Method for rapidly synthesizing graphdiyne and graphdiyne composite material through irradiation

Abstract

The invention belongs to the technical field of material synthesis, and particularly discloses a method for rapidly synthesizing graphdiyne and a graphdiyne composite material through irradiation, and the method comprises the following steps: uniformly mixing HEB-TMS and metal salt in a solvent in an ultrasonic manner to obtain a mixed solution; the obtained mixed solution is placed under an irradiation source for irradiation treatment, and after irradiation treatment, cleaning, centrifugal separation and freeze drying treatment are performed to obtain the graphdiyne composite material. According to the method, in-situ desilicication coupling of HEB-TMS is achieved through high-energy ionizing radiation, the time-consuming and air-sensitive deprotection step is omitted, the time cost and the economic cost are greatly reduced, the high sensitivity of a monomer after a silicon protecting group is removed is avoided, and the method has universality; the graphdiyne yield, the metal load state and the graphdiyne composite material morphology can be regulated and controlled by adjusting parameters such as the monomer amount, the solvent, the type and dosage of the metal salt, the irradiation dose and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of material synthesis, and in particular relates to a method for rapidly synthesizing graphyne and graphyne composite materials by irradiation. Background Art

[0002] Graphdiyne (GDY), a novel two-dimensional carbon material, has emerged in the materials field due to its unique structural properties. Composed of sp- and sp2-hybridized carbon atoms, it possesses a unique alkyne-rich structure and a large π-conjugated network. This special structure endows GDY with a uniformly distributed and tunable pore structure, enabling it to precisely screen molecules in gas storage and filtration separation. Its high carrier mobility and inherent electronic band gap give it enormous potential in electronic devices, energy conversion, and energy storage, for example, by accelerating electron transport in battery electrode materials. In 2010, Li Yuliang's team successfully prepared GDY for the first time via a hexaethynylbenzene (HEB) cross-coupling reaction using copper foil as a catalyst and substrate. Since then, new preparation methods such as interfacial coupling, explosive methods, and microwave synthesis have emerged, enabling the controllable adjustment of GDY's morphology, structure, and thickness, opening up new possibilities for its application research. However, current GDY preparation methods still have many shortcomings. Lengthy reaction times, with some preparation processes often requiring days, severely hinder large-scale production. Harsh reaction conditions, requiring high temperatures, high pressures, or specialized equipment, significantly increase preparation costs and operational complexity. Some synthesis processes utilize toxic solvents, posing a health risk to operators and causing environmental pollution. This is due to the difficulty in activating monomers containing protecting groups, and the highly sensitive free monomers after deprotection, making optimization of the preparation process difficult.

[0003] The unique structure of graphyne enables it to exhibit excellent performance when composited with other materials. With its abundant acetylenic bonds and active sites, graphyne can form strong interactions with metal atoms and other materials, significantly enhancing its catalytic performance; its inherent intrinsic band gap can promote charge transfer and improve electrical properties. Preparation methods such as in situ compounding and solution mixing have emerged one after another, but the actual synthesis is full of difficulties. The precursor is unstable in air, making it difficult to precisely control the reaction; some raw materials are expensive and difficult to obtain; high temperature and high pressure conditions can easily cause structural defects in graphyne; the mixing and dispersion between materials are uneven, and the interface bonding strength and stability are insufficient. In addition, the optimization of composite material performance is huge, the performance consistency is poor, the energy storage performance needs to be improved, the research on multifunctional materials is scarce, the relationship between microstructure and macroscopic performance is not in-depth, the characterization technology is imperfect, the actual application progress is slow, and commercial products are scarce.

[0004] Therefore, it is particularly important to develop efficient, mild and environmentally friendly methods for synthesizing graphyne and its composite materials. Summary of the Invention

[0005] The present invention aims to overcome the shortcomings of existing technologies by providing a method for the rapid synthesis of graphyne and graphyne composites by irradiation. The method utilizes high-energy particles generated by irradiation to directly activate the entire reaction system, producing highly active substances, thereby driving ultrafast chemical transformations under mild conditions. This method not only fully utilizes high-energy particles to activate protected, stable graphyne monomers (HEB-TMS), thereby eliminating the time-consuming and air-sensitive deprotection step, but also significantly shortens the synthesis time from days or hours to seconds.

[0006] In order to achieve the above objectives, one of the technical solutions of the present invention is: a method for rapid synthesis of graphyne composite materials by irradiation, comprising the following steps:

[0007] (1) uniformly mixing HEB-TMS and metal salt in a solvent by ultrasonication to obtain a mixed solution;

[0008] (2) placing the mixed solution obtained in step (1) under an irradiation source for irradiation treatment, and then washing, centrifuging, and freeze-drying to obtain a graphene composite material.

[0009] In a preferred embodiment of the present invention, the metal salt in step (1) is at least one of Cu salt, Ni salt, Co salt, Ag salt, Fe salt and Au salt.

[0010] In a preferred embodiment of the present invention, the solvent in step (1) is at least one of tetrahydrofuran, dichloromethane, acetone, ethanol, N,N-dimethylformamide, pyridine, dimethyl sulfoxide, and deionized water.

[0011] In a preferred embodiment of the present invention, the mass ratio of HEB-TMS to metal salt in step (1) is 1:(0.1-10).

[0012] In a preferred embodiment of the present invention, the radiation source in step (2) is one of high-energy electron beams, gamma rays, X-rays, and alpha rays.

[0013] In a preferred embodiment of the present invention, the atmosphere for the irradiation treatment in step (2) is one of air, oxygen, nitrogen, argon and hydrogen.

[0014] In a preferred embodiment of the present invention, the irradiation temperature in the irradiation treatment in step (2) is 10-100° C., and the absorbed irradiation dose is 5-300 kGy.

[0015] In a preferred embodiment of the present invention, after the mixed solution in step (2) is irradiated, it is washed twice with ethanol, tetrahydrofuran and water respectively.

[0016] In order to achieve the above purpose, the second technical solution of the present invention is: a graphene composite material is prepared by the above-mentioned method for synthesizing a graphene composite material.

[0017] In order to achieve the above objectives, the third technical solution of the present invention is: application of the above-mentioned graphyne composite material in a catalyst.

[0018] In order to achieve the above objectives, the fourth technical solution of the present invention is: a graphyne obtained by treating the above-mentioned graphyne composite material with hydrochloric acid.

[0019] In a preferred embodiment of the present invention, the concentration of hydrochloric acid is 0.2-0.8M.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. The present invention achieves in-situ desilication coupling of HEB-TMS through high-energy ionizing radiation, eliminating the time-consuming and air-sensitive deprotection step, significantly reducing time and economic costs, and avoiding the high sensitivity of the monomer after removal of the silicon protecting group. The method is also universally applicable.

[0022] 2. The present invention can adjust the parameters such as monomer amount, solvent, metal salt type and amount, irradiation dose, etc. to control the gydnyle yield, metal loading state and morphology of the gydnyle composite material;

[0023] 3. The method of the present invention is simple to operate, has simple steps, and has good reproducibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 : This is the Raman spectrum of the graphyne composite material Cu2O / GDY prepared by absorbing different radiation doses in Example 2 of the present invention;

[0025] Figure 2 TEM images of graphene composite materials and graphene GDY prepared from different metal salts in Example 6 of the present invention, wherein a, c, e, g, and i are TEM images of graphene composite materials prepared from CuCl, AgOAc, CuSO4, and Cu(MeCN)4PF6, respectively, and b, d, f, h, and j are TEM images of graphene GDY prepared from CuCl, AgOAc, CuSO4, and Cu(MeCN)4PF6, respectively;

[0026] Figure 3 The Raman spectra of the graphyne composite material Cu2O / GDY prepared with different metal salts in Example 6 of the present invention;

[0027] Figure 4 The performance of nitrate reduction to ammonia production by Cu2O / GDY as an electrocatalyst at different voltages in Example 7. DETAILED DESCRIPTION

[0028] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is described in more detail below with reference to the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited to these embodiments.

[0029] The experimental methods in the following examples are conventional methods unless otherwise specified.

[0030] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0031] HEB-TMS in the following examples were prepared according to the following literature method: Li, G.; Li, Y.; Liu, H.; Guo, Y.; Li, Y.; Zhu, D., Architecture of graphene nanoscale films. Chemical Communications 2010, 46(19), 3256-3258.

[0032] A method for rapidly synthesizing a graphene composite material by irradiation comprises the following steps:

[0033] (1) Ultrasonic mixing of HEB-TMS and metal salt in a solvent;

[0034] (2) placing the mixed solution obtained in step (1) under an irradiation source for irradiation treatment, and then washing, centrifuging, and freeze-drying to obtain a graphene composite material.

[0035] The metal salt in step (1) is at least one of Cu salt, Ni salt, Co salt, Ag salt, Fe salt and Au salt.

[0036] The solvent in step (1) is at least one of tetrahydrofuran, dichloromethane, acetone, ethanol, N,N-dimethylformamide, pyridine, dimethyl sulfoxide, and deionized water.

[0037] The mass ratio of HEB-TMS to the metal salt in step (1) is 1:(0.1-10), specifically 1:1, 1:2, 1:3, or 1:5.

[0038] In the step (2), the radiation source is one of high-energy electron beams, gamma rays, X-rays, and alpha rays.

[0039] The atmosphere for the irradiation treatment in step (2) is one of air, nitrogen, argon, oxygen and hydrogen.

[0040] The irradiation temperature of the irradiation treatment in step (2) is 10-100° C., and the irradiation absorbed dose is 5-300 kGy.

[0041] After the mixed solution in step (2) is irradiated, it is washed twice with ethanol, tetrahydrofuran and water.

[0042] The graphene composite material is prepared by the method for synthesizing the graphene composite material.

[0043] Application of the above-mentioned graphyne composite material in catalyst.

[0044] A graphene is obtained by treating the graphene composite material with hydrochloric acid.

[0045] The concentration of the hydrochloric acid is 0.2-0.8M.

[0046] The copper salts used in the following Examples 1-5 are all cuprous chloride.

[0047] Example 1

[0048] A graphene-based yttrium composite material is prepared by the following process and steps: 30 mg of each HEB-TMS solution is added to three glass bottles containing 10 mL of dimethyl sulfoxide, followed by the addition of 10 mg, 30 mg, and 50 mg of copper salt, respectively, and ultrasonically dispersed uniformly. The three mixed solutions are then irradiated under a high-energy electron beam source in air at room temperature to an absorbed dose of 80 kGy. The irradiated mixed solutions are then washed twice each with ethanol, tetrahydrofuran, and water, centrifuged, and freeze-dried to obtain the graphene-based yttrium composite material Cu2O / GDY.

[0049] Example 2

[0050] A graphene composite material is prepared by the following process and steps: taking 30 mg of each HEB-TMS solution and adding them to four glass bottles containing 10 mL of dimethyl sulfoxide, then adding 30 mg of copper salt to each of the four glass bottles, and ultrasonically dispersing the mixture uniformly; then placing the four mixed solutions under a high-energy electron beam irradiation source, irradiating them in air at room temperature, and absorbing irradiation doses of 6 kGy, 50 kGy, 80 kGy, and 150 kGy, respectively; then washing the irradiated mixed solutions twice with ethanol, tetrahydrofuran, and water, respectively; and centrifuging and freeze-drying the mixed solutions to obtain graphene composite materials Cu2O / GDY obtained by absorbing different irradiation doses. The Raman spectra thereof are as follows: Figure 1 shown.

[0051] Example 3

[0052] A graphene composite material has the following preparation process and steps: 30 mg of HEB-TMS is added to a glass bottle containing 10 mL of dimethyl sulfoxide, 30 mg of copper salt is added, and the mixture is uniformly dispersed by ultrasonication; the obtained mixed solution is then placed under a gamma-ray irradiation source and irradiated in air at room temperature to absorb a radiation dose of 80 kGy; the irradiated mixed solution is then washed twice with ethanol, tetrahydrofuran, and water, respectively; and the mixture is centrifuged and freeze-dried to obtain the graphene composite material Cu2O / GDY.

[0053] Example 4

[0054] A graphene composite material has the following preparation process and steps: taking two portions of 30 mg each of HEB-TMS and adding them respectively into two glass bottles containing 10 mL of dimethyl sulfoxide, then adding 30 mg of copper salt to each of the two glass bottles, and ultrasonically dispersing them uniformly; then placing the two mixed solutions under a high-energy electron beam irradiation source, and irradiating them in nitrogen and oxygen atmospheres at room temperature to absorb an irradiation dose of 80 kGy; then washing the irradiated mixed solutions twice with ethanol, tetrahydrofuran, and water, respectively, and obtaining graphene composite materials Cu2O / GDY prepared under different irradiation atmospheres after centrifugal separation and freeze-drying.

[0055] Example 5

[0056] A graphene composite material has the following preparation process and steps: taking 30 mg of HEB-TMS in four portions and adding them respectively into four glass bottles containing 10 mL of dimethyl sulfoxide, then adding 30 mg of copper salt to each of the four glass bottles, and uniformly dispersing them by ultrasonication; then placing the obtained four mixed solutions under a high-energy electron beam irradiation source for irradiation treatment, absorbing an 80 kGy irradiation dose, and irradiation temperatures of 10°C, 25°C, 50°C, and 100°C, respectively; then washing the irradiated mixed solutions twice with ethanol, tetrahydrofuran, and water, respectively, and centrifuging and freeze-drying to obtain graphene composite materials Cu2O / GDY prepared at different irradiation temperatures.

[0057] Example 6

[0058] A graphene composite material is prepared by the following process and steps: 30 mg of HEB-TMS is added to four glass bottles containing 10 mL of dimethyl sulfoxide, and 30 mg of metal salts CuCl, AgOAc, CuSO4, and Cu(MeCN)4PF6 are added to each of the bottles and ultrasonically dispersed. The four mixed solutions are then placed under a high-energy electron beam irradiation source and irradiated in air at room temperature with an absorbed dose of 80 kGy. The irradiated mixed solutions are then washed twice with ethanol, tetrahydrofuran, and water, respectively. After centrifugation and freeze-drying, graphene composite materials Cu2O / GDY, Ag2O / GDY, Cu2O / GDY, and Cu2O / GDY are obtained, respectively. TEM images thereof are shown in FIG. Figure 2 As shown in a, c, e, and g, the Raman spectrum is as follows Figure 3 shown.

[0059] The graphene composite materials prepared from the above different metal salts AgOAc, CuSO4, CuCl, and Cu(MeCN)4PF6 were treated with 0.5M hydrochloric acid to obtain four types of graphene GDY. The TEM images are shown in Figure 2. Figure 2 As shown in b, d, f, and h.

[0060] Example 7

[0061] The graphyne composite material prepared in Example 1 was used as a catalyst for electrocatalytic reduction of nitrate to produce ammonia.

[0062] Take 30 mg of copper salt prepared in Example 1, add 1 mg of graphene composite material Cu2O / GDY to 180 μL of isopropanol, then add 20 μL of Nafion solution and sonicate for 15 minutes to obtain a uniformly dispersed catalyst suspension. Then, drop 50 μL of catalyst suspension into a 0.25×0.25 cm 2 1 mg / cm was obtained on hydrophilic carbon paper 2 Catalyst loading of the working electrode.

[0063] The nitrate reduction to ammonia production experiment was carried out using an H-type cell three-electrode system. 1M KOH solution was used as the electrolyte, 0.1M KNO3 was added, and constant potential electrolysis was performed for 1 hour. After the reaction, a certain amount of the reaction solution was diluted and the ammonia concentration in the electrolyte was determined by the indophenol blue method and the nitrite concentration was quantified by N-(1-naphthyl)ethylenediamine spectrophotometry. The nitrate reduction to ammonia production performance at different voltages is shown in Figure 2. Figure 4 As shown, from Figure 4 It can be seen that at -1.7V vs. RHE, 94% Faradaic efficiency and 26997μgh were achieved. -1 mg -1 Ammonia yield of cat.

[0064] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for rapid synthesis of graphyne composite materials by irradiation, characterized in that: The steps include: (1) uniformly mixing HEB-TMS and metal salt in a solvent by ultrasonication to obtain a mixed solution; (2) placing the mixed solution obtained in step (1) under an irradiation source for irradiation treatment, and then washing, centrifuging, and freeze-drying to obtain a graphene composite material.

2. The method for rapid synthesis of graphyne composite materials by irradiation according to claim 1, characterized in that: In the step (1), the metal salt is at least one of Cu salt, Ni salt, Co salt, Ag salt, Fe salt, and Au salt, and the solvent is at least one of tetrahydrofuran, dichloromethane, acetone, ethanol, N,N-dimethylformamide, pyridine, dimethyl sulfoxide, and deionized water.

3. The method for rapid synthesis of graphyne composite materials by irradiation according to claim 1, characterized in that: The mass ratio of HEB-TMS to metal salt in step (1) is 1:(0.1-10).

4. The method for rapid synthesis of graphyne composite materials by irradiation according to claim 1, characterized in that: In the step (2), the radiation source is one of high-energy electron beams, gamma rays, X-rays, and alpha rays.

5. The method for rapid synthesis of graphyne composite materials by irradiation according to claim 1, characterized in that: The atmosphere for the irradiation treatment in step (2) is one of air, nitrogen, argon, oxygen and hydrogen.

6. The method for rapid synthesis of graphyne composite materials by irradiation according to claim 1, characterized in that: The irradiation temperature of the irradiation treatment in step (2) is 10-100° C., and the irradiation absorbed dose is 5-300 kGy.

7. A graphene composite material obtained by the method for rapid synthesis of graphene composite material by irradiation according to any one of claims 1 to 6.

8. Use of the graphene composite material according to claim 7 in a catalyst.

9. A graphene obtained by treating the graphene composite material according to claim 8 with hydrochloric acid.

10. The graphyne according to claim 9, wherein: The concentration of hydrochloric acid used in the hydrochloric acid treatment is 0.2-0.8M.

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