A preparation method of a graphite diacetylene / graphene / graphite diacetylene sandwich structure composite material

Abstract

The application discloses a preparation method of a graphite diacetylene / graphene / graphite diacetylene sandwich structure composite material, and can obtain good graphite diacetylene / graphene / graphite diacetylene sandwich structures in different sizes of graphene carriers and different solvents, and is a bridge from a small size in a laboratory to large-scale industrialization. The yield of the graphite diacetylene / graphene / graphite diacetylene sandwich structure obtained by a single experiment unit volume reactor is high, and the industrial production is facilitated.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of material preparation, and particularly relates to a synthesis method of a graphite diradical / graphene / graphite diradical sandwich structure composite material. BACKGROUND

[0002] Graphite diradical (GDY) is a new allotrope of carbon composed of sp 2 and sp hybridized carbon atoms. Theoretical studies show that graphite diradical has a natural band gap and is an intrinsic semiconductor, has special charge transport performance, and the high-density planar channel structure is conducive to the rapid transmission of ions between planes with high flux and low energy barrier (X. Gao, J. Zhang, Chem. Soc. Rev. 48, (2019), 908-936). Compared with other carbon materials (graphene, carbon nanotubes, and fullerene), the uneven distribution of surface charges of graphite diradical can cause high intrinsic activity. These excellent properties make graphite diradical have important application prospects in the fields of energy, catalysis, biomedicine, and separation.

[0003] Since the first successful preparation of GDY thin film by the team of Li Yuliang from the Chinese Academy of Sciences in 2010, researchers have been committed to the controllable synthesis of high-quality graphite diradical thin films, but the yield of the thin film is relatively low, and there are problems such as small single crystal domain and low surface cleanliness. How to prepare high-quality graphite diradical powder is an inevitable key problem in its practical application. In 2019, our research group invented the growth of high-quality graphite diradical on a graphene substrate and constructed a graphite diradical / graphene / graphite diradical sandwich structure (GDY / G) (J. Li, J. Zhang, Adv. Funct. Mater., 29, (2019), 1905423). The graphene is selected as the substrate, on the one hand, the π-conjugated system in graphene and the synthesis monomer of graphite diradical have π-π interaction and van der Waals interaction, which restricts the coupling reaction of monomer molecules on the graphene surface and inhibits the free rotation, which is conducive to the formation of two-dimensional planar network structure. On the other hand, graphene has hydrophobic properties, and the reaction solvent has hydrophobic interaction with the graphene surface, which can prevent the aggregation of monomers and is also conducive to the flat arrangement of monomers. SUMMARY

[0004] The above method realizes the preparation of high-quality graphite diradical / graphene / graphite diradical composite material, but still has the following limitations: the solubility of monomers in dichloromethane is poor, and the yield of unit volume of solvent is low.

[0005] The inventors found through experiments that, based on the conventional reaction of the prior art, if a solvent with higher monomer solubility, such as toluene, tetrahydrofuran, dimethyl sulfoxide, etc., is directly used instead of adding dichloromethane in order to improve the solubility of the monomer, the reaction is more difficult to proceed, and the yield of the obtained graphdiyne / graphene / graphdiyne powder is lower.

[0006] To solve the above technical problems and improve the yield of the graphdiyne / graphene / graphdiyne powder per unit volume of solvent in a single experiment, the present application provides a preparation method of a graphdiyne / graphene / graphdiyne sandwich structure composite material, specifically comprising the following steps:

[0007] S1, preparing hexaethynylbenzene;

[0008] S2, mixing a copper salt and an organic solvent, dissolving, then adding graphene powder and uniformly dispersing to obtain a copper salt / graphene organic dispersion liquid;

[0009] S3, uniformly mixing the hexaethynylbenzene and the copper salt / graphene organic dispersion liquid to obtain a hexaethynylbenzene / copper salt / graphene mixed liquid;

[0010] S4, subjecting the hexaethynylbenzene / copper salt / graphene mixed liquid to microwave reaction, centrifuging, washing, and drying to obtain the graphdiyne / graphene / graphdiyne sandwich structure composite material.

[0011] The solvent generally used in the prior art for preparing hexaethynylbenzene is dichloromethane (DCM) or a mixed solvent containing dichloromethane, and the general operation method is to use a DCM solution of hexaethynylbenzene as the raw material for the reaction. However, the solubility of dichloromethane (DCM) or the mixed solvent thereof in HEB-TMS and hexaethynylbenzene (HEB) is low, and the yield of the composite material per unit volume of solvent in a single experiment is low. However, if a solvent with higher monomer solubility, such as toluene, tetrahydrofuran, dimethyl sulfoxide, etc., is used, it is found through experiments that it is more difficult for the reaction to proceed, and the yield of the obtained graphdiyne / graphene / graphdiyne powder is lower. The present application uses a microwave method to synthesize the above composite material, which can overcome the technical problem in the prior art that using a solvent with higher solubility in HEB-TMS and hexaethynylbenzene (HEB) is not conducive to the reaction, and can directly use hexaethynylbenzene as the raw material for preparing the graphdiyne composite material, without using a DCM solution of hexaethynylbenzene as the raw material for the reaction, and using a solvent with higher solubility in the reaction process, which is conducive to improving the yield of the graphdiyne / graphene / graphdiyne composite material per unit volume of solvent in a single experiment.

[0012] According to a specific embodiment of the present application, there is no dichloromethane in the reaction system of step S3 or step S4. The technical problem that the solvent must contain dichloromethane in the prior art is overcome.

[0013] According to an embodiment of the present application, step S1 specifically comprises the following steps: dissolving monomer HEB-TMS in an organic solvent, which is one or more of toluene, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, adding the solution of monomer HEB-TMS into a magnetically stirred reactor, adding tetrabutylammonium fluoride thereto, reacting in an ice water bath in the dark, and rotary evaporation to obtain the product of hexaethynylbenzene.

[0014] The monomer HEB-TMS is a compound shown in formula (I),

[0015]

[0016] The purpose of adding tetrabutylammonium fluoride is to perform desiliconization of HEB-TMS.

[0017] According to an embodiment of the present application, step S1 is performed under an inert atmosphere. The purpose of performing under an inert atmosphere is to prevent oxidation of HEB.

[0018] According to an embodiment of the present application, the organic solvent in step S2 is one or more of toluene, tetrahydrofuran, pyridine, chlorobenzene, dimethyl sulfoxide. Using this solvent, the solubility of monomer HEB-TMS and hexaethynylbenzene (HEB) is higher, especially significantly higher than that of dichloromethane.

[0019] According to an embodiment of the present application, the copper salt is one or more of copper acetate, copper nitrate, copper sulfate, copper chloride.

[0020] Preferably, the concentration of the copper salt is 4 mmol / L to 12 mmol / L.

[0021] According to an embodiment of the present application, the graphene has a sheet diameter of 0.01-50 μm and a layer number of 1-10 layers. Using graphene as a substrate, compared with substrates such as silica, hydrogel, and NaCl, on the one hand, it serves as a substrate for the growth of graphdiyne, and on the other hand, it is also part of the final product. Compared with single graphdiyne, the graphdiyne / graphene / graphdiyne sandwich structure composite material has higher conductivity and wider application in the field of electrochemistry.

[0022] According to an embodiment of the present application, the mass ratio of graphene to hexaethynylbenzene is 3:1-1:3. Using this mass ratio, the sandwich structure is well generated. If the amount of graphene is greater than this range, there will be no graphdiyne generated on part of the graphene; if less than this range, there will be separate graphdiyne.

[0023] According to a specific embodiment of the present application, the microwave reaction has a power of 200-700 W and a reaction time of 30 s-5 min.

[0024] Advantages:

[0025] This method is universal and can be used in different sizes of graphene carriers and different solvents to obtain good graphdiyne / graphene / graphdiyne sandwich structures, which is a bridge from small size in the laboratory to large size industrialization. The yield of the graphdiyne / graphene / graphdiyne sandwich structure obtained by a single experiment in a unit volume reactor is high, which is conducive to industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 is a TEM image (a) and a Raman spectrum (b) of the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 1, and a TEM image (c) of graphene;

[0027] Figure 2 is an XPS spectrum of the graphdiyne / graphene / graphdiyne sandwich structure of Example 1;

[0028] Figure 3 is a TEM image (a) and a Raman spectrum (b) of the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 2;

[0029] Figure 4 is a TEM image (a) and a Raman spectrum (b) of the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 3;

[0030] Figure 5 is a TEM image (a) and a Raman spectrum (b) of the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 4;

[0031] Figure 6 The a image in is a TEM image of the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 5;

[0032] Figure 6 The b image in is a TEM image of graphene in the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 5;

[0033] Figure 7 The a image in is a TEM image of the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 6;

[0034] Figure 7 The b image in is a TEM image of graphene in the graphdiyne / graphene / graphdiyne sandwich structure prepared in Example 6. DETAILED DESCRIPTION

[0035] In order to more clearly illustrate the present application, further description will be made through examples. The following examples do not limit the scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

[0036] Example 1

[0037] 60 mg of monomer HEB-TMS was weighed and dissolved in 60 mL of tetrahydrofuran under argon atmosphere, and stirred well to mix uniformly. 2 mL of tetrabutylammonium fluoride was added under ice water bath, and the reaction was carried out for 15 min under ice water bath and in the dark to perform desiliconization operation. The desiliconized monomer was extracted by ethyl acetate and saturated brine solution, and then anhydrous magnesium sulfate was added to remove excess water. After rotary evaporation, hexaethynylbenzene was obtained. 160 mg of copper acetate was added to 120 mL of organic solvent (toluene: tetrahydrofuran: pyridine in a volume ratio of 1:1:1) and placed in a beaker, and ultrasonic was used to make it completely dissolved. Then 20 mg of graphene powder (flake diameter > 50 μm, flake layer 1-3 layers) was added and ultrasonic was used to disperse uniformly. 20 mg of hexaethynylbenzene was poured into the above dispersion, and ultrasonic was used for 2 min until it was completely dissolved. Then the beaker with the mixed solution was placed in a microwave oven, and the reaction was carried out for 1 min under microwave power of 700 W. After the reaction was completed, it was cooled to room temperature, and then acetone, pyridine, dilute hydrochloric acid and water were used for centrifugal washing in sequence, and then freeze-drying was performed to obtain graphene diacetylene / graphene / graphene diacetylene sandwich structure powder. Figure 1 TEM image (a) and Raman spectrum (b) of the material of Example 1 can be seen, and the morphology of GDY / G is consistent with that of graphene (c), and the surface is rough. In the Raman spectrum, the acetylene coupling peak at 2174 cm-1 can be seen. Figure 2 XPS spectrum of the graphene diacetylene / graphene / graphene diacetylene sandwich structure prepared in Example 1, from Figure 2 It can be seen that the C peak is divided into four sub-peaks, which are respectively attributed to C=C (284.4 eV), C≡C (285.1 eV), C-O (286.1 eV) and C=O (288.0 eV). The mass of the finally obtained graphene diacetylene / graphene / graphene diacetylene sandwich structure powder is 36.8 mg.

[0038] Example 2

[0039] Take 60 mg of HEB-TMS monomer under argon atmosphere, dissolve in 60 mL of tetrahydrofuran, fully stirred to mix evenly, add 2 mL of tetrabutylammonium fluoride under ice water bath, react for 15 min under ice water bath and light shielding to carry out desiliconization operation, the desiliconized monomer is extracted by ethyl acetate and saturated brine solution, then anhydrous magnesium sulfate is added to remove excess water, and hexaethynylbenzene is obtained by rotary evaporation. Add 160 mg of copper acetate to 120 mL of organic solvent (volume ratio of toluene: tetrahydrofuran is 1:1) and place in a beaker, ultrasonic to completely dissolve, then add 20 mg of graphene powder (flake diameter > 50 μm, flake layer is 1-3 layers) and ultrasonic to disperse evenly. Pour 20 mg of hexaethynylbenzene into the above dispersion, ultrasonic for 4 min until it is completely dissolved. Then place the beaker with the mixed solution in the microwave oven, react for 2 min under microwave power of 700 W. After the reaction is completed, cool to room temperature, centrifugal wash with acetone, pyridine, dilute hydrochloric acid and water in turn, and freeze-drying to obtain graphene / graphite diacetylene / graphene sandwich structure powder. Figure 3 TEM and Raman spectra of the composite material prepared in Example 2 can be seen that the morphology of GDY / G is consistent with that of graphene, and the surface is rough. In the Raman spectrum, the alkyne coupling peak at 2174 cm-1 and the alkyne copper peak at 1925 cm-1 can be seen. The mass of the finally obtained graphene / graphite diacetylene / graphene sandwich structure powder is 36.2 mg.

[0040] Example 3

[0041] Take 60 mg of HEB-TMS monomer under argon atmosphere, dissolve in 60 mL of tetrahydrofuran, fully stirred to mix evenly, add 2 mL of tetrabutylammonium fluoride under ice water bath, react for 15 min under ice water bath and light shielding to carry out desiliconization operation, the desiliconized monomer is extracted by ethyl acetate and saturated brine solution, then anhydrous magnesium sulfate is added to remove excess water, and hexaethynylbenzene is obtained by rotary evaporation. Add 160 mg of copper acetate to 120 mL of dimethyl sulfoxide and place in a beaker, ultrasonic to completely dissolve, then add 20 mg of graphene powder (flake diameter > 50 μm, flake layer is 1-3 layers) and ultrasonic to disperse evenly. Pour 20 mg of hexaethynylbenzene into the above dispersion, ultrasonic for 4 min until it is completely dissolved. Then place the beaker with the mixed solution in the microwave oven, react for 2 min under microwave power of 700 W. After the reaction is completed, cool to room temperature, centrifugal wash with acetone, pyridine, dilute hydrochloric acid and water in turn, and freeze-drying to obtain graphene / graphite diacetylene / graphene sandwich structure powder. Figure 4TEM and Raman spectra of the composite material prepared in Example 3 can be seen that the morphology of GDY / G is consistent with the morphology of graphene, and the surface is relatively rough. In the Raman spectrum, the alkyne-alkyne coupling peak at 2174 cm-1 can be seen. The mass of the finally obtained graphdiyne / graphene / graphdiyne sandwich structure powder is 36.0 mg.

[0042] Example 4

[0043] 60 mg of HEB-TMS monomer was weighed and dissolved in 60 mL of tetrahydrofuran under an argon inert atmosphere, and stirred to mix well. 2 ml of tetrabutylammonium fluoride was added under an ice water bath, and the desiliconization operation was carried out under an ice water bath and in the dark for 15 min. The desiliconized monomer was extracted with ethyl acetate and saturated brine solution, and then anhydrous magnesium sulfate was added to remove excess water. After rotary evaporation, hexaethynylbenzene was obtained. 160 mg of copper acetate was added to 120 mL of organic solution (volume ratio of toluene: dimethyl sulfoxide is 1:1) in a beaker and ultrasonicated to completely dissolve. Then 20 mg of graphene powder (flake diameter > 50 μm, flake layer is 1-3 layers) was added and ultrasonicated to disperse uniformly. 20 mg of hexaethynylbenzene was poured into the above dispersion liquid and ultrasonicated for 3 min until it was completely dissolved. Then the beaker with the mixed liquid was placed in a microwave oven and reacted for 1.5 min under a microwave power of 600 W. After the reaction was completed, it was cooled to room temperature, and was washed with acetone, pyridine, dilute hydrochloric acid and water in turn, and freeze-dried to obtain a graphdiyne / graphene / graphdiyne sandwich structure powder. Figure 5 TEM and Raman spectra of the material of Example 4 can be seen that the morphology of GDY / G is consistent with the morphology of graphene, and the surface is relatively rough. In the Raman spectrum, the alkyne-alkyne coupling peak at 2174 cm-1 can be seen. The mass of the finally obtained graphdiyne / graphene / graphdiyne sandwich structure powder is 36.3 mg.

[0044] Example 5

[0045] The 60 mg HEB-TMS monomer was dissolved in 60 mL of tetrahydrofuran under an argon atmosphere, and stirred to mix well. 2 mL of tetrabutylammonium fluoride was added under an ice water bath, and the reaction was carried out for 15 min under an ice water bath and in the dark. The desiliconized monomer was extracted by ethyl acetate and saturated brine, and then anhydrous magnesium sulfate was added to remove excess water. After rotary evaporation, hexaethynylbenzene was obtained. 140 mg of copper acetate was added to 120 mL of organic solvent (toluene: tetrahydrofuran: pyridine in a volume ratio of 1:1:1) and placed in a beaker, and ultrasonic was used to completely dissolve it. Then 30 mg of graphene powder (4-8 μm in diameter and 1-3 layers in thickness) was added and ultrasonic was used to disperse it uniformly. 20 mg of hexaethynylbenzene was poured into the above dispersion, and ultrasonic was used for 2 min until it was completely dissolved. Then the beaker with the mixture was placed in a microwave oven, and the reaction was carried out for 1.5 min under a microwave power of 700 W. After the reaction was completed, it was cooled to room temperature, and then acetone, pyridine, dilute hydrochloric acid and water were used for centrifugal washing in sequence, and then freeze-drying was carried out to obtain the graphene diacetylene / graphene / graphene diacetylene sandwich structure powder. Figure 6 For the TEM image of the material of Example 5, it can be seen that the morphology of GDY / G is consistent with that of graphene, and the surface is relatively rough. The mass of the finally obtained graphene diacetylene / graphene / graphene diacetylene sandwich structure powder is 36.6 mg.

[0046] Example 6

[0047] The 60 mg HEB-TMS monomer was dissolved in 60 mL of tetrahydrofuran under an argon atmosphere, and stirred to mix well. 2 mL of tetrabutylammonium fluoride was added under an ice water bath, and the reaction was carried out for 15 min under an ice water bath and in the dark. The desiliconized monomer was extracted by ethyl acetate and saturated brine, and then anhydrous magnesium sulfate was added to remove excess water. After rotary evaporation, hexaethynylbenzene was obtained. 140 mg of copper acetate was added to 120 mL of organic solvent (toluene: tetrahydrofuran: pyridine in a volume ratio of 1:1:1) and placed in a beaker, and ultrasonic was used to completely dissolve it. Then 30 mg of graphene powder (4-8 μm in diameter and 1-3 layers in thickness) was added and ultrasonic was used to disperse it uniformly. 20 mg of hexaethynylbenzene was poured into the above dispersion, and ultrasonic was used for 2 min until it was completely dissolved. Then the beaker with the mixture was placed in a microwave oven, and the reaction was carried out for 1.5 min under a microwave power of 700 W. After the reaction was completed, it was cooled to room temperature, and then acetone, pyridine, dilute hydrochloric acid and water were used for centrifugal washing in sequence, and then freeze-drying was carried out to obtain the graphene diacetylene / graphene / graphene diacetylene sandwich structure powder. Figure 7 For the TEM image of the material of Example 6, it can be seen that the morphology of GDY / G is consistent with that of graphene, and the surface is relatively rough. The mass of the finally obtained graphene diacetylene / graphene / graphene diacetylene sandwich structure powder is 36.5 mg.

[0048] Example 7

[0049] The 60 mg of monomer HEB-TMS was dissolved in 60 mL of dichloromethane under an inert atmosphere of argon, and stirred well to mix. 2 ml of tetrabutylammonium fluoride was added under an ice water bath, and the desilylation reaction was carried out in the dark for 15 min under an ice water bath. The desilylated monomer was extracted by ethyl acetate and saturated brine solution, and then anhydrous magnesium sulfate was added to remove the excess water. After rotary evaporation, hexaethynylbenzene was obtained. 160 mg of copper acetate was added to 120 mL of organic solvent (volume ratio of toluene: tetrahydrofuran: pyridine = 1:1:1) in a beaker and ultrasonicated to completely dissolve. 20 mg of graphene powder (flake diameter > 50 pm, flake layer 1-3 layers) was added and ultrasonicated to disperse uniformly. 20 mg of hexaethynylbenzene was poured into the above dispersion and ultrasonicated for 2 min until it completely dissolved. Then the beaker with the mixture was placed in a microwave oven and reacted for 1 min at a microwave power of 700 W. After the reaction was completed, it was cooled to room temperature, and then centrifuged and washed with acetone, pyridine, dilute hydrochloric acid and water in sequence, and freeze-dried to obtain graphene / hexaethynylbenzene / graphene sandwich structure powder. The mass of the final graphene / hexaethynylbenzene / graphene sandwich structure powder was 36.7 mg.

[0050] Comparative Example 1

[0051] The 60 mg of monomer HEB-TMS was dissolved in 60 mL of dichloromethane under an inert atmosphere of argon, and stirred well to mix. 2 ml of tetrabutylammonium fluoride was added under an ice water bath, and the desilylation reaction was carried out in the dark for 15 min under an ice water bath. The desilylated monomer was extracted by ethyl acetate and saturated brine solution, and then anhydrous magnesium sulfate was added to remove the excess water. After rotary evaporation, hexaethynylbenzene was obtained. 160 mg of copper acetate was added to 120 mL of organic solvent (volume ratio of toluene: tetrahydrofuran: pyridine = 1:1:1) in a beaker and ultrasonicated to completely dissolve. 20 mg of graphene powder (flake diameter > 50 pm, flake layer 1-3 layers) was added and ultrasonicated to disperse uniformly. 20 mg of hexaethynylbenzene was poured into the above dispersion and ultrasonicated for 2 min until it completely dissolved. Then the beaker with the mixture was placed in a microwave oven and reacted for 1 min at a microwave power of 700 W. After the reaction was completed, it was cooled to room temperature, and then centrifuged and washed with acetone, pyridine, dilute hydrochloric acid and water in sequence, and freeze-dried to obtain graphene / hexaethynylbenzene / graphene sandwich structure powder. The mass of the final graphene / hexaethynylbenzene / graphene sandwich structure powder was 36.7 mg.

[0052] Comparative Example 2

[0053] The 60 mg of monomer HEB-TMS was dissolved in 60 mL of dichloromethane under inert atmosphere, and stirred well to mix evenly. Tetra-butyl ammonium fluoride was added under ice water bath, and the reaction was carried out in the ice water bath for 15 min in the dark to remove silicon. The monomer after desiliconization was extracted by ethyl acetate and saturated brine, and then anhydrous magnesium sulfate was added to remove excess water. After rotary evaporation, hexa-ethynyl benzene was obtained. 20 mg of hexa-ethynyl benzene and 160 mg of copper acetate were added to 120 mL of organic solvent (toluene: tetrahydrofuran: pyridine, volume ratio 1:1:1) in a beaker, and the above-mentioned DCM solution containing hexa-ethynyl benzene was added dropwise. The reaction was carried out in the dark for 24 hours under argon protection. The mass of the final obtained graphite diyne / graphene / graphite diyne sandwich structure powder was 26.5 mg.

[0054] The results are summarized in Table 1

[0055]

[0056]

Claims

1. A method for preparing a graphdiyne / graphene / graphdiyne sandwich structure composite material, characterized in that, Specifically comprising the following steps: S1, preparing hexaethynylbenzene; S2, mixing copper salt and organic solvent, dissolving, then adding graphene powder, uniformly dispersing, to obtain copper salt / graphene organic dispersion liquid; S3, mixing the hexaethynylbenzene prepared in step S1 and the copper salt / graphene organic dispersion liquid uniformly, to obtain hexaethynylbenzene / copper salt / graphene mixed liquid; S4, subjecting the hexaethynylbenzene / copper salt / graphene mixed liquid to microwave reaction, centrifuging, washing, and drying, to obtain the graphdiyne / graphene / graphdiyne sandwich structure composite material.

2. The production method according to claim 1, characterized by, Step S1 specifically comprises the following steps: dissolving monomer HEB-TMS in an organic solvent, the organic solvent being one or more of toluene, tetrahydrofuran, dimethyl sulfoxide, dichloromethane, adding the solution dissolving monomer HEB-TMS into a magnetically stirred reactor, adding tetrabutylammonium fluoride thereto, rotary evaporation, to obtain the hexaethynylbenzene.

3. The preparation method according to claim 1, characterized in that, Step S1 is carried out under an inert atmosphere.

4. The method of claim 1, wherein, The organic solvent in step S2 is one or more of toluene, tetrahydrofuran, pyridine, chlorobenzene, dimethyl sulfoxide.

5. The preparation method according to claim 4, characterized in that, The organic solvent in step S2 is toluene / tetrahydrofuran / pyridine, toluene / tetrahydrofuran, or toluene / dimethyl sulfoxide.

6. The preparation method according to claim 4, characterized in that, In the reaction system of step S3 or step S4, there is no dichloromethane.

7. The preparation method according to claim 1, characterized in that, The copper salt is one or more of copper acetate, copper nitrate, copper sulfate, and copper chloride.

8. The method of claim 1, wherein, The concentration of the copper salt is 4 mmol / L to 12 mmol / L.

9. The method of claim 1, wherein, The graphene has a sheet diameter of 0.01-50 and a layer number of 1-10 layers.

10. The method of claim 1, wherein, The mass ratio of graphene to hexaethynylbenzene is 3:1 to 1:

3.

11. The method of claim 1, wherein, The power of the microwave reaction is 200 W to 700 W, and the reaction time is 30 s to 5 min.

12. Application of the composite material prepared by the preparation method of any one of claims 1-11 in the fields of catalysis, energy storage, optics, and biology.

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