A method for preparing graphdiyne-based materials based on Sonogashira-Hagihara cross-coupling reaction

Abstract

This invention discloses a method for preparing graphdiyne-based materials based on the Sonogashira-Hagihara cross-coupling reaction, belonging to the field of Sonogashira-Hagihara cross-coupling reaction technology. This invention uses halogenated aromatic hydrocarbons and alkynyl compounds as raw materials, and a palladium / copper catalyst as the catalytic system. By controlling the basicity and solvent polarity, the protecting groups on the alkynyl bonds of the alkynyl compounds are removed in situ, and then Sonogashira-Hagihara cross-coupling is performed with the halogenated aromatic hydrocarbons to obtain graphdiyne-based materials. The method of this invention allows for the selection of a wide variety of halogenated aromatic hydrocarbons, has low cost, and fewer side reactions during polymerization, which is beneficial for expanding the types of graphdiyne and the development and utilization of high-quality graphdiyne films, while reducing the preparation cost of graphdiyne.

Description

Technical Field

[0001] This invention belongs to the field of Sonogashira-Hagihara cross-coupling reaction technology, and particularly relates to a method for preparing graphdiyne-based materials based on Sonogashira-Hagihara cross-coupling reaction. Background Technology

[0002] Graphdiyne is a novel type of Graphdiyne containing sp and sp 2 Two-dimensional all-carbon materials with hybrid carbon atoms are internationally recognized as a major breakthrough in carbon materials research. One of the most important structural features of graphyne is the presence of sp carbon, which endows it with many unique properties not found in traditional carbon materials, such as abundant carbon chemical bonds, natural band gaps, ultra-large continuous pores, and uneven surface charge distribution. Since the successful preparation of graphodyne (γ-GDY) by Academician Li Yuliang's research group in 2010, it has shown great potential in basic and applied sciences in many fields such as catalysis, energy conversion and storage, optoelectronics, information, and smart devices (Chem. Commun. 2010, 46, 3256-3258). Scientists previously synthesized alkynyl monomers and prepared γ-GDY films by selecting suitable planar templates to confine the monomers along the two-dimensional direction through alkynyl-alkynyl coupling (Glaser-Hay, Eglinton, and Hiyama coupling). However, the synthesis of alkynyl monomers is difficult, the types are limited, and side reactions easily occur during polymerization, which to some extent limits the development and utilization of graphyne varieties and high-quality graphyne films. Summary of the Invention

[0003] To address the aforementioned technical problems, this invention proposes a method for preparing graphynylene-based materials based on the Sonogashira-Hagihara cross-coupling reaction. This invention allows for the selection of a wide variety of halogenated aromatic hydrocarbons, has low cost, and involves fewer side reactions during polymerization. This is beneficial for the development and utilization of graphynylene species and high-quality graphynylene films, and reduces the preparation cost of graphynylene-based materials.

[0004] To achieve the above objectives, the present invention provides the following technical solution:

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

[0006] A method for preparing graphdiyne-based materials based on the Sonogashira-Hagihara cross-coupling reaction is disclosed. The method uses haloaromatic hydrocarbons and alkynyl compounds as starting materials and palladium / copper catalysts as catalytic systems. By controlling the basicity and solvent polarity, the protecting groups on the alkynyl bonds of the alkynyl compounds are removed in situ, and the compounds undergo a Sonogashira-Hagihara cross-coupling reaction with haloaromatic hydrocarbons to prepare graphdiyne-based materials.

[0007] Preferably, the alkynyl compound has a silicon-based protecting group on its alkynyl bond.

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

[0009] Preferably, the haloaromatic hydrocarbon is a highly symmetric polyhalogenated aromatic hydrocarbon, wherein 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] This invention uses halobenzene and alkynyl compounds as starting materials and a palladium / copper catalyst as the catalytic system to carry out the Sonogashira-Hagihara cross-coupling reaction in a polar solvent. By controlling the basicity and solvent polarity, the protecting group on the alkynyl bond of the alkynyl compound is removed in situ (the silicon on the C-Si bond of the alkynyl compound is a positively charged center, which can react with the nucleophile OH in solution). - (Reaction), and then coupled with a haloaromatic hydrocarbon via Sonogashira-Hagihara to obtain a graphynyne-based material. 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 Cu(I) complex dissolved from the surface of the copper sheet;

[0015] The polar solvents include at least two of N,N-dimethylformyl, tetrahydrofuran, toluene, and water, which ensure efficient Sonogashira-Hagihara cross-reactions between monomers.

[0016] Preferably, the alkalinity is adjusted by adding an alkali to the solvent, and the pH of the solvent is controlled to be 8-13; the alkali 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, tetra(4-bromophenyl)methane, 2,3,6,7,12,13-hexabromotripterene or 2,4,6-triiodophenol.

[0018] More preferably, the method for preparing graphitic monoyne (γ-GY) using halogenated aromatic hydrocarbons and alkynyl compounds as starting materials is as follows: accurately weigh 0.036 mmol of hexabromobenzene into 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, purge with nitrogen for 15 minutes, and then add 10 mg of Pd(PPh3)2Cl2 and 3 mg of Pd(PPh3)2Cl2 sequentially. CuI, 0.216 mmol trimethylsilylacetylene, the above system was sealed and allowed to stand at 90 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction was completed, the mixture was filtered, and the resulting black film was washed three times in sequence with hydrochloric acid, distilled water, anhydrous ethanol and dichloromethane, and then dried. The treated film was further placed in a hot pyridine solution (70-110 °C, the purpose of which is to remove Pd and Cu elements from the film). After reacting for 72 hours, the mixture was filtered, and the solid film was then washed in sequence with dichloromethane, methanol and anhydrous ethanol, and dried to obtain the γ-GY film.

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

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

[0021]

[0022] Note: Table 1 only lists common polyhalogenated aromatic hydrocarbons. Other polyhalogenated aromatic hydrocarbons can also be synthesized into graphyne derivatives with novel topological structures by Sonogashira-Hagihara cross-coupling with trimethylsilylacetylene according to the carbon-halogen bond extension direction.

[0023] More preferably, the method for preparing graphitic diyne (γ-GDY) using halogenated aromatic hydrocarbons and alkynyl compounds as starting materials is as follows: accurately weigh 0.036 mmol of hexabromobenzene into 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, purge with nitrogen for 15 minutes, and then add 10 mg of Pd(PPh3)2Cl2 and 3 mg of CuI sequentially, along with 0.216 mmol of... 1,4-Bis(trimethylsilyl)-1,3-butadiyne was used. The above system was sealed and allowed to stand at 90°C for 72 hours (the reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, the mixture was filtered, and the resulting black film was washed three times in sequence with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film was further placed in a hot pyridine solution (70-110°C, to remove Pd and Cu elements from the film). After reacting for 72 hours, the film was filtered, and the solid film was washed again in sequence with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the γ-GDY film.

[0024] In the method for preparing γ-GDY derivative films using polyhalogenated aromatic hydrocarbons and alkynyl compounds as starting materials in this invention, other polyhalogenated aromatic hydrocarbons (such as 1,3,5-triiodobenzene, 1,2,4,5-tetrabromobenzene, tetra(4-bromophenyl)methane, 2,3,6,7,12,13-hexabromotripterene, or 2,4,6-triiodophenol) can be used instead of hexabromobenzene. Two-dimensional halogenated aromatic hydrocarbons with C2, C3, C4, and C6 symmetry can be used to obtain γ-GDY derivatives with rhombic, hexagonal, quadrilateral, and triangular pores.

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

[0026] This invention also provides the application of graphdiyne-based materials prepared according to the above method in the field of photocatalysis. For example, the two-dimensional graphitic monoyne OH-GY prepared by the method of this invention can be used for photocatalytic water splitting to produce hydrogen, exhibiting a hydrogen evolution activity as high as 0.93 mmol g under visible light. -1· h -1 .

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

[0028] This invention introduces a protecting group at the terminal alkyne of an alkyne compound, and prepares graphitic alkyne materials by in-situ deprotection and Sonogashira-Hagihara coupling with polyhalogenated aromatic hydrocarbons, which can be used in the field of photocatalysis. Attached Figure Description

[0029] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0030] Figure 1 The structure characterization of the two-dimensional graphdiyne monoyne γ-GY prepared in Example 1 includes (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; and (e, f) EDS mapping images of γ-GY.

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

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

[0033] Figure 4 The structure of the two-dimensional graphdiyne monoyne OH-GY prepared in Example 3 is characterized, including (a) a schematic diagram of the synthesis of OH-GY; (b) an optical photograph of OH-GY; (c) a SEM image of OH-GY; and (d) an infrared spectrum of OH-GY.

[0034] Figure 5 The structure of the two-dimensional graphdiyne monoyne F-GY prepared in Example 4 is characterized, wherein (a) is the SEM image of F-GY; and (b) is the infrared spectrum of F-GY.

[0035] Figure 6 The graph shows the change in hydrogen production over time of the two-dimensional graphynyne monoacetylene OH-GY prepared in Example 3.

[0036] Figure 7 The structure of the two-dimensional graphdiyne γ-GDY prepared in Example 8 is characterized, wherein (a) is a schematic diagram of the synthesis of γ-GDY; and (b) is a SEM image of γ-GDY. Detailed Implementation

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

[0038] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0039] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0040] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

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

[0042] All raw materials used in this invention were obtained through commercial purchase.

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

[0044] Typical examples of preparing graphitic acetylation materials using haloaromatic hydrocarbons and acetylation monomers containing protecting groups as starting materials are as follows:

[0045] Example 1: Synthesis of Two-Dimensional Graphynyne Monoyne γ-GY

[0046] Accurately weigh 0.036 mmol of hexabromobenzene and dissolve it 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, and purge with nitrogen for 15 minutes. Then, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.216 mmol of trimethylsilylacetylene sequentially. Seal the system and allow it to react at 90 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the solution. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the solution. The solid film is then washed sequentially with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain 10 mg of a black γ-GY film. Its structural characterization is shown in [link to relevant documentation]. Figure 1 (a) Schematic diagram of γ-GY synthesis, yellow represents the γ-GY structure simulated by Materials Studio; (b) Optical photograph of γ-GY dispersed in water; (c, d) SEM images of γ-GY; (e, f) EDS mapping images of γ-GY, showing that the γ-GY film is a two-dimensional film; Infrared spectra are shown below. Figure 2 1618cm -1 Belongs to the stretching vibration of the benzene ring; 2183 cm -1 The peak represents the stretching vibration of the alkynyl group; see elemental distribution diagram below. Figure 3 This indicates that the γ-GY film is mainly composed of carbon, and the oxygen comes from water adsorbed in the pores of the γ-GY film and oxygen in the air.

[0047] Example 2: Synthesis of Two-Dimensional Graphdiyne Monoyne H-GY

[0048] Accurately weigh 0.036 mmol of 1,3,5-triiodobenzene and dissolve it in 4 mL of a tetrahydrofuran / methanol / water (V / V / V = 2 / 1 / 1) mixed solution. Add 216 mg of potassium carbonate and control the pH of the system to 12. After purging with nitrogen for 15 minutes, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.216 mmol of trimethylsilylacetylene sequentially. Seal the system and allow it to react at 70 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the solution. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the solution. The solid film is then washed sequentially with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain 12 mg of yellow H-GY film.

[0049] Example 3: Synthesis of Two-Dimensional Graphynyne Monoyne OH-GY

[0050] Accurately weigh 0.036 mmol of 2,4,6-triiodophenol and dissolve it in 4 mL of a tetrahydrofuran / methanol / water mixture (V / V / V = 2 / 1 / 1). Add 216 mg of potassium carbonate, control the pH of the system to 12, and purge with nitrogen for 15 minutes. Then, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.108 mmol of trimethylsilylacetylene sequentially. Seal the system and allow it to react at 70 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the film. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the film. The solid film is then washed sequentially with dichloromethane, methanol, and anhydrous ethanol, and dried to obtain 13 mg of an orange OH-GY film. Its structural characterization is shown in [link to relevant documentation]. Figure 4 (a) Schematic diagram of OH-GY synthesis; (b, c) Optical photographs and SEM images of OH-GY, illustrating that OH-GY is a two-dimensional thin film; (d) Infrared spectrum of OH-GY, 1582 cm⁻¹ -1 This is the stretching vibration peak of the carbon-carbon double bond on the benzene ring, at 2149 cm⁻¹. -1 2114cm -1 The peak represents the asymmetric stretching vibration of the acetylene group.

[0051] Example 4: Synthesis of Two-Dimensional Graphdiyne Monoyne F-GY

[0052] Accurately weigh 0.036 mmol of 1,3,5-triiodo-2,4,6-trifluorobenzene and dissolve it in 4 mL of a tetrahydrofuran / methanol / water mixture (V / V / V = 2 / 1 / 1). Add 216 mg of potassium carbonate, control the pH of the system to 12, and purge with nitrogen for 15 minutes. Then, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.108 mmol of trimethylsilylacetylene sequentially. Seal the system and allow it to react at 70 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the film. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the film. The solid film is then washed sequentially with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain 15 mg of F-GY film. Its structural characterization diagram is shown below. Figure 5(a) SEM image of F-GY, showing that F-GY is a two-dimensional thin film; (b) Infrared spectrum of F-GY, 1588 cm⁻¹. -1 This is the stretching vibration peak of the carbon-carbon double bond on the benzene ring, at 2147 cm⁻¹. -1 2104cm -1 The peak represents the asymmetric stretching vibration of the acetylene group.

[0053] Example 5: Synthesis of Two-Dimensional Graphdiyne Monoyne N-GY

[0054] Accurately weigh 0.036 mmol of 2,4,6-bromopyridine and dissolve it in 4 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 2 / 1 / 1). Add 1 mL of triethylamine and control the pH of the system to 8. After purging with nitrogen for 15 minutes, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.108 mmol of trimethylsilylacetylene sequentially. Seal the system and allow it to react at 80 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the solution. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the solution. The solid film is then washed sequentially with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the N-GY film.

[0055] Example 6 Synthesis of Two-Dimensional Graphite Monoacetylene Pyr-GY

[0056] Accurately weigh 0.036 mmol of 1,3,6,8-tetrabromopyrene and dissolve it in 4 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 2 / 1 / 1). Add 1 mL of triethylamine and control the pH of the system to 8. After purging with nitrogen for 15 minutes, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.144 mmol of trimethylsilylacetylene sequentially. Seal the system and allow it to react at 90 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the solution. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the solution. The solid film is then washed sequentially with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the Pyr-GY film.

[0057] Example 7 Synthesis of Three-Dimensional Graphite Monoacetylene T-GY

[0058] Accurately weigh 0.036 mmol of 1,3,6,8-tetrabromopyrene and dissolve it in 4 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 2 / 1 / 1). Add 1 mL of triethylamine and control the pH of the system to 8. After purging with nitrogen for 15 minutes, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.144 mmol of trimethylsilylacetylene sequentially. Seal the system and allow it to react at 90 °C for 72 hours. After the reaction, filter the solution. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film) and reacted for 72 hours. After filtration, the solid film is washed again sequentially with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the T-GY film.

[0059] Application Example 1: Application of two-dimensional graphdiyne OH-GY (prepared in Example 3) in photocatalytic water splitting for hydrogen production.

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

[0061] Typical examples of preparing graphynyne-based materials using haloaromatic hydrocarbons and 1,4-bis(trimethylsilyl)-1,3-butadiyne as starting materials are as follows:

[0062] Example 8 Synthesis of Two-Dimensional Graphynyne Diyne γ-GDY

[0063] Accurately weigh 0.036 mmol of hexabromobenzene and dissolve it in 7 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 3 / 3 / 1). Add 1 mL of triethylamine and control the pH of the system to 8. After purging with nitrogen for 15 minutes, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.216 mmol of 1,4-bis(trimethylsilyl)-1,3-butadiene. Seal the system and allow it to react at 90 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the solution. The resulting black film is washed three times with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the solution. The solid film is then washed three times with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain 14 mg of black γ-GDY film. Its structural characterization diagram is shown below. Figure 7 (a) Schematic diagram of the synthesis of γ-GDY; (b) SEM image of γ-GDY, showing that the prepared graphdiyne is a two-dimensional thin film.

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

[0065] Accurately weigh 0.036 mmol of 2,4,6-triiodophenol and dissolve it in 4 mL of a tetrahydrofuran / methanol / water (V / V / V = 2 / 1 / 1) mixed solution. Add 216 mg of potassium carbonate and control the pH of the system to 12. After purging with nitrogen for 15 minutes, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.108 mmol of 1,4-bis(trimethylsilyl)-1,3-butadiene. Seal the system and allow it to react at 70 °C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, filter the film. The resulting black film is washed three times with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the film. The solid film is then washed with dichloromethane, methanol, and anhydrous ethanol, and dried to obtain the OH-GDY film.

[0066] Example 10 Synthesis of Two-Dimensional Graphynyne Diyne CH3-GDY

[0067] Accurately weigh 0.036 mmol of 1,3,5-tribromo-2,4,6-trimethylbenzene and dissolve it in 4 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 2 / 1 / 1). Add 1 mL of triethylamine, control the pH of the system to 8, purge with nitrogen for 15 minutes, and then add 10 mg of Pd(PPh3)2Cl2 and 3 mg of CuI sequentially. 1,4-Bis(trimethylsilyl)-1,3-butadiyne was used. The above system was sealed and allowed to stand at 90°C for 72 hours (the reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, the mixture was filtered, and the resulting black film was washed three times in sequence with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film was further placed in a hot pyridine solution (80°C, to remove Pd and Cu elements from the film). After reacting for 72 hours, the film was filtered, and the solid film was washed again in sequence with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the CH3-GDY film.

[0068] Example 11 Synthesis of Two-Dimensional Graphynyne Diyne N-GDY

[0069] Accurately weigh 0.036 mmol of 2,4,6-tribromopyridine and dissolve it in 4 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 2 / 1 / 1). Add 1 mL of triethylamine, control the pH of the system to 8, purge with nitrogen for 15 minutes, and then add 10 mg of Pd(PPh3)2Cl2 and 3 mg of CuI sequentially. 1,4-Bis(trimethylsilyl)-1,3-butadiyne was used. The above system was sealed and allowed to stand at 80°C for 72 hours (this reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, the mixture was filtered, and the resulting black film was washed three times in sequence with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film was further placed in a hot pyridine solution (80°C, to remove Pd and Cu elements from the film) and reacted for 72 hours. After filtration, the solid film was washed again in sequence with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the N-GDY film.

[0070] Example 12 Synthesis of Two-Dimensional Graphynyne Diyne Pyr-GDY

[0071] Accurately weigh 0.036 mmol of 1,3,6,8-tetrabromopyrene and dissolve it in 4 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 2 / 1 / 1). Add 1 mL of triethylamine, control the pH of the system to 8, purge with nitrogen for 15 minutes, and then add 10 mg of Pd(PPh3)2Cl2 and 3 mg of CuI sequentially. 1,4-Bis(trimethylsilyl)-1,3-butadiyne was used. The above system was sealed and allowed to stand at 80°C for 72 hours (the reaction confines the monomer growth along the two-dimensional direction through the self-templating effect of the polymerization intermediate). After the reaction, the mixture was filtered, and the resulting black film was washed three times in sequence with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film was further placed in a hot pyridine solution (80°C, to remove Pd and Cu elements from the film) and reacted for 72 hours. After filtration, the solid film was washed again in sequence with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the Pyr-GDY film.

[0072] Example 13 Synthesis of Three-Dimensional Graphynyne Diyne T-GDY

[0073] Accurately weigh 0.036 mmol of tetra(4-bromophenyl)methane and dissolve it in 4 mL of a mixed solution of N,N-dimethylformamide / toluene / water (V / V / V = 2 / 1 / 1). Add 1 mL of triethylamine and control the pH of the system to 8. After purging with nitrogen for 15 minutes, add 10 mg of Pd(PPh3)2Cl2, 3 mg of CuI, and 0.144 mmol of 1,4-bis(trimethylsilyl)-1,3-butadiene sequentially. Seal the system and allow it to react at 80 °C for 72 hours. After the reaction, filter the solution. The resulting black film is washed three times sequentially with hydrochloric acid, distilled water, anhydrous ethanol, and dichloromethane, and then dried. The treated film is further placed in a hot pyridine solution (80 °C to remove Pd and Cu elements from the film). After reacting for 72 hours, filter the solution. The solid film is then washed sequentially with dichloromethane, methanol, and anhydrous ethanol, and then dried to obtain the T-GDY film.

[0074] The above are merely preferred embodiments of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A method for preparing graphdiyne-based materials based on the Sonogashira-Hagihara cross-coupling reaction, characterized in that, Using halogenated aromatic hydrocarbons and alkynyl compounds as raw materials, and palladium and copper catalysts as catalytic systems, the protecting groups on the alkynyl bonds of the alkynyl compounds are removed in situ by adjusting the basicity and the polarity of the solvent, and then the compounds undergo a Sonogashira-Hagihara cross-coupling reaction with halogenated aromatic hydrocarbons to prepare graphitic alkynyl materials. The alkynyl compounds include trimethylsilylacetylene, bis(trimethylsilyl)acetylene, 1,4-bis(trimethylsilyl)-1,3-butadiene or 4-trimethylsilane-1,3-butadiene; The haloaromatic hydrocarbon is a highly symmetric polyhalogenated aromatic hydrocarbon, with ≥3 carbon-halogen bonds in its structure, and the symmetry of the carbon-halogen bond orientation is D. 2h D 3h D 4h D 6h or T d ; The solvent used in the Sonogashira-Hagihara cross-coupling reaction is a polar solvent, which includes at least two of N,N-dimethylformamide, tetrahydrofuran, methanol, and water; the alkalinity of the solvent is adjusted by adding a base to the solvent to control the pH of the solvent to 8-13, and the base includes triethylamine, diisopropylamine, potassium carbonate, or sodium carbonate.

2. The method for preparing graphdiyne-based materials based on the 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.

3. The method for preparing graphdiyne-based materials based on the Sonogashira-Hagihara cross-coupling reaction according to claim 2, characterized in that, The monovalent copper catalyst includes CuCl, CuBr, CuI, or Cu(I) complexes dissolved from the surface of copper sheets.

4. The method for preparing graphdiyne-based materials based on the Sonogashira-Hagihara cross-coupling reaction according to claim 1, characterized in that, The Sonogashira-Hagihara cross-coupling reaction was carried out at a temperature of 70–90 °C for 72 h.

5. The application of a graphdiyne-based material prepared by the method according to any one of claims 1 to 4 in the field of photocatalysis.

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