts for 5% of the total volume (water phase and oil phase);
mixing the oil phase and the water phase, stirring at 5000R/min by a homogenizer, adding into a three-necked bottle, mechanically stirring for 30min, and adding phenylenediamine after the emulsion is stabilized, wherein the phenylenediamine accounts for 20% of the solid content of GO; the reaction was carried out at 85 ℃ and 700R/min for 5 hours.
After the reaction is finished, washing the graphene microspheres with petroleum ether, n-hexane and ethanol in sequence, and drying to obtain the graphene microspheres.
Tests show that the average particle size is 30 mu m, the emulsion is unstable, the microsphere forming degree is poor, the particle size distribution is wide, and the specific surface area is 87m through the BET test2/g。
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the appended claims be embraced thereby.
Claims (12)
1. A preparation method of graphene microspheres is characterized in that monolayer graphene oxide is used as a raw material and is obtained by a reverse emulsion method, and the preparation method comprises the following steps:
1) adjusting the pH value of an aqueous phase system of the aqueous solution of the graphene oxide to 9-11 by using an alkaline compound;
2) preparing a composite oil phase system of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 6: 1-15: 1;
3) adding a surfactant into the composite oil phase system, then adding the water phase system in the step 1), wherein the volume ratio of the oil phase to the water phase is 2:1-8:1, then adding a diamino compound, and stirring and reacting for 3-8 hours at 40-100 ℃ to obtain the graphene oxide microspheres.
2. The preparation method of the graphene microsphere according to claim 1, wherein the process comprises the following steps:
1) preparation of graphene oxide slurry
Preparing graphene oxide slurry by using deionized water as a dispersing solvent, controlling the concentration of the graphene oxide slurry to be 0.5-20 mg/mL, performing ultrasonic treatment for 10-60 min, and then adding an alkaline compound until the pH value of a water phase is 9-11;
2) preparation of composite oil phase
Preparing a composite oil phase of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 6: 1-15: 1, and adding a surfactant, wherein the adding amount of the surfactant accounts for 0.5% -5% of the total volume of the water phase and the oil phase;
3) mixing of aqueous phase and oil phase
Mixing the composite oil phase and the graphene oxide slurry, stirring for 0.1-2 hours at 10-100 ℃, wherein the stirring speed is 2000-5000 r/min to form an emulsion system, and the volume ratio of the composite oil phase to the graphene oxide slurry is 2-8;
4) formation of crosslinked microspheres
Adding a diamine compound into the emulsion system, wherein the amount of the diamine compound accounts for 10-50% of the amount of the graphene oxide, reacting for 3-8 hours at 40-100 ℃ under stirring at 500-.
3. The preparation method of the graphene microsphere according to claim 2, wherein the process comprises the following steps:
1) preparation of graphene oxide slurry
Preparing graphene oxide slurry by using deionized water as a dispersing solvent, controlling the concentration of the graphene oxide slurry to be 2-15 mg/mL, performing ultrasonic treatment for 20-40 min, and adding an alkaline compound until the pH value of a water phase is 9-11;
2) preparation of composite oil phase
Preparing a composite oil phase of liquid paraffin and carbon tetrachloride, wherein the volume ratio of the liquid paraffin to the carbon tetrachloride is 8: 1-10: 1, and adding a surfactant, wherein the adding amount of the surfactant accounts for 0.5-5% of the total volume of the water phase and the oil phase;
3) mixing of aqueous phase and oil phase
Mixing the composite oil phase and the graphene oxide slurry, stirring for 0.1-2 hours at 10-100 ℃, and forming an emulsion system at a stirring speed of 2000-5000 r/min, wherein the volume ratio of the composite oil phase to the graphene oxide slurry is 3-5;
4) formation of crosslinked microspheres
Adding a diamine compound into the emulsion system, wherein the amount of the diamine compound accounts for 10-50% of the amount of the graphene oxide, reacting for 3-8 hours at 40-100 ℃ under stirring at 500-.
4. The method for preparing graphene microspheres according to any one of claims 1 to 3, wherein the basic compound is a basic compound of various types capable of ionizing OH-in an aqueous solution.
5. The method for preparing graphene microspheres according to claim 4, wherein the basic compound is sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium hydroxide or ammonia water.
6. The method for preparing graphene microspheres according to claim 5, wherein the basic compound is ammonia.
7. The method for preparing graphene microspheres according to any one of claims 1 to 3, wherein the surfactant is selected from an anionic surfactant, a cationic surfactant or a polymeric surfactant.
8. The method for preparing graphene microspheres according to claim 7, wherein the surfactant is C12-C28Long-chain oleic acid ester polymer surfactant.
9. The method for preparing graphene microspheres according to claim 8, wherein the surfactant is (Z) -mono-9-octadecenoic acid sorbitan ester or polyoxyethylene sorbitan monooleate.
10. The method for preparing graphene microspheres according to any one of claims 1 to 3, wherein the diamine-based compound is selected from C2-C25The diamine compound of (1).
11. According to claimThe method for preparing graphene microspheres according to claim 10, wherein the diamine-based compound is selected from C2-C12Diamine compounds.
12. The method for preparing graphene microspheres according to claim 11, wherein the diamine-based compound is selected from ethylenediamine, propylenediamine, hexamethylenediamine, and p-phenylenediamine.
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| CN113679660A (en) * | 2020-05-19 | 2021-11-23 | 北京智慧客科技创新有限公司 | Slow-release drug carrier and preparation method and application thereof |
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| WO2021140139A1 (en) * | 2020-01-09 | 2021-07-15 | Empa Eidgenössische Materialprüfungs- Und Forschungsanstalt | Homogeneous emulsions and dispersions of 2-dimensional materials |
| CN113679660A (en) * | 2020-05-19 | 2021-11-23 | 北京智慧客科技创新有限公司 | Slow-release drug carrier and preparation method and application thereof |
| CN114957897A (en) * | 2022-06-27 | 2022-08-30 | 苏福（深圳）科技有限公司 | High-performance graphene film and preparation method thereof |
| CN114957897B (en) * | 2022-06-27 | 2022-12-13 | 苏福（深圳）科技有限公司 | High-performance graphene film and preparation method thereof |
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