CN109650381B - Sea urchin-shaped graphene and preparation method thereof - Google Patents
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Abstract
The invention discloses echinoid graphene and a preparation method thereof, and relates to the field of graphene material preparation. The invention utilizes nickel salt and reducing agent to react under alkaline condition, self-assemble and form sea urchin-shaped three-dimensional nickel substrate; depositing graphene on a sea urchin-shaped three-dimensional nickel substrate by a chemical vapor deposition technology; and (4) adding acid to remove the nickel substrate, thus obtaining the sea urchin-shaped three-dimensional graphene. The sea urchin-shaped three-dimensional graphene disclosed by the invention has a good dispersion type, and the problems of stacking, porosity, unstable configuration and the like are effectively prevented. The preparation method disclosed by the invention is simple in preparation process, mild in condition, wide in raw material source, suitable for batch production and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of graphene materials, and particularly relates to echinoid graphene and a preparation method thereof.
Background
The graphene material is a monoatomic layer material with a unique two-dimensional honeycomb structure and has excellent electrical, thermal and mechanical properties. Based on its unique properties, graphene materials are known as "the king of new materials in the 21 st century" by the scientific community, and are being used in various fields including energy, environment, biology and the like. However, in the application process, some problems of the graphene material are found, for example, the graphene with a two-dimensional structure is very easy to curl due to its ultra-thin thickness, so that the corresponding performance is greatly reduced, and the graphene material is greatly limited in some practical applications. In addition, due to the strong pi-pi action and van der waals force, the two-dimensional structure of the graphene is easy to seriously stack and agglomerate, and the inherent properties of the graphene are seriously influenced. Scientists have found that two-dimensional graphene structures are assembled into three-dimensional graphene structures, such as foams, hydrogels. Aerogel and spherical structures, etc., which can effectively solve these problems. In view of this, the construction of a three-dimensional structure of graphene has been started to solve the above-mentioned problems in the prior art.
The three-dimensional graphene is a mode of existence of two-dimensional graphene in a three-dimensional space, and specifically can be a graphene network, graphene fibers, graphene gel, graphene sponge and other structures. The three-dimensional graphene not only retains various original physicochemical properties of the two-dimensional graphene, but also has an ultra-large specific surface area and higher conductivity due to a special microstructure. The existing method for preparing the three-dimensional graphene mainly comprises a self-assembly method and a template auxiliary method. The self-assembly method is to gel the graphene oxide by adding a cross-linking agent, build the graphene oxide into a three-dimensional framework and reduce the three-dimensional framework to obtain the three-dimensional graphene.
For example, in the method for preparing three-dimensional graphene disclosed in chinese patent CN 201810175676, graphene oxide is used as an initiator, an emulsifier, a cross-linking agent, and a reducing agent are added to form spherical graphene hydrogel in an oil phase, and then three-dimensional self-assembled graphene is obtained by water evaporation and high-temperature calcination. In the preparation process of the method, other components such as an oil phase, an emulsifier, a cross-linking agent, a reducing agent and the like are required to be introduced, the components are not easy to remove and clean, and simultaneously, the defects of porosity, interlayer looseness, difficult forming and the like exist, so that the performance and the application of the oil phase are limited. The template-assisted method is characterized in that a pre-designed three-dimensional structure is used as a template, graphene is directly grown on the three-dimensional template through a chemical vapor deposition method, and the graphene prepared by the method has few defects and controllable morphology and performance. The existing three-dimensional graphene prepared by a template-assisted chemical vapor deposition method mainly uses graphene sponge prepared by taking porous metal foam as a substrate, and the structure is single. The preparation of echinoid graphene by a chemical vapor deposition method and a nickel substrate is not disclosed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides echinoid graphene and a preparation method thereof, and aims to solve the technical problems that two-dimensional graphene is easy to curl and three-dimensional graphene is single in structure in the prior art.
In order to solve the above problems, the present invention provides the following technical solutions:
in one aspect, the present invention provides a echinoid graphene having a three-dimensional hollow echinoid structure.
Further, sea urchin-shaped graphene comprises spheres and needle-shaped whiskers, wherein the needle-shaped whiskers are distributed on the surfaces of the spheres, the diameters of the spheres are 500-700 nm, and the lengths of the whiskers are about 300 nm.
On the other hand, the invention also provides a preparation method of the echinoid graphene, which comprises the following specific steps:
1) in a solvent, reacting nickel salt under the action of alkali and a reducing agent to prepare sea urchin-shaped nickel nanocrystals;
2) taking the nickel nanocrystal as a template, and adhering and growing graphene on the surface of the nickel nanocrystal by a chemical vapor deposition method to obtain nickel-based echinoid graphene;
3) and removing the nickel substrate through reagent corrosion to obtain the sea urchin-shaped three-dimensional graphene.
Further, the solvent may be one of ethanol, water, ethylene glycol, methanol, propanol, isopropanol, propylene glycol, glycerol, kerosene, mineral spirits, or a combination thereof, further, the dissolution solvent may be ethanol, water, ethylene glycol, propanol, isopropanol, propylene glycol, and preferably, the dissolution solvent of the present invention is ethylene glycol.
Further, the nickel salt may be NiSO4·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O、NiCl2·6H2O、NiBr2、NiI2、NiF2Preferably, the nickel salt of the invention is NiSO4·6H2O、Ni(NO3)2·6H2O、NiCl2·6H2O。
Further, the alkali may be ammonia, NaOH, KOH, Na2CO3、Na3PO4、Na3BO4、K2CO3Sodium methoxide, sodium ethoxide and potassium tert-butoxide, or their mixture, and the alkali may be ammonia, NaOH, KOH or Na2CO3、Na3PO4Preferably, the base of the present invention is NaOH.
Further, the molar ratio of the alkali to the nickel salt is 1-20:1, further the molar ratio of the alkali to the nickel salt is 2-10: 1, and preferably the molar ratio of the alkali to the nickel salt is 2:1, 4:1, 10: 1.
Further, the reducing agent is one or a combination of hydrazine hydrate, sodium borohydride, oxalic acid, formic acid, sodium hypophosphite, L-ascorbic acid, citric acid, potassium hypophosphite, calcium hypophosphite, sodium hypophosphite, DTT and formaldehyde, and preferably, the reducing agent is one of hydrazine hydrate, sodium borohydride and oxalic acid.
Further, the molar ratio of the reducing agent to the nickel salt is 1-1000:1, further the molar ratio of the reducing agent to the nickel salt is 4-1000: 1, and preferably the molar ratio of the reducing agent to the nickel salt is 4:1,40:1, 1000:1.
Further, the reaction temperature in the step 1) is 10-100 ℃, further, the temperature is 50-100 ℃, preferably, the temperature is 50 ℃, 70 ℃ and 100 ℃; the reaction time is 1-5 hours, preferably, the reaction time is 1, 2 or 4 hours.
Further, the sea urchin-shaped nickel nanocrystal is prepared by the following steps: dissolving nickel salt in a solvent to obtain a nickel salt solution, sequentially adding alkali and a reducing agent into the nickel salt solution, stirring to completely dissolve the nickel salt solution to obtain a green solution, transferring the green solution into a flask, heating the flask for stirring in a water bath, gradually changing the color of the solution into black, performing suction filtration on the liquid after the reaction is finished, washing the obtained floccule with deionized water and absolute ethyl alcohol for three times respectively to remove impurities, and drying to obtain the sea urchin-shaped nickel nanocrystal.
Further, after the reaction in the step 1) is finished, the obtained solution is filtered to obtain floccules, and the floccules are washed and dried to obtain the sea urchin-shaped nickel nanocrystals. The drying temperature can be 10-100 ℃, and further, the drying temperature is 40-100 ℃, and preferably, the drying temperature is 40 ℃, 60 ℃ and 100 ℃.
Further, in step 2), the process of the chemical vapor deposition method is as follows: putting the nickel nanocrystals into a CVD tubular furnace, introducing a mixed atmosphere consisting of hydrogen and argon, heating to raise the temperature, adjusting the hydrogen flow rate after the temperature is raised, introducing a carbon source gas, preserving the temperature, closing the hydrogen and carbon source gases, and cooling to room temperature in the argon atmosphere to complete the reaction.
Further, in the step 2), the flow rate ratio of the hydrogen to the argon is 1-3: 20-200.
Further, in step 2), the heating and temperature raising process is as follows: heating to 800-1000 ℃ at a speed of 5 ℃/min.
Further, after the temperature rise is finished, the ratio of the hydrogen flow rate to the argon flow rate is adjusted to be 1-3: 5-100.
Further, the ratio of the flow rate of the carbon source gas to the flow rate of the argon gas is 1-3: 10-200.
Further, the heat preservation time is 10-30 min, preferably 10, 15 and 20 min.
Further, the reagent in step 3) may be nitric acid, hydrochloric acid, sulfuric acid with a concentration of 5% to 30%, further, the reagent may be nitric acid, hydrochloric acid with a concentration of 5% to 20%, and preferably, the reagent may be nitric acid with a concentration of 20%.
Further, after removing the nickel substrate by corroding the reagent in the step 3), centrifuging, washing the solid with deionized water, and drying to obtain the sea urchin-shaped three-dimensional graphene.
Further, the drying temperature is 50 ℃ to 200 ℃, further, the drying temperature is 50 ℃ to 100 ℃, preferably, the drying temperature is 50 ℃, 60 ℃, 80 ℃.
Further, the preparation method comprises the following specific steps:
1) dissolving nickel salt in a solvent to obtain a nickel salt solution, sequentially adding alkali and a reducing agent into the nickel salt solution, stirring to completely dissolve the nickel salt solution to obtain a green solution, transferring the green solution into a flask, heating the flask for stirring in a water bath, gradually changing the color of the solution into black, performing suction filtration on the liquid after the reaction is finished, washing the obtained floccule with deionized water and absolute ethyl alcohol for three times respectively to remove impurities, and drying to obtain the sea urchin-shaped nickel nanocrystal;
2) putting the sea urchin-shaped nickel nanocrystals obtained in the step 1) into a CVD (chemical vapor deposition) tube furnace, heating the tube furnace to 800-1000 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen (the flow rate is 10-30 sccm) and argon (the flow rate is 600-1000 sccm), then adjusting the flow rate of the hydrogen to 80-120 sccm, introducing a carbon source gas at the flow rate of 10-50 sccm, preserving heat for 10-20 min, turning off the hydrogen and the carbon source gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the sea urchin-shaped graphene growing on the surface of a nickel substrate;
3) immersing the material obtained in the step 2) in nitric acid (HNO)3:H2And (4) centrifuging the liquid after the nickel substrate is completely corroded and disappears, washing the liquid for several times by using deionized water, and drying the obtained black solid at 50-80 ℃ to obtain the echinoid graphene.
According to the invention, nickel salt is reduced into needle-shaped nickel under a certain pH value in a specific solution system through the reduction action of a reducing agent, the needle-shaped nickel can generate a magnetization effect mutually, and self-assembly is carried out to form nickel nanocrystals with sea urchin-shaped appearance, then graphene is grown on the surface of the nickel nanocrystals by taking the nickel nanocrystal structure as a template through a Chemical Vapor Deposition (CVD) method, and finally the nickel substrate is removed through corrosion, so that sea urchin-shaped graphene is obtained (the preparation process is shown in figure 1).
Advantageous effects
The invention provides sea urchin-shaped graphene and a preparation method thereof.
The sea urchin-shaped graphene prepared by the method can overcome the defects of the existing three-dimensional graphene prepared by a self-assembly method, and can overcome the problem that the three-dimensional graphene prepared by a template-assisted chemical vapor deposition method has a single structure; the sea urchin-shaped graphene has the advantages of novel structure and small number of defects, and has good dispersibility and no problems of stacking, porosity, unstable configuration and the like because the structure of the sea urchin-shaped graphene diverges from the center to the periphery;
electrons in the sea urchin-shaped graphene structure can migrate on the surface of the sea urchin-shaped graphene structure along all directions, and the electron migration direction of the traditional two-dimensional sheet graphene or the dimensional graphene built by graphene sheets is limited by the structure of the graphene, so that compared with the traditional two-dimensional sheet graphene or the dimensional graphene, various physical and chemical properties of the graphene structure are improved;
the echinoid graphene is in a hollow echinoid shape, has the characteristics of small density and large specific surface area, and can be used as a catalyst carrier or an adsorption material; the product microstructure and the structural unit thereof have good monodispersity, uniform appearance, clean surface, no impurities and a shape similar to sea urchin, the diameter of a sphere is 500-700 nm, a large number of needle-shaped whiskers are distributed on the surface of the sphere, the whiskers are straight along the length direction, the dimension is uniform, and the length is about 300 nm.
The preparation process is simple, the conditions are mild, the raw material sources are wide, various used chemical agents are easy to remove, no residue is generated, and the stability and other properties of the graphene are further ensured; the sea urchin-shaped graphene has ultrahigh electric conductivity and heat conductivity, and has potential application value in the fields of electric heating coatings, fuel cells, sensors, supercapacitors and the like.
Drawings
FIG. 1 is a schematic diagram of a preparation process of sea urchin-shaped three-dimensional graphene. (A) Needle-like nickel; (B) sea urchin-like nickel; (C) nickel-based graphene loading; (D) sea urchin-like graphene.
Fig. 2 shows electrochemical ac impedance spectra of graphene with different structures.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described below with reference to specific embodiments.
Example 1
A preparation method of sea urchin-shaped graphene comprises the following steps:
1) 1.19g of NiCl2·6H2O is added into 100mL of ethylene glycol and centrifugally stirred at 900r/min to obtain 0.05mol/L NiCl2A solution;
0.8g NaOH was added to the NiCl2In the solution, no precipitate is ensured to be separated out, and the solution is stirred for 5 minutes;
adding 10.0g of hydrazine hydrate into the solution, and fully stirring to obtain a green mixed solution;
then transferring the solution into a flask, keeping the temperature of the solution in a water bath at 70 ℃, stirring the solution for 2 hours, and gradually changing the color of the solution into black;
after the reaction is finished, carrying out suction filtration on the solution to obtain a floccule, washing the floccule with deionized water and absolute ethyl alcohol for three times respectively, and drying the floccule at the temperature of 60 ℃ for 30 minutes to obtain sea urchin-shaped nickel nanocrystals;
2) putting the obtained sea urchin-shaped nickel nanocrystal into a CVD (chemical vapor deposition) tubular furnace, and introducing mixed atmosphere consisting of hydrogen with the flow rate of 20sccm and argon with the flow rate of 800 sccm;
heating a tubular furnace to 1000 ℃ at the speed of 5 ℃/min, then adjusting the hydrogen flow rate to 100sccm, introducing methane gas at the flow rate of 30sccm, keeping the temperature for 15min, turning off the hydrogen and the methane gas, cooling to room temperature in an argon atmosphere, and taking out a sample to obtain the nickel-based echinoid graphene;
3) adding the obtained nickel-based echinoid graphene into 50ml of 20% nitric acid, centrifuging the liquid after the nickel substrate is completely corroded and disappears, taking the solid, washing the solid with deionized water for 3 times, then placing the solid into a drying furnace, adjusting the temperature to be 60 ℃, and drying the solid for 30 minutes to obtain the echinoid graphene.
Example 2
A preparation method of sea urchin-shaped graphene comprises the following steps:
1) 0.26g of NiSO4·6H2Adding O into 100mL of ethylene glycol, and centrifugally stirring at 900r/min to obtain 0.01mol/L NiSO4A solution;
0.4g NaOH was added to the above NiSO4In solution, ensure no precipitateSeparating out and stirring for 5 minutes;
adding 40.0g of sodium borohydride into the solution, and fully stirring to obtain a green mixed solution;
then transferring the solution into a flask, keeping the temperature of the solution in a water bath at 50 ℃, stirring the solution for 4 hours, and gradually changing the color of the solution into black;
after the reaction is finished, carrying out suction filtration on the solution to obtain a floccule, washing the floccule with deionized water and absolute ethyl alcohol for three times respectively, and drying the floccule at the temperature of 40 ℃ for 30 minutes to obtain sea urchin-shaped nickel nanocrystals;
2) putting the obtained sea urchin-shaped nickel nano crystal into a CVD (chemical vapor deposition) tubular furnace, and introducing mixed atmosphere consisting of hydrogen with the flow rate of 10sccm and argon with the flow rate of 600 sccm;
heating a tubular furnace to 800 ℃ at the speed of 5 ℃/min, then adjusting the hydrogen flow rate to 80sccm, introducing ethylene gas at the flow rate of 10sccm, keeping the temperature for 20min, turning off the hydrogen and the ethylene gas, cooling to room temperature in an argon atmosphere, and taking out a sample to obtain the nickel-based echinoid graphene;
3) adding the obtained nickel-based echinoid graphene into 30ml of 20% nitric acid, centrifuging the liquid after the nickel substrate is completely corroded and disappears, taking the solid, washing the solid with deionized water for 3 times, then placing the solid into a drying furnace, adjusting the temperature to 50 ℃, and drying for 30 minutes to obtain the echinoid graphene.
Example 3
A preparation method of sea urchin-shaped graphene comprises the following steps:
1) 2.91g of Ni (NO)3)2·6H2O is added into 100mL of ethylene glycol and centrifugally stirred at 900r/min to obtain 0.1mol/L NiCl2A solution;
0.8g NaOH was added to the NiCl2In the solution, no precipitate is ensured to be separated out, and the solution is stirred for 5 minutes;
adding 4.0g of oxalic acid into the solution, and fully stirring to obtain a green mixed solution;
then transferring the solution into a flask, keeping the temperature of the solution in a water bath at 100 ℃, and stirring the solution for 1 hour until the color of the solution gradually becomes black;
after the reaction is finished, carrying out suction filtration on the solution to obtain floccule, washing the floccule with deionized water and absolute ethyl alcohol for three times respectively, and drying at the temperature of 80 ℃ to obtain the sea urchin-shaped nickel nanocrystal.
2) Putting the obtained sea urchin-shaped nickel nanocrystal into a CVD (chemical vapor deposition) tubular furnace, and introducing mixed atmosphere consisting of hydrogen with the flow rate of 30sccm and argon with the flow rate of 1000 sccm;
heating a tubular furnace to 900 ℃ at the speed of 5 ℃/min, then adjusting the hydrogen flow rate to 120sccm, introducing acetylene gas at the flow rate of 50sccm, keeping the temperature for 10min, turning off the hydrogen and the acetylene gas, cooling to room temperature in an argon atmosphere, and taking out a sample to obtain the nickel-based sea urchin-shaped graphene;
3) adding the obtained nickel-based echinoid graphene into 100ml of 20% nitric acid, centrifuging the liquid after the nickel substrate is completely corroded and disappears, taking the solid, washing the solid with deionized water for 3 times, then placing the solid into a drying furnace, adjusting the temperature to 80 ℃, and drying for 30 minutes to obtain the echinoid graphene.
Example 4
The sea urchin-shaped nickel nanocrystals in example 1 were replaced with nickel sheets, and graphene was prepared using this as a substrate by a CVD method under the same conditions as in example 1, thereby finally obtaining two-dimensional sheet-layer graphene.
Specific surface area and electrochemical alternating current impedance tests are respectively carried out on the graphene prepared in the embodiment 1 and the graphene prepared in the embodiment 4, wherein the specific surface area is measured by adopting a BET nitrogen adsorption specific surface instrument of American Micromeritics corporation ASAP2010MC, the electrochemical alternating current impedance test is carried out on a CHI 660D type electrochemical workstation (Beijing, China), a three-electrode system is adopted, the graphene is used as a working electrode, a platinum wire is used as an auxiliary electrode, and a saturated calomel electrode is used as a reference electrode. The results are shown in Table 1 and FIG. 2
TABLE 1
| Group of | Example 1 | Example 4 |
| Material | Hemicentrotus Seu Strongylocentrotus-like graphene | Two-dimensional lamellar graphene |
| Specific surface area (m)2/g) | 1764 | 537 |
Due to the influence of a plurality of experimental factors and the properties of graphene, the graphene prepared in a laboratory has agglomeration in different degrees, so that the actual specific surface area is far lower than the theoretical value (2630 m)2As can be seen from table 1, the specific surface area of the echinoid graphene is lower than the theoretical value but is significantly higher than that of the traditional two-dimensional lamellar graphene due to the special microstructure of the echinoid graphene, which indicates good dispersibility of the echinoid graphene.
In an electrochemical alternating-current impedance spectrum, the semicircular diameter corresponds to the interface charge transfer resistance, so that the conductivity of the material can be represented, the smaller the semicircular diameter is, namely the smaller the interface charge transfer resistance is, namely the better the conductivity is, and as can be seen from fig. 2, the conductivity of the sea urchin-shaped graphene is superior to that of two-dimensional lamellar graphene.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and these changes and modifications are also considered to be included in the scope of the invention.
Claims (5)
1. A preparation method of sea urchin-shaped graphene is characterized by comprising the following specific steps: 1) dissolving nickel salt in a solvent to obtain a nickel salt solution, sequentially adding alkali and a reducing agent into the nickel salt solution, stirring to completely dissolve the nickel salt solution to obtain a green solution, transferring the green solution into a flask, heating the flask for stirring in a water bath, gradually changing the color of the solution into black, performing suction filtration on the liquid after the reaction is finished, washing the obtained floccule with deionized water and absolute ethyl alcohol for three times respectively to remove impurities, and drying to obtain the sea urchin-shaped nickel nanocrystal; 2) putting the sea urchin-shaped nickel nanocrystals obtained in the step 1) into a CVD (chemical vapor deposition) tube furnace, heating the tube furnace to 800-1000 ℃ at the speed of 5 ℃/min under the mixed atmosphere of hydrogen and argon, then adjusting the flow rate of the hydrogen to 80-120 sccm, introducing a carbon source gas at the flow rate of 10-50 sccm, keeping the temperature for 10-20 min, turning off the hydrogen and the carbon source gas, cooling to room temperature in the argon atmosphere, and taking out a sample to obtain the sea urchin-shaped graphene growing on the surface of the nickel substrate; 3) immersing the material obtained in the step 2) in nitric acid, centrifuging the liquid after the nickel substrate is completely corroded and disappears, washing the liquid for several times by using deionized water, and drying the obtained black solid at 50-80 ℃ to obtain sea urchin-shaped graphene; the sea urchin-shaped graphene comprises a sphere and needle-shaped whiskers, wherein the needle-shaped whiskers are distributed on the surface of the sphere and have a three-dimensional hollow sea urchin-shaped structure, the diameter of the sphere is 500-700 nm, and the length of the whiskers is about 300 nm.
2. The method for preparing echinoid graphene according to claim 1, wherein the solvent is one or more of ethanol, water, ethylene glycol, methanol, propanol, isopropanol, propylene glycol, glycerol, kerosene and solvent oil; the nickel salt is NiSO4·6H2O、Ni(NO3)2·6H2O、Ni(CH3COO)2·4H2O、NiCl2·6H2O、NiBr2、NiI2、NiF2One or more of; the alkali is ammonia water, NaOH, KOH, Na2CO3、Na3PO4、Na3BO4、K2CO3One or more of sodium methoxide, sodium ethoxide and potassium tert-butoxide.
3. The method for preparing echinoid graphene according to claim 1, wherein the molar ratio of the alkali to the nickel salt is 1-20: 1.
4. The method for preparing echinoid graphene according to claim 1, wherein the reducing agent is one or more of hydrazine hydrate, sodium borohydride, oxalic acid, formic acid, sodium hypophosphite, L-ascorbic acid, citric acid, potassium hypophosphite, calcium hypophosphite, sodium hypophosphite, DTT and formaldehyde; the molar ratio of the reducing agent to the nickel salt is 1-1000: 1.
5. The method for preparing echinoid graphene according to claim 1, wherein the reaction temperature in the step 1) is 10-100 ℃; the reaction time is 1-5 hours.
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