CN113952927B - Dual-channel 3D graphene ball prepared by CVD method and application thereof in emulsion separation - Google Patents
Dual-channel 3D graphene ball prepared by CVD method and application thereof in emulsion separation Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 239000000839 emulsion Substances 0.000 title claims abstract description 37
- 238000000926 separation method Methods 0.000 title claims abstract description 33
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002569 water oil cream Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 3
- 239000008041 oiling agent Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 16
- 239000000203 mixture Substances 0.000 description 5
- 238000005457 optimization Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a dual-channel 3D graphene ball prepared by a CVD method and application thereof in emulsion separation, and belongs to the technical field of oil-water filter materials. The technical proposal is as follows: mesoporous MgO particles are prepared firstly, then 3D graphene spheres are prepared by a CVD method, and emulsion separation is realized by utilizing the high-efficiency separation capacity of the graphene spheres. The beneficial effects of the invention are as follows: the graphene balls prepared by the method disclosed by the invention can be recycled for 10 times, the emulsion separation efficiency of the graphene materials is still kept above 95%, the graphene balls have high-efficiency emulsion separation capacity for different oiling agents and organic solvents, and the oiling agents and organic solvents with toxicity and volatility are recovered, so that the pollution of experiments to the environment is effectively solved.
Description
Technical Field
The invention relates to the technical field of oil-water filtering materials, in particular to a CVD method for preparing a double-channel 3D graphene ball and application of the double-channel 3D graphene ball in emulsion separation.
Background
With the increasing attention and protection of the environment, there is an increasing demand for materials that address organic pollutants and petroleum leaks. Existing adsorption materials include membrane materials (fabrics, fibrous membranes, webs, etc.), porous materials (sponges, aerogels, etc.), and some powder materials, etc., which, although widely used in research and practical applications, have limitations. Membrane materials and porous materials are not suitable for cleaning large areas of spilled oil or organic contaminants, and reported powder materials including carbon nanoparticles, calcium carbonate particles, silica particles, etc. have poor dispersion in systems and cannot be used for emulsion separation. Many of the current wastewater contaminants are not simply oil-water mixtures, but are present in an emulsion system, which greatly increases the difficulty of separation.
In recent years, carbon materials, particularly graphene materials, are considered suitable candidates for superhydrophobic surfaces due to their low surface energy and tunable topological nanostructures. In particular, porous graphene is also widely used as an electrode material for batteries and supercapacitors, as an adsorbent for separation processes and gas storage, and as a carrier for many important catalytic processes due to its high surface area and large pore volume. The combination of superhydrophobicity and porosity can widen the potential application range of the graphene material, especially in the aspects of water filtration or water/oil separation and the like. Currently, many techniques have been developed by researchers to synthesize graphene materials, including chemical or physical activation, wet chemical routes, template replication processes, chemical Vapor Deposition (CVD), and the like. Among these methods, CVD is one of the most commonly used methods for graphene material preparation.
Graphene materials usually have a channel, a hydrophobic channel or an oleophobic channel, and at present, organic synthesis is generally performed in an organic solvent, but the organic solvent is often high in volatility and toxic, so that the environment is greatly polluted, and in addition, some 2D graphene sheets in the past are easy to agglomerate in the solvent and cannot be well dispersed. Therefore, we propose a method for preparing 3D mesoporous graphene materials with dual channels by spray drying and CVD techniques.
Disclosure of Invention
The invention aims to provide a dual-channel 3D graphene ball prepared by a CVD method and application thereof in emulsion separation, mesoporous MgO particles are prepared first, then the 3D graphene ball is prepared by the CVD method, and emulsion separation is realized by utilizing the high-efficiency separation capacity of the dual-channel graphene ball.
In order to achieve the above object, the present invention adopts the following technical scheme: a CVD method for preparing a double-channel 3D graphene ball and application thereof in emulsion separation comprise the following steps:
step 1, na is added 2 CO 3 Particles and MgCl 2 The particles are respectively added into deionized water and stirred uniformly, and then Na is added 2 CO 3 The solution was slowly added dropwise to MgCl with stirring 2 In solution, the resulting milky Mg 2 CO 3 Filtering the solution, washing with deionized water, repeating for three times, spray drying the obtained solution,obtaining powder particles;
step 2, placing the powder particles obtained in the step 1 in a muffle furnace for pretreatment; then CVD catalysis is carried out, ar is introduced in the whole process 2 Then acetonitrile is introduced, then a carbon source is replaced, the acetonitrile is closed, methane is introduced, and after the completion, the temperature is naturally reduced to the room temperature;
step 3, etching the sample catalyzed in the step 2 by hydrochloric acid, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally carrying out suction filtration and drying to obtain 3D graphene powder;
step 4, mixing oil and water according to a volume ratio of 1:9, and stirring for 2 hours at 25-30 ℃ to obtain surfactant-free oil-water emulsion; dissolving Sodium Dodecyl Sulfate (SDS) in water as an emulsifier, adding related oil into the water, fixing the volume ratio of the oil to the water to be 1:99, and stirring at 25-30 ℃ for 1h to obtain oil-water emulsion with stable surfactant;
and 5, respectively adding the two emulsions in the step 4 into the 3D graphene powder in the step 3, stirring for 10min, filtering, and observing the emulsion separation effect.
As a further optimization scheme for preparing the double-channel 3D graphene balls by the CVD method and applying the double-channel 3D graphene balls to emulsion separation, in the step 1, na is adopted 2 CO 3 The particle is 7-10g, mgCl 2 The particles are 7-10g, and added into 50-80ml and 80-160ml deionized water respectively.
As a further optimization scheme for preparing the double-channel 3D graphene balls by the CVD method and applying the double-channel 3D graphene balls to emulsion separation, in the step 2, the muffle furnace is heated to 600 ℃ at a heating rate of 5 ℃/min and is kept at a constant temperature for two hours; ar is led to 2 The flow rate is 500sccm, and the temperature is increased to 900 ℃ at the heating rate of 10 ℃/min; acetonitrile is introduced for 10min at 65 ℃ with the flow rate of 150sccm; the methane flow time was 20min and the flow rate was 400sccm.
As a further optimization scheme for preparing the double-channel 3D graphene balls by the CVD method and the application of the double-channel 3D graphene balls in emulsion separation, in the step 3, the concentration of hydrochloric acid is 1mol/L, and etching is performed at 60-70 ℃.
As a further optimization scheme for preparing the double-channel 3D graphene spheres by the CVD method and applying the double-channel 3D graphene spheres to emulsion separation, in the step 4, the surfactant-free water-oil emulsion is stable for 4 hours; the surfactant-stabilized oil-in-water emulsion is stable for at least 24 hours.
Compared with the prior art, the invention has the beneficial effects that: the graphene ball prepared by the method has good reusability, and can be circulated for 10 times, and the emulsion separation efficiency of the graphene material is still maintained above 95%. The graphene spheres have high-efficiency emulsion separation capability for different oiling agents and organic solvents. The oil solution and the organic solvent with toxicity and volatility are recovered, so that the pollution of the experiment to the environment is effectively solved.
Drawings
Fig. 1 is a schematic diagram of a preparation flow of a 3D graphene ball according to the present invention.
In FIG. 2, (a) is the MgO pellets of the present invention; (b) is graphene/MgO spheres; (c) is an SEM photograph of 3D graphene spheres; (D-f) is a TEM photograph of a 3D graphene sphere; (g-i) elemental scan of 3D graphene spheres.
In FIG. 3, (a) is MgCO according to the present invention 3 XRD patterns of spheres, mgO/graphene spheres, and 3D graphene spheres; (b) is a raman spectrum of a 3D graphene sphere; XPS spectra of (C) C1s and (D) N1s in the 3D graphene spheres; (e, f) nitrogen adsorption-desorption analysis chart of MgO spheres and 3D graphene spheres.
In FIG. 4, (a) is a diagram showing the oil-water emulsion separation process according to the present invention; (b) is a contact angle picture of a pure graphene material.
FIG. 5 is a graph of optical microscopy analysis of emulsifier free (SFE) and emulsifier (SSE) systems of the invention before and after separation.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention. The experimental procedures and reagents not shown in the formulation of the examples were all in accordance with the conventional conditions in the art.
Example 1
Step 1, mixing 8.836g of Na 2 CO 3 Particles and 8g of MgCl 2 The particles were added to 80ml and 160ml deionized water, respectively, and stirred well, then Na was added 2 CO 3 The solution was slowly added dropwise to MgCl with stirring 2 In solution, the resulting milky Mg 2 CO 3 And (3) carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder.
Step 2, placing the powder particles in the step 1 in a muffle furnace for pretreatment, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for two hours; then CVD catalysis is carried out, ar is introduced in the whole process 2 The flow rate is 500sccm, the temperature is increased to 900 ℃ at the heating rate of 10 ℃/min, then acetonitrile is introduced for 10min, the temperature is 65 ℃, the flow rate is 150sccm, then a carbon source is replaced, acetonitrile is closed, methane is introduced for 20min, the flow rate is 400sccm, and after the completion, the temperature is naturally reduced to room temperature.
And step 3, etching the sample catalyzed in the step 2 with 1mol/L hydrochloric acid at 60 ℃, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally carrying out suction filtration and drying to obtain the double-channel 3D graphene powder.
Step 4, surfactant-free oil-water emulsion: mixing oil and water according to a volume ratio of 1:9, and stirring for 2 hours at 25-30 ℃ to obtain emulsion. Surfactant-stabilized oil-water emulsions: SDS was first dissolved in water as an emulsifier and then the relevant oil was added to the water with the volume ratio of oil to water fixed at 1:99. Then, the mixture was stirred at 25-30℃for 1 hour to obtain an emulsion.
And 5, adding the 3D graphene powder in the step 3 into the emulsion in the step 4, stirring for 10min, and observing the separation condition of the system.
As shown in fig. 1 (a), the preparation flow of the 3D graphene spheres in this embodiment is schematically shown. First by Na 2 CO 3 And MgCl 2 The MgCO is obtained after the reaction 3 The particles are then subjected to a spray drying process to obtain mesoporous MgO spheres, followed by subjecting the resulting MThe gO ball is catalyzed by CVD, the MgO ball can be used as a template and a catalyst for in-situ growth of graphene, and can effectively promote the formation of a regular graphene shell in the CVD process, and in order to obtain a double channel, two carbon sources are used: acetonitrile and methane, forming a super-hydrophilic N-doped graphene layer by using acetonitrile, forming a super-hydrophobic graphene layer by using methane, and finally etching away an MgO template by using a hydrochloric acid solution to obtain the double-channel 3D graphene ball.
The emulsion is separated by the 3D graphene spheres prepared in the embodiment, the separation process and the dispersion condition are shown in figure 3, the graphene layering of the water phase and the adsorbed oil phase is observed, and the clear and transparent water phase is obtained through filtration, so that the separation efficiency is high. Example 2
Step 1, mixing 8.836g of Na 2 CO 3 Particles and 8g of MgCl 2 The particles were added to 50ml and 80ml deionized water respectively and stirred well, then Na was added 2 CO 3 The solution was slowly added dropwise to MgCl with stirring 2 In solution, the resulting milky Mg 2 CO 3 And (3) carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder.
Step 2, placing the powder particles in the step 1 in a muffle furnace for pretreatment, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for two hours; then CVD catalysis is carried out, ar is introduced in the whole process 2 The flow rate is 500sccm, the temperature is increased to 900 ℃ at the heating rate of 10 ℃/min, then acetonitrile is introduced for 10min, the temperature is 65 ℃, the flow rate is 150sccm, and after the completion, the temperature is naturally reduced to the room temperature.
And step 3, etching the sample catalyzed in the step 2 with 1mol/L hydrochloric acid at 65 ℃ to remove impurities in the step 1, repeatedly etching and washing for 3 times, and finally carrying out suction filtration and drying to obtain the N-doped 3D graphene powder.
Step 4, surfactant-free oil-water emulsion: mixing oil and water according to a volume ratio of 1:9, and stirring for 2 hours at 25-30 ℃ to obtain emulsion. Surfactant-stabilized oil-water emulsions: SDS was first dissolved in water as an emulsifier and then the relevant oil was added to the water with the volume ratio of oil to water fixed at 1:99. Then, the mixture was stirred at 25-30℃for 1 hour to obtain an emulsion.
And 5, adding the 3D graphene powder in the step 3 into the emulsion in the step 4, stirring for 10min, and observing the separation condition of the system. .
The N-doped 3D graphene spheres prepared in this embodiment have only hydrophilic groups, and cannot separate the emulsion, and the obtained oil-water mixture is still obtained by filtration.
Example 3
Step 1, 9g of Na 2 CO 3 Particles and 7g of MgCl 2 The particles were added to 80ml and 160ml deionized water, respectively, and stirred well, then Na was added 2 CO 3 The solution was slowly added dropwise to MgCl with stirring 2 In solution, the resulting milky Mg 2 CO 3 And (3) carrying out suction filtration and deionized water washing on the solution, repeating the steps for three times, and finally carrying out spray drying on the obtained solution to obtain powder.
Step 2, placing the powder particles in the step 1 in a muffle furnace for pretreatment, heating to 600 ℃ at a heating rate of 5 ℃/min, and keeping the temperature for two hours; then CVD catalysis is carried out, ar is introduced in the whole process 2 The flow rate is 500sccm, the temperature is increased to 900 ℃ at the heating rate of 10 ℃/min, methane is introduced for 40min, the flow rate is 400sccm, and the temperature is naturally reduced to the room temperature after the completion.
And step 3, etching the sample catalyzed in the step 2 with 1mol/L hydrochloric acid at 70 ℃, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally carrying out suction filtration and drying to obtain the 3D graphene powder.
Step 4, surfactant-free oil-water emulsion: mixing oil and water according to a volume ratio of 1:9, and stirring for 2 hours at 25-30 ℃ to obtain emulsion. Surfactant-stabilized oil-water emulsions: SDS was first dissolved in water as an emulsifier and then the relevant oil was added to the water with the volume ratio of oil to water fixed at 1:99. Then, the mixture was stirred at 25-30℃for 1 hour to obtain an emulsion.
And 5, adding the 3D graphene powder in the step 3 into the emulsion in the step 4, stirring for 10min, and observing the separation condition of the system.
The 3D graphene spheres prepared by the embodiment show superhydrophobicity, have no hydrophilic groups, are easy to agglomerate in a system, and have low separation efficiency.
The dual-channel 3D graphene spheres prepared by the examples were tested as shown in fig. 1.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention, but any partial variations of the formulation and process thereof are within the scope of the present invention.
Claims (1)
1. The application of the double-channel 3D graphene spheres prepared by the CVD method in emulsion separation is characterized by comprising the following steps:
step 1, na is added 2 CO 3 Particles and MgCl 2 The particles are respectively added into deionized water and stirred uniformly, and then Na is added 2 CO 3 The solution was slowly added dropwise to MgCl with stirring 2 In solution, the resulting milky Mg 2 CO 3 Filtering the solution, washing with deionized water, repeating for three times, and finally spray-drying the obtained solution to obtain powder particles;
in the step 1, the Na 2 CO 3 The particle is 7-10g, mgCl 2 7-10g of particles are respectively added into 50-80mL and 80-160mL of deionized water;
step 2, placing the powder particles obtained in the step 1 in a muffle furnace for pretreatment; then carrying out CVD catalysis, introducing Ar in the whole process, then introducing acetonitrile, replacing a carbon source, closing the acetonitrile, introducing methane, and naturally cooling to room temperature after the completion of the reaction;
in the step 2, the muffle furnace in pretreatment is heated to 600 ℃ at a heating rate of 5 ℃/min and is kept at a constant temperature for two hours; the flow speed is 500sccm when Ar is introduced into the CVD catalysis, and the temperature is increased to 900 ℃ at the heating rate of 10 ℃/min; acetonitrile is introduced for 10min, and the flow speed is 150sccm; the methane-introducing time is 20min, and the flow rate is 400sccm;
step 3, etching the sample catalyzed in the step 2 by hydrochloric acid, removing impurities in the step 1, repeatedly etching and washing for 3 times, and finally carrying out suction filtration and drying to obtain 3D graphene powder;
in the step 3, the concentration of hydrochloric acid is 1mol/L, and etching is carried out at 60-70 ℃;
step 4, mixing oil and water according to a volume ratio of 1:9, and stirring for 2 hours at 25-30 ℃ to obtain surfactant-free oil-water emulsion; dissolving Sodium Dodecyl Sulfate (SDS) in water as an emulsifier, adding oil into the water, fixing the volume ratio of the oil to the water to be 1:99, and stirring at 25-30 ℃ for 1h to obtain oil-water emulsion with stable surfactant;
in the step 4, the oil-water emulsion without the surfactant is stabilized for 4 hours; the surfactant-stabilized oil-water emulsion is stable for at least 24 hours;
and 5, respectively adding the 3D graphene powder in the step 3 into the two emulsions in the step 4, stirring for 10min, filtering, and observing the emulsion separation effect.
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