Method for preparing graphdiynyl material based on Sonogashira-Hagihara cross-coupling reaction

Abstract

The invention discloses a method for preparing a graphdiynyl material based on a Sonogashira-Hagihara cross-coupling reaction, and belongs to the technical field of Sonogashira-Hagihara cross-coupling Reaction. According to the method, halogenated aromatic hydrocarbon and an alkynyl compound are used as raw materials, a palladium catalyst / copper catalyst is used as a catalytic system, and the graphdiynyl material is prepared by regulating the alkalinity and the polarity of a solvent. According to the present invention, the graphitized alkynyl material is obtained through the in-situ removal of the protection group on the acetylenic bond of the alkynyl compound and the Sonogashira-Hagihara cross coupling with the halogenated aromatic hydrocarbon, such that the method can select the variety of the halogenated aromatic hydrocarbon, the cost is low, the side reaction during the polymerization process is less, the variety of the graphitized alkynyl can be easily expanded, the development and the utilization of the high-quality graphitized alkynyl film can be easily achieved, and the method can be used for the preparation of the graphitized alkynyl material. The preparation cost of graphdiyne is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of Sonogashira-Hagihara cross-coupling reaction, and in particular relates to a method for preparing a graphene-based material based on the Sonogashira-Hagihara cross-coupling reaction. Background Art

[0002] Graphdiyne is a new type of sp and sp 2 Two-dimensional all-carbon materials of hybridized carbon atoms are internationally recognized as a major breakthrough in carbon material research. One of the most important structural features of graphyne is the presence of sp carbon, which gives it many unique properties that traditional carbon materials do not have, such as abundant carbon chemical bonds, natural band gaps, ultra-large continuous holes, and uneven surface charge distribution. Since the first successful preparation of graphene diyne (γ-GDY) by the research group of Academician Li Yuliang in 2010, it has shown great potential in basic science and applied science in many fields such as catalysis, energy conversion and storage, optoelectronics, information, and smart devices (Chem. Commun. 2010, 46, 3256-3258). Scientists synthesized alkynyl monomers in the early stage, and selected suitable planar templates to confine monomers to grow in two-dimensional directions to prepare γ-GDY films through alkynyl-alkynyl coupling (Glaser-Hay, Eglinton and Hiyama coupling). However, the synthesis of alkynyl monomers is difficult, the types are few, and side reactions are prone to occur during the polymerization process, which to a certain extent limits the types of graphyne and the development and utilization of high-quality graphyne films. Summary of the invention

[0003] In order to solve the above technical problems, the present invention proposes a method for preparing graphyne-based materials based on the Sonogashira-Hagihara cross-coupling reaction. The present invention can select a variety of halogenated aromatic hydrocarbons with low cost, and has fewer side reactions during the polymerization process, which is beneficial to the development and utilization of graphyne types and high-quality graphyne films, and reduces the preparation cost of graphyne-based materials.

[0004] To achieve the above object, the present invention provides the following technical solutions:

[0005] One of the technical solutions of the present invention:

[0006] A method for preparing graphene-based materials based on the Sonogashira-Hagihara cross-coupling reaction, using halogenated aromatic hydrocarbons and alkynyl compounds as starting materials, using a palladium catalyst / copper catalyst as a catalytic system, and regulating the basicity and polarity of the solvent to remove the protecting group on the acetylenic bond of the alkynyl compound in situ, and undergoing a Sonogashira-Hagihara cross-coupling reaction with the halogenated aromatic hydrocarbon to prepare the graphene-based material.

[0007] Preferably, the acetylenic bond of the acetylenic compound has a silicon-based protecting group.

[0008] More preferably, the alkynyl compound includes trimethylsilyl acetylene, bis(trimethylsilyl)acetylene, 1,4-bis(trimethylsilyl)-1,3-butadiyne or 4-trimethylsilane-1,3-butadiyne.

[0009] Preferably, the halogenated aromatic hydrocarbon is a highly symmetrical polyhalogenated aromatic hydrocarbon, the number of carbon-halogen bonds in its structure is ≥3, and the symmetry of the carbon-halogen bond orientation is D 2h , D 3h , D 4h , D 6h or T d .

[0010] The invention uses halogenated benzene and alkynyl compounds as starting materials, uses palladium catalyst / copper catalyst as catalytic system, carries out Sonogashira-Hagihara cross-coupling reaction in polar solvent, and controls the in-situ removal of protective groups on the acetylenic bonds of acetylenic compounds by regulating the alkalinity and polarity of the solvent (the silicon on the C-Si bond of the acetylenic bond compound is a positive center, which can react with the nucleophilic reagent OH in the solution). - Reaction), and Sonogashira-Hagihara coupling with halogenated aromatic hydrocarbons to obtain graphene-based materials. The reaction route is as follows:

[0011]

[0012] Preferably, the solvent used in the Sonogashira-Hagihara cross-coupling reaction is a polar solvent, the reaction temperature is 70-90° C., and the reaction time is 72 h.

[0013] Preferably, the palladium catalyst comprises Pd(PPh3)4, Pd(dba)2, Pd(PPh3)2Cl2 or Pd(dppf)Cl2;

[0014] The copper catalyst is a monovalent copper catalyst, including CuCl, CuBr, CuI or a Cu(I) complex dissolved from the surface of a copper sheet;

[0015] The polar solvent includes at least two of N,N-dimethylformyl, tetrahydrofuran, toluene and water, and these solvents can ensure efficient Sonogashira-Hagihara cross reaction between monomers.

[0016] Preferably, the alkalinity is regulated by adding a base to the solvent to control the pH of the solvent to be 8 to 13; the base includes triethylamine, diisopropylamine, potassium carbonate or sodium carbonate.

[0017] More preferably, the halogenated aromatic hydrocarbon is a polyhalogenated aromatic hydrocarbon, which may have a two-dimensional structure or a three-dimensional structure, including hexabromobenzene, 1,3,5-triiodobenzene, 1,2,4,5-tetrabromobenzene, tetrakis(4-bromophenyl)methane, 2,3,6,7,12,13-hexabromotriptycene or 2,4,6-triiodophenol.

[0018] More preferably, the method for preparing graphene monoacetylene (γ-GY) using halogenated aromatic hydrocarbons and alkynyl compounds as starting materials is as follows: accurately weigh 0.036 mmol of hexabromobenzene in 7 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V=3 / 3 / 1), add 1 mL of triethylamine, control the pH of the system to 8, introduce nitrogen for 15 minutes, then add 10 mg of Pd(PPh3)2Cl2 and 3 mg of CuI, 0.216mmol trimethylsilyl acetylene, seal the above system, and let it stand at 90℃ for 72 hours to react (the reaction limits the growth of monomers in two dimensions through the self-template effect of the polymerization intermediate), filter after the reaction, and wash the obtained black film with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane three times in turn, and dry. The treated film is further placed in a hot pyridine solution (70-110℃, the purpose is to remove Pd and Cu elements in the film), filter after reaction for 72 hours, and the solid film is washed with dichloromethane, methanol and anhydrous ethanol in turn, and dried to obtain a γ-GY film.

[0019] In the method of preparing γ-GY film using polyhalogenated aromatic hydrocarbons and alkynyl compounds as starting materials, other polyhalogenated aromatic hydrocarbons (such as 1,3,5-triiodobenzene, 1,2,4,5-tetrabromobenzene, tetrakis(4-bromophenyl)methane, 2,3,6,7,12,13-hexabromotriptycene or 2,4,6-triiodophenol) are used instead of hexabromobenzene to prepare two-dimensional halogenated aromatic hydrocarbons with C2, C3, C4 and C6 symmetries to obtain γ-GY derivatives with rhombus, hexagonal, quadrilateral and triangular pores (Table 1); halogenated aromatic hydrocarbons with three-dimensional structure can obtain three-dimensional graphyne, which has a larger specific surface area and exposes more active sites, which is beneficial to gas adsorption and energy storage (Adv.Energy Mater.2021,11,2101197). Using polyhalogenated aromatic hydrocarbons and acetylenic compounds as starting materials, a variety of γ-GY derivative films (such as H-GY, OH-GY and F-GY) can be prepared. For example, OH-GY is synthesized using 2,4,6-triiodophenol as a monomer. The phenolic hydroxyl group on the benzene ring of this material can provide protons in situ, and the electron-rich acetylenic bond is conducive to the adsorption of protons, which has potential applications in the field of photocatalytic hydrogen or carbon dioxide production.

[0020] Table 1. Structures of γ-GY derivative films prepared with polyhalogenated aromatic hydrocarbons and trimethylsilyl acetylene as monomers

[0021]

[0022] Note: Table 1 only lists common polyhalogenated aromatic hydrocarbons. Other polyhalogenated aromatic hydrocarbons can be cross-coupled with trimethylsilyl acetylene through Sonogashira-Hagihara cross-coupling according to the extension direction of the carbon-halogen bond to synthesize graphyne derivatives with novel topological structures.

[0023] More preferably, the method for preparing graphene diyne (γ-GDY) using halogenated aromatic hydrocarbons and alkynyl compounds as starting materials is as follows: accurately weigh 0.036 mmol of hexabromobenzene in 7 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V=3 / 3 / 1), add 1 mL of triethylamine, control the pH of the system to 8, introduce nitrogen for 15 minutes, then add 10 mg of Pd(PPh3)2Cl2 and 3 mg of CuI, 0.216 mmol of 1,4-bis(trimethylsilyl)-1,3-butadiyne, the above system is sealed and allowed to react at 90°C for 72 hours (the reaction limits the growth of monomers in two dimensions through the self-template effect of the polymerization intermediate), filtered after the reaction, and the obtained black film is washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in turn, and dried. The treated film is further placed in a hot pyridine solution (70-110°C, the purpose is to remove Pd and Cu elements in the film), filtered after the reaction for 72 hours, and the solid film is washed with dichloromethane, methanol and anhydrous ethanol in turn, and dried to obtain a γ-GDY film.

[0024] In the method of preparing a γ-GDY derivative film using polyhalogenated aromatic hydrocarbons and alkynyl compounds as starting materials, other polyhalogenated aromatic hydrocarbons (such as 1,3,5-triiodobenzene, 1,2,4,5-tetrabromobenzene, tetrakis(4-bromophenyl)methane, 2,3,6,7,12,13-hexabromotriptycene or 2,4,6-triiodophenol) are used to replace hexabromobenzene, and two-dimensional halogenated aromatic hydrocarbons with C2, C3, C4 and C6 symmetries can obtain γ-GDY derivatives with rhombus, hexagonal, quadrilateral and triangular holes.

[0025] The second technical solution of the present invention:

[0026] The present invention also provides the application of the graphene-based material prepared by the above method in the field of photocatalysis. For example, the two-dimensional graphene monoacetylene OH-GY prepared by the method of the present invention can be used for photolysis of water to produce hydrogen, and the hydrogen evolution activity under visible light is as high as 0.93mmol g -1· h -1 .

[0027] Compared with the prior art, the present invention has the following advantages and technical effects:

[0028] The invention introduces a protecting group into the terminal alkyne of the alkynyl compound, and prepares a graphene-based material by in-situ deprotection and Sonogashira-Hagihara coupling with polyhalogenated aromatic hydrocarbons, which can be used in the field of photocatalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The drawings constituting a part of the present application are used to provide a further understanding of the present application. The illustrative embodiments and descriptions of the present application are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0030] Figure 1 The structural characterization of the two-dimensional graphene monoacetylene γ-GY prepared in Example 1, wherein (a) a schematic diagram of the synthesis of γ-GY; (b) an optical photograph of γ-GY dispersed in water; (c, d) SEM images of γ-GY; (e, f) EDS mapping images of γ-GY;

[0031] Figure 2 The infrared spectrum of the two-dimensional graphene monoyne γ-GY prepared in Example 1;

[0032] Figure 3 The element distribution diagram of the two-dimensional graphene monoyne γ-GY prepared in Example 1;

[0033] Figure 4 The structure characterization of the two-dimensional graphene monoacetylene OH-GY prepared in Example 3, wherein (a) a schematic diagram of the synthesis of OH-GY; (b) an optical photograph of OH-GY; (c) a SEM image of OH-GY; (d) an infrared spectrum of OH-GY;

[0034] Figure 5 The structure characterization of the two-dimensional graphene monoacetylene F-GY prepared in Example 4, wherein (a) SEM image of F-GY; (b) infrared spectrum of F-GY;

[0035] Figure 6 This is a graph showing the change in hydrogen production over time of the two-dimensional graphene monoacetylene OH-GY prepared in Example 3;

[0036] Figure 7 This is the structural characterization of the two-dimensional graphene diyne γ-GDY prepared in Example 8, including (a) schematic diagram of the synthesis of γ-GDY; and (b) SEM image of γ-GDY. DETAILED DESCRIPTION

[0037] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0038] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0039] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0040] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0041] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0042] All raw materials used in the present invention are purchased from commercial sources.

[0043] The technical solution of the present invention is further illustrated by the following embodiments.

[0044] A typical example of preparing graphene alkynyl materials using halogenated aromatic hydrocarbons and alkynyl monomers containing protective groups as starting materials is as follows:

[0045] Example 1 Synthesis of two-dimensional graphene monoyne γ-GY

[0046] 0.036mmol hexabromobenzene was accurately weighed and dissolved in 7mL N,N-dimethylformamide / toluene / water (V / V / V=3 / 3 / 1) mixed solution, 1mL triethylamine was added, the pH of the system was controlled to 8, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.216mmol trimethylsilyl acetylene were added in sequence, the above system was sealed, and allowed to react at 90°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate), after the reaction was completed, the black film was filtered, and the obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after the reaction for 72 hours, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain 10mg black γ-GY film, its structural characterization is shown in Figure 1 , where (a) schematic diagram of the synthesis of γ-GY, yellow is the structure of γ-GY simulated by Materials Studio; (b) optical photo of γ-GY dispersed in water; (c, d) SEM images of γ-GY; (e, f) EDS mapping images of γ-GY, it can be seen that the γ-GY film is a two-dimensional film; infrared spectrum is shown in Figure 2 , of which 1618cm -1 Belongs to the stretching vibration of the benzene ring; 2183cm -1 is the stretching vibration peak of the alkynyl group; the element distribution diagram is shown in Figure 3 , indicating that the γ-GY film is mainly composed of carbon elements, and the oxygen elements come from the water adsorbed in the pores of the γ-GY film and the oxygen in the air.

[0047] Example 2 Synthesis of two-dimensional graphene monoacetylene H-GY

[0048] 0.036mmol 1,3,5-triiodobenzene was accurately weighed and dissolved in 4mL tetrahydrofuran / methanol / water (V / V / V=2 / 1 / 1) mixed solution, 216mg potassium carbonate was added, the pH of the system was controlled to be 12, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.216mmol trimethylsilyl acetylene were added in sequence, the above system was sealed, and the reaction was allowed to stand at 70°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate), and the reaction was filtered after the reaction was completed. The obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after the reaction for 72 hours, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain 12mg yellow H-GY film.

[0049] Example 3 Synthesis of two-dimensional graphene monoacetylene OH-GY

[0050] 0.036mmol 2,4,6-triiodophenol was accurately weighed and dissolved in 4mL tetrahydrofuran / methanol / water (V / V / V=2 / 1 / 1) mixed solution, 216mg potassium carbonate was added, the pH of the system was controlled to 12, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.108mmol trimethylsilyl acetylene were added in sequence, the above system was sealed, and the reaction was allowed to stand at 70°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate). After the reaction, the film was filtered, and the obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after the reaction for 72 hours, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain 13mg orange OH-GY film, its structural characterization is shown in Figure 4 , where (a) schematic diagram of the synthesis of OH-GY; (b, c) optical photographs and SEM images of OH-GY, indicating that OH-GY is a two-dimensional film; (d) infrared spectrum of OH-GY, 1582cm -1 The stretching vibration peak of the carbon-carbon double bond on the benzene ring is 2149 cm -1 、2114cm -1 It is the asymmetric stretching vibration peak of the alkynyl group.

[0051] Example 4 Synthesis of two-dimensional graphene monoacetylene F-GY

[0052] 0.036mmol 1,3,5-triiodo-2,4,6-trifluorobenzene was accurately weighed and dissolved in 4mL tetrahydrofuran / methanol / water (V / V / V=2 / 1 / 1) mixed solution, 216mg potassium carbonate was added, the pH of the system was controlled to 12, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.108mmol trimethylsilyl acetylene were added in sequence, the above system was sealed, and the reaction was allowed to stand at 70°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate). After the reaction, the black film was filtered and washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after reaction for 72 hours, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain 15mg F-GY film, the structural characterization diagram of which is shown in Figure 5, where (a) SEM image of F-GY, indicating that F-GY is a two-dimensional film; (b) IR spectrum of F-GY, 1588cm -1 The stretching vibration peak of the carbon-carbon double bond on the benzene ring is 2147 cm -1 、2104cm -1 It is the asymmetric stretching vibration peak of the alkynyl group.

[0053] Example 5 Synthesis of two-dimensional graphene monoacetylene N-GY

[0054] 0.036mmol 2,4,6-bromopyridine was accurately weighed and dissolved in 4mL N,N-dimethylformamide / toluene / water (V / V / V=2 / 1 / 1) mixed solution, 1mL triethylamine was added, the pH of the system was controlled to 8, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.108mmol trimethylsilyl acetylene were added in sequence, the above system was sealed, and the reaction was allowed to stand at 80°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate). After the reaction was completed, the black film was filtered, and the obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film was further placed in a hot pyridine solution (80°C, in order to remove Pd and Cu elements in the film), filtered after reaction for 72 hours, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain an N-GY film.

[0055] Example 6 Synthesis of two-dimensional graphene monoacetylene Pyr-GY

[0056] 0.036mmol 1,3,6,8-tetrabromopyrene was accurately weighed and dissolved in 4mL N,N-dimethylformamide / toluene / water (V / V / V=2 / 1 / 1) mixed solution, 1mL triethylamine was added, the pH of the system was controlled to 8, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.144mmol trimethylsilyl acetylene were added in sequence, the above system was sealed, and allowed to react at 90°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate). After the reaction, it was filtered, and the obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after reaction for 72 hours, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain a Pyr-GY film.

[0057] Example 7 Synthesis of three-dimensional graphene monoacetylene T-GY

[0058] 0.036mmol 1,3,6,8-tetrabromopyrene was accurately weighed and dissolved in 4mL N,N-dimethylformamide / toluene / water (V / V / V=2 / 1 / 1) mixed solution, 1mL triethylamine was added, the pH of the system was controlled to 8, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.144mmol trimethylsilyl acetylene were added in sequence, the above system was sealed, and allowed to react at 90°C for 72 hours. After the reaction was completed, it was filtered, and the obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after reaction for 72 hours, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain a T-GY film.

[0059] Application Example 1 Application of two-dimensional graphene OH-GY (prepared in Example 3) in photolysis of water to produce hydrogen

[0060] 10 mg OH-GY as a photocatalyst, 150 mg sodium ascorbate (sacrificial agent), 0.8 mg chloroplatinic acid (co-catalyst) and 50 mL PBS buffer solution (pH = 7.2) were added to a 100 mL photocatalytic reactor with a quartz lid. Before illumination, the reactor was placed on a stirrer and stirred for 30 min to evenly disperse the catalyst, and nitrogen was continuously bubbled in for 30 min. Subsequently, a 300W xenon lamp (incident light wavelength ≥ 400 nm) equipped with a UV cutoff filter was used as a light source to irradiate the top of the reactor (the distance between the light source and the reactor lid was controlled at 10 cm), and the reactor was maintained at 5 ° C using a circulating condenser for 6 hours, and the hydrogen production was measured every hour. The hydrogen production was measured by gas chromatography (GC model: GC-2014, manufacturer: Shimadzu, Japan). The change of hydrogen production of two-dimensional graphene monoacetylene OH-GY over time is shown in the figure below Figure 6 As shown in Figure 2, the hydrogen evolution activity of OH-GY under visible light is as high as 0.93 mmol g -1· h -1 .

[0061] A typical example of preparing graphene-based materials using halogenated aromatic hydrocarbons and 1,4-bis(trimethylsilyl)-1,3-butadiyne as starting materials is as follows:

[0062] Example 8 Synthesis of two-dimensional graphene diyne γ-GDY

[0063] 0.036mmol hexabromobenzene was accurately weighed and dissolved in 7mL N,N-dimethylformamide / toluene / water (V / V / / V=3 / 3 / 1) mixed solution, 1mL triethylamine was added, the pH of the system was controlled to 8, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.216mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne were added in sequence, the above system was sealed, and allowed to react at 90°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate), filtered after the reaction, the obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried, the treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after 72 hours of reaction, the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain 14mg black γ-GDY film. Its structural representation is shown in Figure 7 , where (a) schematic diagram of the synthesis of γ-GDY; (b) SEM image of γ-GDY, indicating that the prepared graphdiyne is a two-dimensional morphology film.

[0064] Example 9 Synthesis of Two-Dimensional Graphyne Diyne OH-GDY

[0065] 0.036mmol 2,4,6-triiodophenol was accurately weighed and dissolved in 4mL tetrahydrofuran / methanol / water (V / V / V=2 / 1 / 1) mixed solution, 216mg potassium carbonate was added, the pH of the system was controlled to 12, nitrogen was introduced for 15 minutes, 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.108mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne were added in sequence, the above system was sealed, and allowed to react at 70°C for 72 hours (the reaction confined the monomer to grow in two dimensions through the self-template effect of the polymerization intermediate), filtered after the reaction, the obtained black film was washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried, the treated film was further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after 72 hours of reaction, and the solid film was washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain an OH-GDY film.

[0066] Example 10 Synthesis of two-dimensional graphene diyne CH3-GDY

[0067] Accurately weigh 0.036mmol 1,3,5-tribromo-2,4,6-trimethylbenzene and dissolve it in 4mL N,N-dimethylformamide / toluene / water (V / V / V=2 / 1 / 1) mixed solution, add 1mL triethylamine, control the pH of the system to 8, pass nitrogen for 15 minutes, then add 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.108mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne, the above system is sealed and allowed to react at 90°C for 72 hours (the reaction limits the growth of monomers in two dimensions through the self-template effect of the polymerization intermediate), filtered after the reaction, and the obtained black film is washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in turn, and dried. The treated film is further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after the reaction for 72 hours, and the solid film is washed with dichloromethane, methanol and anhydrous ethanol in turn, and dried to obtain a CH3-GDY film.

[0068] Example 11 Synthesis of two-dimensional graphene diyne N-GDY

[0069] Accurately weigh 0.036mmol 2,4,6-tribromopyridine and dissolve it in 4mL N,N-dimethylformamide / toluene / water (V / V / V=2 / 1 / 1) mixed solution, add 1mL triethylamine, control the pH of the system to 8, pass nitrogen for 15 minutes, then add 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.216mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne, the above system is sealed and allowed to react at 80°C for 72 hours (the reaction limits the growth of monomers in two dimensions through the self-template effect of the polymerization intermediate), filtered after the reaction, and the obtained black film is washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in turn, and dried. The treated film is further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after the reaction for 72 hours, and the solid film is washed with dichloromethane, methanol and anhydrous ethanol in turn, and dried to obtain an N-GDY film.

[0070] Example 12 Synthesis of two-dimensional graphene diyne Pyr-GDY

[0071] 0.036mmol of 1,3,6,8-tetrabromopyrene was accurately weighed and dissolved in 4mL of N,N-dimethylformamide / toluene / water (V / V / V=2 / 1 / 1) mixed solution, 1mL of triethylamine was added, the pH of the system was controlled to 8, nitrogen was introduced for 15 minutes, and then 10mg of Pd(PPh3)2Cl2 and 3mg of CuI were added in sequence. 1,4-bis(trimethylsilyl)-1,3-butadiyne, the above system is sealed and allowed to react at 80°C for 72 hours (the reaction limits the growth of monomers in two dimensions through the self-template effect of the polymerization intermediate), filtered after the reaction, and the obtained black film is washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in turn, and dried. The treated film is further placed in a hot pyridine solution (80°C, the purpose is to remove Pd and Cu elements in the film), filtered after the reaction for 72 hours, and the solid film is washed with dichloromethane, methanol and anhydrous ethanol in turn, and dried to obtain a Pyr-GDY film.

[0072] Example 13 Synthesis of three-dimensional graphene diyne T-GDY

[0073] Accurately weigh 0.036mmol tetrakis(4-bromophenyl)methane and dissolve it in 4mL N,N-dimethylformamide / toluene / water (V / V / V=2 / 1 / 1) mixed solution, add 1mL triethylamine, control the pH of the system to 8, and after nitrogen is introduced for 15 minutes, add 10mg Pd(PPh3)2Cl2 and 3mg CuI, 0.144mmol 1,4-bis(trimethylsilyl)-1,3-butadiyne in sequence. The above system is sealed and allowed to react at 80℃ for 72 hours. After the reaction is completed, filter the mixture, and the obtained black film is washed three times with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane in sequence, and dried. The treated film is further placed in a hot pyridine solution (80℃, in order to remove Pd and Cu elements in the film), filtered after reaction for 72 hours, and the solid film is washed with dichloromethane, methanol and anhydrous ethanol in sequence, and dried to obtain a T-GDY film.

[0074] The above are only preferred specific implementations of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed in the present application should be included in the protection scope of the present application. Therefore, the protection scope of the present application should be based on the protection scope of the claims.

Claims

1. A method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction, characterized in that: Using halogenated aromatic hydrocarbons and alkynyl compounds as raw materials and palladium catalyst / copper catalyst as the catalytic system, the protecting group on the acetylenic bond of the alkynyl compound is removed in situ by regulating the alkalinity and the polarity of the solvent, and a Sonogashira-Hagihara cross-coupling reaction is carried out with the halogenated aromatic hydrocarbon to prepare graphene acetylene-based materials.

2. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 1, characterized in that: The alkynyl compound has a silicon-based protecting group on the acetylene bond.

3. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 2, characterized in that: The alkynyl compound includes trimethylsilyl acetylene, bis(trimethylsilyl)acetylene, 1,4-bis(trimethylsilyl)-1,3-butadiyne or 4-trimethylsilane-1,3-butadiyne.

4. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 1, characterized in that: The halogenated aromatic hydrocarbon is a highly symmetrical polyhalogenated aromatic hydrocarbon, the number of carbon-halogen bonds in its structure is ≥3, and the symmetry of the carbon-halogen bond orientation is D 2h , D 3h , D 4h , D 6h or T d .

5. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 1, characterized in that: The palladium catalyst includes Pd(PPh3)4, Pd(dba)2, Pd(PPh3)2Cl2 or Pd(dppf)Cl2; the copper catalyst is a monovalent copper catalyst.

6. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 5, characterized in that: The monovalent copper catalyst includes CuCl, CuBr, CuI or a Cu(I) complex dissolved from the surface of a copper sheet.

7. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 1, characterized in that: The solvent used in the Sonogashira-Hagihara cross-coupling reaction is a polar solvent, the reaction temperature is 70-90° C., and the reaction time is 72 h.

8. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 7, characterized in that: The polar solvent includes at least two of N,N-dimethylformamide, tetrahydrofuran, methanol and water.

9. The method for preparing graphene-based materials based on Sonogashira-Hagihara cross-coupling reaction according to claim 1, characterized in that: The alkalinity is regulated by adding a base into the solvent, and the pH value of the solvent is controlled to be 8-13; the base includes triethylamine, diisopropylamine, potassium carbonate or sodium carbonate.

10. Use of a graphene-based material prepared by the method according to any one of claims 1 to 9 in the field of photocatalysis.

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