Preparation method and device of large-area two-dimensional acetylene-rich carbon material film

Abstract

The invention provides a preparation method and device of a large-area two-dimensional acetylene-rich carbon material film, and belongs to the technical field of chemical synthesis. By controlling the directional movement of the copper substrate in the precursor solution, the retention time of the copper substrate in unit area in the precursor solution is controlled, so that the growth of the two-dimensional acetylene-rich carbon material on the copper substrate in unit area in fixed reaction time is realized, and the two-dimensional acetylene-rich carbon material with uniform thickness and high crystallinity is obtained. And in the deposition polymerization reaction process, the copper substrate in the precursor solution is continuously updated, so that large-area and continuous preparation of the two-dimensional alkyne-rich carbon material can be realized, and the method is suitable for industrial and batch production of the two-dimensional alkyne-rich carbon material. Furthermore, the concentration of the precursor solution is monitored in real time by utilizing an ultraviolet visible light spectrum, and the stability and invariability of the precursor concentration in the reaction process are ensured through continuous flowing and continuous updating of the precursor solution, so that the two-dimensional alkyne-rich carbon material film is grown at a certain reaction rate.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical synthesis, and particularly relates to a preparation method and device for a large-area two-dimensional polyyne carbon material film. Background Art

[0002] Due to its unique structure and excellent properties, two-dimensional polyyne carbon materials have broad application prospects in the fields of catalysis, energy storage, electronic devices, adsorption and separation, etc. The copper template method for synthesizing two-dimensional polyyne carbon materials can achieve gram-scale preparation, but there are the following problems: First, this method is a discontinuous preparation. If a large amount is to be prepared, the pre- and post-treatment processes are relatively cumbersome and errors are likely to occur during the preparation process. Second, the film thickness is uncontrollable. Depending on the placement method of the copper sheet in the reaction vessel, there may be a phenomenon where two-dimensional polyyne carbon materials do not grow in some areas. Third, during the growth process of two-dimensional polyyne carbon materials, a template replacement phenomenon occurs. The initial two-dimensional polyyne carbon materials grow on the copper substrate. After the copper sheet is completely covered by the two-dimensional polyyne carbon materials, growth continues with the two-dimensional polyyne carbon materials as the template. This template replacement will cause a large number of defects in the two-dimensional polyyne carbon materials, thereby reducing the crystallinity of the two-dimensional polyyne carbon materials.

[0003] Currently, methods such as the interfacial method, chemical vapor deposition method, and van der Waals epitaxy method have been developed to prepare two-dimensional polyyne carbon materials. These methods have greatly improved the crystallinity of two-dimensional polyyne carbon materials. And the film thickness is controllable, and oligolayer two-dimensional polyyne carbon materials have been prepared. However, these methods can only achieve yields at the milligram or even microgram level and are not suitable for large-scale production. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a preparation method and device for a large-area two-dimensional polyyne carbon material film. The preparation method provided by the present invention can achieve large-area and continuous preparation of two-dimensional polyyne carbon material films, and the obtained two-dimensional polyyne carbon material films have high crystallinity and controllable thickness.

[0005] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions: The present invention provides a preparation method for a large-area two-dimensional polyyne carbon material film, comprising the following steps: Pass the directionally moving copper substrate through the precursor solution for deposition polymerization reaction to obtain a two-dimensional polyyne carbon material film on the surface of the copper substrate; The moving rate of the copper substrate is 0.01 - 10 cm / min; The components of the precursor solution include monomers for preparing two-dimensional polyyne carbon materials and polar organic solvents.

[0006] Preferably, the two-dimensional polyyne carbon material has one or more of the structures shown in Formula I - Formula IX; Formula I; Formula II; Formula III; Formula IV; Formula V; Formula VI; Formula VII; Formula VIII; Formula IX; wherein, in Formula II, X, Y, and Z are independently H, F, Cl, CH 3 , OCH 3 , CF 3 , CN, NH 2 , NO 2 , or COOCH 3 groups; in Formula III, W, X, Y, and Z are independently H, F, Cl, OCH 3 , CN, CF 3 , NH 2 , NO 2 , or COOCH 3 groups; in Formula IV, X is B or P; in Formula V, X is C, Si, Ge, Sn, Pb, Ti, Zr, or ; in Formulas VI and VII, X and Y are independently H, F, Cl, OCH 3 , CF 3 , CN, NH 2 , NO 2 or COOCH 3 groups; in Formula VIII, X is C or N, and Y is H, F, Cl, CH 3 , OCH 3 , CF 3 , CN, NH 2 , NO 2 or COOCH 3 groups; in Formula IX, W is C or N, and X, Y, and Z are independently H, F, Cl, OCH 3 , CF 3 , CN, NH 2 , NO 2 or COOCH 3 groups.

[0007] Preferably, the monomer corresponding to the two-dimensional full-yne carbon material with the structure shown in Formula I has the structure shown in Formula a; The monomer corresponding to the two-dimensional full-yne carbon material with the structure shown in Formula II has the structure shown in Formula b; The monomer corresponding to the two-dimensional full-yne carbon material with the structure shown in Formula III has the structure shown in Formula c; The monomer corresponding to the two-dimensional full-yne carbon material with the structure shown in Formula IV has the structure shown in Formula d; The monomer corresponding to the two-dimensional full-yne carbon material with the structure shown in Formula V has the structure shown in Formula e; The monomer corresponding to the two-dimensional full-yne carbon material with the structures shown in Formula VI and Formula VII has the structure shown in Formula f; The monomer corresponding to the two-dimensional full-yne carbon material with the structure shown in VIII has the structure shown in Formula g; The monomer corresponding to the two-dimensional full-yne carbon material with the structure shown in IX includes a compound with the structure shown in Formula h and tribromobenzene; Formula a; Formula b; Formula c; Formula d; Formula e; Formula f; Formula g; Formula h.

[0008] Preferably, the concentration of the monomer in the precursor solution is 0.0001 - 5 mg / mL.

[0009] Preferably, the precursor solution further includes a catalyst, and the mass concentration of the catalyst in the precursor solution is 0 - 5%.

[0010] Preferably, the polar organic solvent includes essential components and non-essential components. The essential component includes pyridine; the non-essential components include one or more of triethylamine, diethylamine, tetrahydrofuran, dichloromethane, trichloromethane, acetone, N, N-dimethylformamide, N-methylpyrrolidone, toluene, p-xylene, dimethyl sulfoxide, acetonitrile, and N, N, N, N-tetramethylethylenediamine; The volume ratio of the essential component to the non-essential components is 1:0 - 20.

[0011] Preferably, the thickness of the copper substrate is 10 - 100 μm; The temperature of the deposition polymerization reaction is 20 - 120 °C; The thickness of the two-dimensional full-yne carbon material film is 100 nm - 200 μm.

[0012] Preferably, the precursor solution is a flowing liquid, and the flow rate of the precursor solution is 1-20 mL / min.

[0013] The present invention provides a preparation device for a large-area two-dimensional carbon-rich alkyne material film, comprising a winding machine, a pre-cleaning tank, a reaction tank and a post-cleaning tank; The pre-cleaning tank, the reaction tank and the post-cleaning tank are connected in sequence; The winding machine includes an unwinding part and a winding part. The unwinding part is arranged at the inlet end of the pre-cleaning tank, and the winding part is arranged at the outlet end of the post-cleaning tank. The winding machine drives the copper substrate to pass through the pre-cleaning tank, the reaction tank and the post-cleaning tank in sequence.

[0014] Preferably, an ultraviolet-visible spectrophotometer is further provided above the reaction tank.

[0015] The present invention provides a preparation method for a large-area two-dimensional carbon-rich alkyne material film, comprising the following steps: passing a directionally moving copper substrate through a precursor solution to carry out a deposition polymerization reaction to obtain a two-dimensional carbon-rich alkyne material film on the surface of the copper substrate; the moving rate of the copper substrate is 0.01-10 cm / min; the components of the precursor solution include monomers for preparing the two-dimensional carbon-rich alkyne material and polar organic solvents. By controlling the directional movement of the copper substrate in the precursor solution, the present invention controls the residence time of the copper substrate per unit area in the precursor solution, so as to realize the growth of the two-dimensional carbon-rich alkyne material on the copper substrate per unit area with a fixed reaction time, and further obtain a two-dimensional carbon-rich alkyne material with uniform thickness and high crystallinity. During the deposition polymerization reaction, the copper substrate in the precursor solution is continuously updated, so that the large-area and continuous preparation of the two-dimensional carbon-rich alkyne material can be realized, which is suitable for the industrialized and batch production of the two-dimensional carbon-rich alkyne material.

[0016] Furthermore, the present invention uses ultraviolet-visible light spectroscopy to monitor the concentration of the precursor solution in real time, and ensures the stable concentration of the precursor during the reaction process by the continuous flow and continuous update of the precursor solution, so as to realize the growth of the two-dimensional carbon-rich alkyne material film at a certain reaction rate.

[0017] Furthermore, the present invention controls the growth thickness of the two-dimensional carbon-rich alkyne material film by controlling the precursor concentration and the reaction temperature.

[0018] The present invention provides a preparation device for a large-area two-dimensional alkyne-rich carbon material film, which includes a winding machine, a pre-cleaning tank, a reaction tank, and a post-cleaning tank; the pre-cleaning tank, the reaction tank, and the post-cleaning tank are connected in sequence; the winding machine includes an unwinding part and a winding part, the unwinding part is arranged at the inlet end of the pre-cleaning tank, the winding part is arranged at the outlet end of the post-cleaning tank, and the winding machine drives a copper substrate to pass through the pre-cleaning tank, the reaction tank, and the post-cleaning tank in sequence. In the present invention, the copper substrate is fixed to the winding machine, and the movement of the copper substrate is driven by the winding machine to realize the large-area and continuous preparation of the two-dimensional alkyne-rich carbon material film. Description of the Drawings

[0019] Figure 1 It is a schematic structural diagram of a preparation device for a large-area two-dimensional alkyne-rich carbon material film; Figure 2 It is the XPS total spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1; Figure 3 It is the C-XPS spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1; Figure 4 It is the infrared spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1; Figure 5 It is the Raman spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1; Figure 6 It is the high-resolution transmission electron microscope image of the two-dimensional alkyne-rich carbon material obtained in Example 1; Figure 7 It is the scanning electron microscope image of the two-dimensional alkyne-rich carbon material obtained in Example 2 by reacting in a pyridine / acetone mixed solution for 2 min, 10 min, 30 min, and 1 h on a copper foil, Figure 7 wherein, (a) is for 2 min, (b) is for 10 min, (c) is for 30 min, and (d) is for 1 h; Figure 8 It is the physical image of the two-dimensional alkyne-rich carbon material obtained in Example 2 by reacting in a pyridine / acetone mixed solution for 2 min, 10 min, 30 min, and 1 h on a copper foil, Figure 8 wherein, (a) is for 2 min, (b) is for 10 min, (c) is for 30 min, and (d) is for 1 h; Figure 9 It is the scanning electron microscope image of the two-dimensional alkyne-rich carbon material obtained in Example 1 by reacting in a pyridine solution for 2 min, 10 min, 30 min, and 1 h on a copper foil, Figure 9 wherein, (a) is for 2 min, (b) is for 10 min, (c) is for 30 min, and (d) is for 1 h; Figure 10Photographs of the two-dimensional alkyne-rich carbon materials obtained in Example 1 by reacting in a pyridine solution for 2 min, 10 min, 30 min, and 1 h on a copper foil. Figure 10 Among them, (a) is 2 min, (b) is 10 min, (c) is 30 min, and (d) is 1 h. Detailed implementation mode

[0020] The present invention provides a method for preparing a large-area two-dimensional alkyne-rich carbon material film, comprising the following steps: Pass a directionally moving copper substrate through a precursor solution to carry out a deposition polymerization reaction, and obtain a two-dimensional alkyne-rich carbon material film on the surface of the copper substrate; The moving rate of the copper substrate is 0.01 - 10 cm / min; The composition of the precursor solution includes monomers for preparing two-dimensional alkyne-rich carbon materials and polar organic solvents.

[0021] In the present invention, a directionally moving copper substrate is passed through a precursor solution to carry out a deposition polymerization reaction, and a two-dimensional alkyne-rich carbon material film is obtained on the surface of the copper substrate. In the present invention, the copper substrate is preferably a copper foil, specifically preferably a commercial copper foil.

[0022] In the present invention, the thickness of the copper substrate is preferably 10 - 100 μm, more preferably 30 - 70 μm, and specifically can be 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 μm. In the present invention, the length of the copper substrate is preferably 20 - 100 m, more preferably 40 - 80 m. Before the deposition polymerization reaction, the present invention preferably cleans the copper substrate, and the cleaning reagent is preferably one or several of hydrochloric acid, water, and ethanol, and the concentration of the hydrochloric acid is preferably 1 mol / L.

[0023] In the present invention, the moving rate of the copper substrate is 0.01 - 10 cm / min, preferably 0.1 - 1 cm / min, and specifically can be 0.01 cm / min, 0.05 cm / min, 0.1 cm / min, 0.5 cm / min, 1 cm / min, 2 cm / min, 5 cm / min, 8 cm / min, or 10 cm / min. In the present invention, starting from the position where the copper substrate begins to contact the precursor solution, the residence time of the copper substrate from entering the reaction tank to leaving the reaction tank is preferably 0.5 - 10 h, more preferably 1 - 8 h, more preferably 3 - 6 h, and specifically can be 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, or 10 h.

[0024] In the present invention, the composition of the precursor solution includes monomers for preparing two-dimensional carbon-rich alkyne materials and polar organic solvents. In the present invention, the concentration of the monomers in the precursor solution is preferably 0.0001 - 5 mg / mL, more preferably 0.001 - 4 mg / mL, further preferably 0.01 - 3 mg / mL, and even more preferably 0.1 - 1 mg / mL.

[0025] In the present invention, the polar organic solvent preferably includes essential components and non-essential components. The essential components preferably include pyridine; the non-essential components preferably include one or more of triethylamine, diethylamine, tetrahydrofuran, dichloromethane, trichloromethane, acetone, N, N-dimethylformamide, N-methylpyrrolidone, toluene, p-xylene, dimethyl sulfoxide, acetonitrile, and N, N, N, N-tetramethylethylenediamine; the volume ratio of the essential components to the non-essential components is preferably 1:0 - 20, more preferably 1:5 - 10, and specifically can be 1:0, 1:1, 1:5, 1:8, 1:10, 1:15, or 1:20.

[0026] In the present invention, the precursor solution preferably further includes a catalyst, and the catalyst is preferably palladium acetate. In the present invention, the mass concentration of the catalyst in the precursor solution is preferably 0 - 5%, and specifically can be 0, 0.5%, 1%, 2%, 3%, 4%, or 5%. In the present invention, the catalyst is preferably added in the form of an aqueous solution.

[0027] In the present invention, the deposition polymerization reaction is preferably carried out under a protective atmosphere, and the protective atmosphere is preferably nitrogen or argon. In the present invention, the temperature of the deposition polymerization reaction is preferably 20 - 120 °C, more preferably 40 - 80 °C, and specifically can be 20 °C, 40 °C, 60 °C, 80 °C, 100 °C, or 120 °C.

[0028] In the present invention, during the deposition polymerization reaction, it further includes real-time monitoring of the concentration of the precursor solution by ultraviolet-visible spectroscopy.

[0029] In the present invention, the precursor solution is preferably a flowing liquid, and the flow rate of the precursor solution is preferably 1 - 20 mL / min, more preferably 5 - 15 mL / min, and specifically can be 5 mL / min, 10 mL / min, 15 mL / min, or 20 mL / min.

[0030] In the present invention, after the deposition polymerization reaction, the present invention preferably performs post-treatment on the copper substrate and the two-dimensional carbon-rich alkyne material film on the surface of the copper substrate. The post-treatment preferably includes washing and drying carried out in sequence. In the present invention, the reagent used for washing is preferably acetone and / or N-methylpyrrolidone. The present invention has no special requirements for the drying method, and any drying method well-known in the art can be used.

[0031] After obtaining the two-dimensional alkyne-rich carbon material film on the surface of the copper substrate, the present invention preferably peels the two-dimensional alkyne-rich carbon material film from the surface of the copper substrate. In the present invention, the peeling method preferably includes the following steps: Immerse the copper substrate with the two-dimensional alkyne-rich carbon material film in hydrochloric acid solution or ammonia water to peel the two-dimensional alkyne-rich carbon material from the copper substrate.

[0032] In the present invention, the concentration of the hydrochloric acid solution is preferably 1 mol / L hydrochloric acid; the ammonia water is preferably commercial concentrated ammonia water. In the present invention, the immersion time is preferably 10 - 600 min, more preferably 30 - 240 min, and specifically can be 10 min, 30 min, 60 min, 120 min, 180 min, 240 min, 300 min, 400 min, 500 min or 600 min.

[0033] In the present invention, the thickness of the two-dimensional alkyne-rich carbon material film is 100 nm - 200 μm, more preferably 500 nm - 20 μm, and specifically can be 100 nm, 500 nm, 1 μm, 5 μm, 10 μm, 50 μm, 100 μm, 150 μm or 200 μm.

[0034] In the present invention, the two-dimensional alkyne-rich carbon material preferably has one or more of the structures shown in Formula I - Formula IX; Formula I; Formula II; Formula III; Formula IV; Formula V; Formula VI; Formula VII; Formula VIII; Formula IX; Among them, in Formula II, X, Y, and Z are independently H, F, Cl, CH 3 , OCH 3 , CF 3 , CN, NH 2 , NO 2 , or COOCH 3 groups, and X, Y, and Z can be the same group at the same time; In Formula III, W, X, Y, and Z are independently H, F, Cl, OCH 3 , CN, CF 3, NH 2 , NO 2 , or COOCH 3 group, and W, X, Y, Z can be the same group simultaneously; In formula IV, X is B or P; In formula V, X is C, Si, Ge, Sn, Pb, Ti, Zr, (tetraphenylmethane) or (tetraphenylsilane); In formula VI and formula VII, X and Y are independently H, F, Cl, OCH 3 , CF 3 , CN, NH 2 , NO 2 , or COOCH 3 group, and X and Y can be the same group simultaneously; In formula VIII, X is C or N, and Y is H, F, Cl, CH 3 , OCH 3 , CF 3 , CN, NH 2 , NO 2 , or COOCH 3 group; In formula IX, W can be C or N, and X, Y, Z are independently H, F, Cl, OCH 3 , CF 3 , CN, NH 2 , NO 2 , or COOCH 3 group, and X, Y, Z can be the same group simultaneously.

[0035] In the present invention, in the above structural formula, " " represents the connection site.

[0036] In the present invention, the source of the monomer for preparing the two-dimensional rich-alkyne carbon material is preferably commercially available or self-prepared. In the present invention, the monomer corresponding to the two-dimensional rich-alkyne carbon material shown in formula I has the structure shown in formula a.

[0037] Formula a.

[0038] In the present invention, the preparation method of the monomer having the structure shown in formula a preferably includes the following steps: Add hexabromobenzene, ethynyltrimethylsilane, and catalyst to triethylamine in sequence, and carry out a substitution reaction under a nitrogen atmosphere to obtain hexakis[(trimethylsilyl)ethynyl]benzene; Mix a tetrahydrofuran solution of hexakis[(trimethylsilyl)ethynyl]benzene and a tetrahydrofuran solution of a deprotection reagent to carry out a deprotection reaction to obtain hexaethynylbenzene, that is, a monomer having the structure shown in formula a.

[0039] In the present invention, the catalyst preferably comprises PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P; the molar ratio of PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P is preferably 1:8:8.

[0040] In the present invention, the molar ratio of the hexabromobenzene to ethynyltrimethylsilane is preferably 1:4; the sum of the molar amounts of the hexabromobenzene and the catalyst is preferably in a ratio of 10:1; the dosage ratio of the hexabromobenzene to triethylamine is preferably 10 mmol: 20 - 80 mL, more preferably 4 mmol: 50 mL.

[0041] In the present invention, the temperature of the substitution reaction is preferably 80 °C and the time is preferably 3 - 5 days. In the present invention, after the substitution reaction, it preferably further includes successively concentrating, purifying by column chromatography, and removing the solvent by evaporation the system obtained from the substitution reaction. The eluent for the column chromatography purification is preferably a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1.

[0042] In the present invention, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the hexakis[(trimethylsilyl)ethynyl]benzene to the deprotection reagent is preferably 0.1 - 0.15:0.4, more preferably 0.1 - 0.12:0.4.

[0043] In the present invention, the concentration of the tetrahydrofuran solution of the hexakis[(trimethylsilyl)ethynyl]benzene is preferably 0.008 - 0.015 mol / L, more preferably 0.01 - 0.012 mol / L; the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L. In the present invention, the temperature of the deprotection reaction is preferably 0 °C and the time is preferably 30 min. In the present invention, the deprotection reaction is preferably carried out under stirring conditions. In the present invention, after the deprotection reaction, it preferably further includes diluting the system after the deprotection reaction with dichloromethane, then successively washing with distilled water, drying with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain hexaethynylbenzene, that is, a monomer having the structure shown in formula a.

[0044] In the present invention, the monomer corresponding to the two-dimensional polyacetylene carbon material having the structure shown in formula II has the structure shown in formula b.

[0045] Formula b.

[0046] In the present invention, the preparation method of the monomer having the structure shown in Formula b preferably includes the following steps: Adding a tribromo derivative having the structure shown in Formula 1-1, ethynyltrimethylsilane, and a catalyst into a polar solvent in sequence, and performing a substitution reaction under a nitrogen atmosphere to obtain an intermediate having the structure shown in Formula 1-2; Mixing a tetrahydrofuran solution of the intermediate having the structure shown in Formula 1-2 and a tetrahydrofuran solution of a deprotection reagent, and performing a deprotection reaction to obtain the monomer having the structure shown in Formula b.

[0047] Formula 1-1; Formula 1-2.

[0048] In the present invention, the catalyst preferably includes PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P; the molar ratio of PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P is preferably 1:2:2.

[0049] In the present invention, the molar ratio of the tribromo derivative having the structure shown in Formula 1-1 to ethynyltrimethylsilane is preferably 1:10; the sum of the molar amounts of the tribromo derivative having the structure shown in Formula 1-1 and the catalyst is preferably 2:1; in the present invention, the polar solvent is preferably tetrahydrofuran, and the dosage ratio of the tribromo derivative having the structure shown in Formula 1-1 to the polar solvent is preferably 4 mmol:20~80 mL, more preferably 4 mmol:50 mL.

[0050] In the present invention, the temperature of the substitution reaction is preferably 80°C, and the time is preferably 3 to 5 days. In the present invention, after the substitution reaction, it preferably further includes concentrating, column chromatography purification, and desolvation of the system obtained from the substitution reaction in sequence. The eluent for the column chromatography purification is preferably a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1.

[0051] In the present invention, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure shown in Formula 1-2 to the deprotection reagent is preferably 0.1~0.15:0.4, more preferably 0.1~0.12:0.4.

[0052] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate having the structure shown in Formula 1-2 is preferably 0.008 to 0.015 mol / L, more preferably 0.01 to 0.012 mol / L; the concentration of the deprotecting reagent in the tetrahydrofuran solution of the deprotecting reagent is preferably 1 mol / L. In the present invention, the temperature of the deprotection reaction is preferably 0 °C, and the time is preferably 30 min. In the present invention, the deprotection reaction is preferably carried out under stirring conditions. In the present invention, after the deprotection reaction, it preferably further includes diluting the system after the deprotection reaction with dichloromethane, washing successively with distilled water, drying with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain the monomer having the structure shown in Formula b.

[0053] In the present invention, the monomer corresponding to the two-dimensional rich-alkyne carbon material having the structure shown in Formula III has the structure shown in Formula c.

[0054] Formula c.

[0055] In the present invention, the preparation method of the monomer having the structure shown in Formula c preferably includes the following steps: Add the compound having the structure shown in Formula 2-1, ethynyltrimethylsilane, and a catalyst to triethylamine in sequence, and carry out a substitution reaction under a nitrogen atmosphere to obtain an intermediate having the structure shown in Formula 2-2; Mix the tetrahydrofuran solution of the intermediate having the structure shown in Formula 2-2 and the tetrahydrofuran solution of the deprotecting reagent, and carry out a deprotection reaction to obtain the monomer having the structure shown in Formula c.

[0056] Formula 2-1; Formula 2-2.

[0057] In the present invention, the preparation process of the monomer having the structure shown in Formula c is basically the same as that of the monomer having the structure shown in Formula b, except that the starting materials are different. The optional ranges of the amounts of the raw materials and the reaction conditions in the preparation process of the monomer having the structure shown in Formula c refer to the preparation process of the monomer having the structure shown in Formula b, and will not be elaborated here.

[0058] In the present invention, the monomer corresponding to the two-dimensional rich-alkyne carbon material having the structure shown in Formula IV has the structure shown in Formula d.

[0059] Formula d.

[0060] In the present invention, the preparation method of the monomer having the structure shown in Formula d preferably includes the following steps: Add the chloride with the structure shown in Formula 3-1, n-butyllithium, and ethynyltrimethylsilane into tetrahydrofuran, and carry out a substitution reaction under a nitrogen atmosphere to obtain an intermediate with the structure shown in Formula 3-2; Formula 3-1; Formula 3-2; Mix the tetrahydrofuran solution of the intermediate with the structure shown in Formula 3-2 and the tetrahydrofuran solution of the deprotection reagent, and carry out a deprotection reaction to obtain a monomer with the structure shown in Formula d.

[0061] In the present invention, it is preferred to add the chloride with the structure shown in Formula 3-1, n-butyllithium, and ethynyltrimethylsilane into tetrahydrofuran in sequence. In the present invention, the molar ratio of the chloride with the structure shown in Formula 3-1 to ethynyltrimethylsilane is preferably 1:5 to 15; the molar ratio of the chloride with the structure shown in Formula 3-1 to n-butyllithium is preferably 1:2.4 to 3; the dosage ratio of the chloride with the structure shown in Formula 3-1 to tetrahydrofuran is preferably 1 to 3 mmol: 20 to 100 mL, more preferably 2 mmol: 50 mL.

[0062] In the present invention, the temperature of the substitution reaction is preferably -80 °C, and the time is preferably 2 to 4 h. In the present invention, after the substitution reaction, it is preferably further included to concentrate, purify by column chromatography, and desolvate the system obtained from the substitution reaction in sequence. The eluent for the column chromatography purification is preferably a mixed solution of n-hexane and dichloromethane with a volume ratio of 5 to 10:1.

[0063] In the present invention, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate with the structure shown in Formula 3-2 to the deprotection reagent is preferably 1:1 to 1:8, more preferably 1:4.

[0064] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate with the structure shown in Formula 3-2 is preferably 8 to 15 mmol / L, more preferably 10 to 12 mmol / L; the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L.

[0065] In the present invention, the temperature of the deprotection reaction is preferably 0 °C, and the time is preferably 30 min. In the present invention, the deprotection reaction is preferably carried out under stirring conditions. In the present invention, after the deprotection reaction, it is preferably further included to dilute the system after the deprotection reaction with dichloromethane, and then wash it with distilled water, dry it with anhydrous sodium sulfate, and remove the solvent by vacuum rotary evaporation to obtain a monomer with the structure shown in Formula d.

[0066] In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material with the structure shown in Formula V has the structure shown in Formula e; Formula e.

[0067] In the present invention, a method for preparing a monomer having the structure shown in Formula e preferably includes the following steps: Add a chloride having the structure shown in Formula 4-1, n-butyllithium, and ethynyltrimethylsilane to tetrahydrofuran in sequence, and carry out a substitution reaction under a nitrogen atmosphere to obtain an intermediate having the structure shown in Formula 4-2; Formula 4-1; Formula 4-2; Mix a tetrahydrofuran solution of the intermediate having the structure shown in Formula 4-2 and a tetrahydrofuran solution of a deprotection reagent, and carry out a deprotection reaction to obtain a monomer having the structure shown in Formula e.

[0068] In the present invention, the molar ratio of the chloride having the structure shown in Formula 4-1 to ethynyltrimethylsilane is preferably 1:5 to 20; the sum of the molar amounts of the chloride having the structure shown in Formula 4-1 and n-butyllithium is preferably 1:3 to 4.8; the dosage ratio of the chloride having the structure shown in Formula 4-1 to tetrahydrofuran is preferably 1 to 3 mmol: 20 to 100 mL, more preferably 2 mmol: 50 mL.

[0069] In the present invention, the temperature of the substitution reaction is preferably -80 °C, and the time is preferably 2 to 4 h. In the present invention, after the substitution reaction, it preferably further includes concentrating, column chromatography purification, and desolvation of the system obtained from the substitution reaction in sequence. The eluent for the column chromatography purification is preferably a mixed solution of n-hexane and dichloromethane with a volume ratio of 5 to 10:1.

[0070] In the present invention, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure shown in Formula 4-2 to the deprotection reagent is preferably 1:1 to 1:8, more preferably 1:4.

[0071] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate having the structure shown in Formula 4-2 is preferably 8 to 15 mmol / L, more preferably 10 to 12 mmol / L; the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L.

[0072] In the present invention, the temperature of the deprotection reaction is preferably 0 °C, and the time is preferably 30 min. In the present invention, the deprotection reaction is preferably carried out under stirring conditions. In the present invention, after the deprotection reaction, it preferably further includes diluting the system after the deprotection reaction with CH 2 Cl 2 and then washing with distilled water in sequence, and anhydrous Na 2 SO4 The solvent was removed by drying and vacuum rotary evaporation to obtain a monomer having the structure shown in Formula e.

[0073] In the present invention, the monomers corresponding to the two-dimensional alkyne-rich carbon materials having the structures shown in Formula VI and Formula VII have the structure shown in Formula f; Formula f.

[0074] In the present invention, the preparation method of the monomer having the structure shown in Formula f preferably includes the following steps: A tetrabromo derivative having the structure shown in Formula 5-1, ethynyltrimethylsilane, and a catalyst were successively added to triethylamine, and a substitution reaction was carried out under a nitrogen atmosphere to obtain an intermediate having the structure shown in Formula 5-2; Formula 5-1; Formula 5-2; The tetrahydrofuran solution of the intermediate having the structure shown in Formula 5-2 and the tetrahydrofuran solution of the deprotection reagent were mixed, and a deprotection reaction was carried out to obtain a monomer having the structure shown in Formula f.

[0075] In the present invention, the catalyst preferably includes PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P; the molar ratio of PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P is preferably 1:2:2.

[0076] In the present invention, the molar ratio of the tetrabromo derivative having the structure shown in Formula 5-1 to ethynyltrimethylsilane is preferably 1:10; the sum of the molar amounts of the tetrabromo derivative having the structure shown in Formula 5-1 and the catalyst is preferably 2:1; the dosage ratio of the tetrabromo derivative having the structure shown in Formula 5-1 to triethylamine is preferably 4 mmol:20 - 80 mL, more preferably 4 mmol:50 mL.

[0077] In the present invention, the temperature of the substitution reaction is preferably 80 °C, and the time is preferably 5 days. In the present invention, after the substitution reaction, it preferably further includes successively concentrating, purifying by column chromatography, and removing the solvent from the system obtained by the substitution reaction. The eluent for the column chromatography purification is preferably a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1.

[0078] In the present invention, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure shown in Formula 5-2 to the deprotection reagent is preferably 0.1~0.15:0.4, more preferably 0.1~0.12:0.4.

[0079] In the present invention, the concentration of the intermediate having the structure shown in Formula 5-2 in the tetrahydrofuran solution is preferably 0.008~0.015 mol / L, more preferably 0.01~0.012 mol / L; the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L.

[0080] In the present invention, the temperature of the deprotection reaction is preferably 0~6 °C, and the time is preferably 30 min. In the present invention, the deprotection reaction is preferably carried out under stirring conditions. In the present invention, after the deprotection reaction, it preferably further includes diluting the system after the deprotection reaction with dichloromethane, washing successively with distilled water, drying with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain the monomer having the structure shown in Formula f.

[0081] In the present invention, when using the monomer having the structure shown in Formula f to prepare the two-dimensional full-yne carbon material having the structure shown in Formula VII, the non-essential component of the polar organic solvent in the precursor solution is preferably a weakly polar organic solvent, specifically preferably one or more of tetrahydrofuran, dichloromethane, and chloroform; when using the monomer having the structure shown in Formula f to prepare the two-dimensional full-yne carbon material having the structure shown in Formula VI, the non-essential component of the polar organic solvent in the precursor solution is preferably a strongly polar organic solvent, specifically preferably one or more of dimethyl sulfoxide, acetonitrile, and dimethylformamide.

[0082] In the present invention, the monomer corresponding to the two-dimensional full-yne carbon material having the structure shown in VIII has the structure shown in Formula g; Formula g.

[0083] In the present invention, the preparation method of the monomer having the structure shown in Formula g preferably includes the following steps: Add the pentabromo derivative having the structure shown in Formula 6-1, ethynyltrimethylsilane, and the catalyst to triethylamine in sequence, and carry out a substitution reaction under a nitrogen atmosphere to obtain an intermediate having the structure shown in Formula 6-2: Formula 6-1; Formula 6-2; Mix the tetrahydrofuran solution of the intermediate having the structure shown in Formula 6-2 and the tetrahydrofuran solution of the deprotection reagent, and carry out a deprotection reaction to obtain the monomer having the structure shown in Formula g.

[0084] In the present invention, the catalyst preferably comprises PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P; the molar ratio of PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P in the catalyst is preferably 1:2:2.

[0085] In the present invention, the molar ratio of the pentabromo derivative having the structure shown in Formula 6-1 and ethynyltrimethylsilane is preferably 1:10; the sum of the molar amounts of the pentabromo derivative having the structure shown in Formula 6-1 and the catalyst is preferably 2:1; the dosage ratio of the pentabromo derivative having the structure shown in Formula 6-1 and triethylamine is preferably 4 mmol: 20-80 mL, more preferably 4 mmol: 50 mL.

[0086] In the present invention, the temperature of the substitution reaction is preferably 80 °C and the time is preferably 5 days. In the present invention, after the substitution reaction, it preferably further includes concentrating, column chromatography purification and solvent removal in sequence for the system obtained from the substitution reaction. The eluent for the column chromatography purification is preferably a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1.

[0087] In the present invention, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure shown in Formula 6-2 and the deprotection reagent is preferably 0.1-0.15:0.4, more preferably 0.1-0.12:0.4.

[0088] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate having the structure shown in Formula 6-2 is preferably 0.008-0.015 mol / L, more preferably 0.01-0.012 mol / L; the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L.

[0089] In the present invention, the temperature of the deprotection reaction is preferably 0 °C and the time is preferably 30 min. In the present invention, the deprotection reaction is preferably carried out under stirring conditions. In the present invention, after the deprotection reaction, it preferably further includes diluting the system after the deprotection reaction with dichloromethane, followed by washing with distilled water, drying with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain the monomer having the structure shown in Formula g.

[0090] In the present invention, the monomers corresponding to the two-dimensional carbon-rich alkyne material with the structure shown in IX include a compound with the structure shown in Formula h and tribromobenzene; in the present invention, the molar ratio of the compound with the structure shown in Formula h to tribromobenzene is preferably 3:1 to 1:3, more preferably 1:1.

[0091] Formula h.

[0092] In the present invention, the preparation method of the monomer with the structure shown in Formula h preferably includes the following steps: Add a tribromo derivative with the structure shown in Formula 7-1, ethynyltrimethylsilane, and a catalyst into triethylamine in sequence, and carry out a substitution reaction under a nitrogen atmosphere to obtain an intermediate with the structure shown in Formula 7-2: Formula 7-1; Formula 7-2; Mix the tetrahydrofuran solution of the intermediate with the structure shown in Formula 7-2 and the tetrahydrofuran solution of the deprotection reagent, and carry out a deprotection reaction to obtain a monomer with the structure shown in Formula g.

[0093] In the present invention, the catalyst preferably includes PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P; the molar ratio of PdCl 2 (PPh 3 ) 2 , CuI and Ph 3 P is preferably 1:2:2.

[0094] In the present invention, the molar ratio of the tribromo derivative with the structure shown in Formula 7-1 to ethynyltrimethylsilane is preferably 1:10; the sum of the molar amounts of the tribromo derivative with the structure shown in Formula 7-1 and the catalyst is preferably 2:1; the dosage ratio of the tribromo derivative with the structure shown in Formula 7-1 to triethylamine is preferably 4 mmol: 20 - 80 mL, more preferably 4 mmol: 50 mL.

[0095] In the present invention, the temperature of the substitution reaction is preferably 80 °C, and the time is preferably 5 days. In the present invention, after the substitution reaction, it preferably further includes concentrating, purifying by column chromatography, and desolvating the system obtained from the substitution reaction in sequence. The eluent for the column chromatography purification is preferably a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1.

[0096] In the present invention, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure shown in Formula 7-2 to the deprotection reagent is preferably 0.1 to 0.15:0.4, more preferably 0.1 to 0.12:0.4.

[0097] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate having the structure shown in Formula 7-2 is preferably 0.008 to 0.015 mol / L, more preferably 0.01 to 0.012 mol / L; the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L.

[0098] In the present invention, the temperature of the deprotection reaction is preferably 0 to 6 °C, and the time is preferably 30 min. In the present invention, the deprotection reaction is preferably carried out under stirring conditions. In the present invention, after the deprotection reaction, it preferably further includes diluting the system after the deprotection reaction with dichloromethane, washing successively with distilled water, drying with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain a monomer having the structure shown in Formula h.

[0099] The present invention provides a preparation device for a large-area two-dimensional rich-alkyne carbon material film, including a winding machine, a pre-cleaning tank, a reaction tank, and a post-cleaning tank; The pre-cleaning tank, the reaction tank, and the post-cleaning tank are connected in sequence; The winding machine includes a unwinding part and a winding part. The unwinding part is arranged at the inlet end of the pre-cleaning tank, and the winding part is arranged at the outlet end of the post-cleaning tank. The winding machine drives the copper substrate to pass through the pre-cleaning tank, the reaction tank, and the post-cleaning tank in sequence.

[0100] In the present invention, the pre-cleaning tank is used to hold a pre-cleaning reagent. The pre-cleaning reagent is preferably one or several of hydrochloric acid, water, and ethanol in sequence, and is used to clean the copper substrate. In the present invention, the concentration of the hydrochloric acid is preferably 1 mol / L. In the present invention, the number of the pre-cleaning tanks is preferably 3, which respectively hold hydrochloric acid, water, and ethanol. In the present invention, the width of a single pre-cleaning tank is preferably 1 to 50 cm, more preferably 10 to 40 cm, and the length is preferably 20 to 480 cm, more preferably 100 to 400 cm.

[0101] In the present invention, the reaction tank is used to hold a precursor solution. The width of the reaction tank is preferably 1 to 50 cm, more preferably 10 to 40 cm, and the length is preferably 20 to 480 cm, more preferably 100 to 400 cm. As a specific embodiment of the present invention, the size of the reaction tank is preferably 25×60 cm.

[0102] In the present invention, the post - cleaning pool is used to hold the post - cleaning reagent, and the post - cleaning reagent is preferably one or more of ethanol, acetone, and N - methyl pyrrolidone. In the present invention, the width of the post - cleaning pool is preferably 1 - 50 cm, more preferably 10 - 40 cm, the length is preferably 20 - 480 cm, and more preferably 100 - 400 cm.

[0103] In the present invention, an ultraviolet - visible spectrophotometer is preferably provided above the reaction pool.

[0104] In the present invention, the structural schematic diagram of the preparation device for the large - area two - dimensional rich - alkyne carbon material film is as Figure 1 shown. From left to right, the device includes an unwinder, three cleaning pools, a reaction pool, a cleaning pool, and a winder.

[0105] The copper substrate comes out of the unwinder and enters the three cleaning pools respectively. 1 mol / L hydrochloric acid, water, and ethanol can be placed in the three cleaning pools respectively to clean the copper substrate. Then the copper substrate enters the reaction pool for reaction, and then enters the post - cleaning pool to clean the obtained product. One or more of ethanol, acetone, and N - methyl pyrrolidone are filled in the post - cleaning pool. Finally, the winder collects the copper substrate and the product.

[0106] The following combines examples to detail the preparation method and device for the large - area two - dimensional rich - alkyne carbon material film provided by the present invention, but they should not be construed as limiting the protection scope of the present invention.

[0107] In the following examples, the size of the reaction pool is 25×60 cm, and the length of the copper substrate immersed in the precursor solution is 50 cm.

[0108] Example 1 (1)Preparation of reaction monomers 5.515 g (10 mmoL) of hexabromobenzene, 11.28 mL (40 mmoL) of ethynyltrimethylsilane ((CH 3 ) 3 SiC≡CH), 0.702 g (0.10 mmoL) of PdCl 2 (PPh 3 ) 2 , 0.152 g (0.8 mmoL) of CuI, and 0.2096 g (0.8 mmoL) of Ph 3 P are successively added to 80 mL of triethylamine. The resulting mixture is stirred in a three - necked flask at 80 °C under a nitrogen atmosphere for a substitution reaction for 3 days.

[0109] The solvent of the system obtained from the substitution reaction was evaporated, and the residue was purified by column chromatography, eluting with a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1 (V 正己烷 :V 二氯甲烷 = 5:1), eluting until no product was detected on the thin-layer chromatography plate to obtain hexakis[(trimethylsilyl)ethynyl]benzene as a white powder.

[0110] To a 15 mL THF solution containing 48.7 mg (0.133 mmol) of hexakis[(trimethylsilyl)ethynyl]benzene was added 0.4 mL of a 1 mol / L THF solution of tetrabutylammonium fluoride. The resulting mixture was stirred at 0 °C for 30 min for the deprotection reaction. After the deprotection reaction system was diluted with dichloromethane, it was washed with distilled water, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under vacuum to obtain hexaethynylbenzene.

[0111] (2) Preparation of large-area two-dimensional alkyne-rich carbon material film The obtained hexaethynylbenzene was diluted with pyridine to obtain a precursor solution with a concentration of 0.02 mg / mL, which was added to the reaction cell. The temperature was raised to 60 °C, and the copper foil was slowly pulled from the left end to the right end of the reaction cell within 1 h (the active surface area was 1000 cm 2 ), and the moving speed was 1 cm / min for the deposition polymerization reaction. After the reaction was completed, the copper foil was washed successively with acetone and N-methylpyrrolidone, and a light yellow film with a thickness of 500 nm appeared on the copper foil, which was a two-dimensional alkyne-rich carbon material film with the structure of Formula I.

[0112] The reaction equation of Example 1 is as follows: .

[0113] Example 2 The difference from Example 1 is only that: The solvent in the precursor solution in the reaction cell was changed to a mixed solvent of acetone and pyridine with a volume ratio of 20:1. The deposition polymerization reaction temperature was changed to 40 °C.

[0114] After the deposition polymerization reaction was completed, a light yellow film with a thickness of 400 nm appeared on the copper foil, which was a two-dimensional alkyne-rich carbon material film with the structure of Formula I.

[0115] Example 3 (1) Preparation of reaction monomer 1.476 g (4 mmol) of 2,4,6-tribromo-1,3,5-trimethylbenzene and 5.64 mL (40 mmol) of (CH 3 ) 3SiC≡CH, 0.2808 g (0.40 mmol) PdCl 2 (PPh 3 ) 2 , 0.152 g (0.8 mmol) CuI and 0.2096 g (0.8 mmol) Ph 3 P were successively added to 80 mL of tetrahydrofuran. The resulting mixture was stirred in a three-necked flask at 80 °C under a nitrogen atmosphere for a substitution reaction for 5 days.

[0116] Then, the solvent of the system obtained from the substitution reaction was evaporated, and the residue was purified by column chromatography, eluted with a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1, (V 正己烷 :V 二氯甲烷 = 5:1), until no product was detected on the thin-layer chromatography plate, and white powdery 1,3,5-tris[(trimethylsilyl)ethynyl]-2,4,6-trimethylbenzene was obtained.

[0117] To a 15 mL THF solution containing 56 mg (0.133 mmol) of 1,3,5-(trimethylsilyl)ethynyl-2,4,6-trimethylbenzene was added 0.4 mL of a 1 mol / L THF solution of TBAF. The resulting mixture was stirred at 6 °C for a deprotection reaction for 30 min. The deprotection reaction system was diluted with CH 2 Cl 2 , washed with distilled water, dried over anhydrous Na 2 SO 4 , and the solvent was removed by rotary evaporation under vacuum to obtain 1,3,5-triethynyl-2,4,6-trimethylbenzene.

[0118] (2) Preparation of large-area two-dimensional polyyne carbon material film The obtained 1,3,5-triethynyl-2,4,6-trimethylbenzene was diluted with pyridine to obtain a precursor solution with a concentration of 0.04 mg / mL. Then, the precursor solution was placed in a reaction cell, heated to 60 °C, and the copper foil was slowly pulled from the left end to the right end of the reaction cell within 1 h (the active surface area was 1000 cm 2 ), and the moving speed was 1 cm / min for a deposition polymerization reaction. After the reaction was completed, the copper foil was washed successively with acetone and N-methylpyrrolidone, and a pale yellow film with a thickness of 300 nm appeared on the copper foil, which was a two-dimensional polyyne carbon material film with the structure shown in Formula II-1.

[0119] Formula II-1.

[0120] The reaction equation of Example 3 is as follows: .

[0121] Example 4 (1) Preparation of reaction monomers 0.117 g (1 mmol) of boron trichloride, 50 mL of tetrahydrofuran, and 1 mL (2.4 mmol) of 2.4 M n-butyllithium were mixed and stirred at -80 °C under a nitrogen atmosphere for 2 h. Then 2.12 mL (15 mmol) of (CH 3 ) 3 SiC≡CH was added, and the substitution reaction was continued with stirring for 2 h.

[0122] After evaporating the solvent from the system obtained from the substitution reaction, the residue was purified by column chromatography and eluted with a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1, (V 正己烷 :V 二氯甲烷 = 5:1), until no product was detected by thin-layer chromatography plate, and a yellow solid substance, tris[(trimethylsilyl)ethynyl]boron, was obtained.

[0123] To a 25 mL THF solution containing 0.12 mg (0.3 mmol) of tris[(trimethylsilyl)ethynyl]boron, 1.2 mL of a 1 mol / L THF solution of TBAF was added, and the resulting mixture was stirred at 0 °C for the deprotection reaction for 30 min. After diluting the deprotection reaction system with ethyl acetate, it was washed with distilled water, and dried over anhydrous Na 2 SO 4 , and the solvent was removed by rotary evaporation under vacuum to obtain a white powdery solid, namely triethynylboron.

[0124] (2) Preparation of large-area two-dimensional alkynyl-rich carbon material film The obtained triethynylboron was diluted with 40 mL of pyridine to obtain a precursor solution with a concentration of 0.1 mg / mL. Then the precursor solution was placed in a reaction cell, heated to 60 °C, and a copper foil was slowly pulled from the left end to the right end of the reaction cell within 1 h (the active surface area was 1000 cm 2 ), and the moving speed was 1 cm / min for the deposition polymerization reaction. After the reaction was completed, the copper foil was washed successively with acetone and N-methylpyrrolidone, and a pale yellow film (thickness 400 nm) appeared on the copper foil, namely the two-dimensional alkynyl-rich carbon material film with the structure of Formula IV-1.

[0125] Formula IV-1.

[0126] The reaction equation of Example 4 is as follows:[[]] .

[0127] Example 5 (1) Preparation of reaction monomers 0.167 g (1 mmol) of silicon tetrachloride, 50 mL of tetrahydrofuran, and 2 mL (4.8 mmol) of 2.4 M n-butyllithium were mixed and stirred at -80 °C under a nitrogen atmosphere for 2 h. Then, 2.83 mL (20 mmol) of (CH 3 ) 3 SiC≡CH was added, and the substitution reaction was continued with stirring for 2 h.

[0128] After evaporating the solvent from the system obtained from the substitution reaction, the residue was purified by column chromatography and eluted with a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1 (V 正己烷 :V 二氯甲烷 = 5:1) until no product was detected on the thin-layer chromatography plate, and a yellow solid substance, namely tetrakis[(trimethylsilyl)ethynyl]silane, was obtained.

[0129] To a 25 mL THF solution containing 12 mg (0.3 mmol) of tetrakis[(trimethylsilyl)ethynyl]silane, 1.6 mL of a 1 mol / L THF solution of TBAF was added, and the resulting mixture was stirred at 0 °C for the deprotection reaction for 30 min. After diluting the deprotection reaction system with ethyl acetate, it was washed with distilled water, dried over anhydrous Na 2 SO 4 and the solvent was removed by rotary evaporation under vacuum to obtain a white powdery solid, namely triethynylsilane.

[0130] (2) Preparation of large-area two-dimensional alkyne-rich carbon material thin film The obtained triethynylsilane was diluted with pyridine to obtain a precursor solution with a concentration of 0.08 mg / mL. Then, the precursor solution was placed in a reaction cell, heated to 60 °C, and the copper foil was slowly pulled from the left end to the right end of the reaction cell within 1 h (the active surface area was 50 cm 2 ), and the moving speed was 1 cm / min for the deposition polymerization reaction. After the reaction was completed, the copper foil was washed successively with acetone and N-methylpyrrolidone, and a pale yellow thin film with a thickness of 400 nm appeared on the copper foil, namely the two-dimensional alkyne-rich carbon material thin film of formula V-1: Formula V-1.

[0131] The reaction equation of Example 5 is shown below.

[0132] .

[0133] Example 6 (1) Preparation of reaction monomer 1.719 g (4 mmol) of 2,3,5,6 - tetrabromo - 1,4 - difluorobenzene, 5.64 mL (40 mmol) of (CH 3 ) 3 SiC≡CH, 0.2808 g (0.40 mmol) of PdCl 2 (PPh 3 ) 2 , 0.152 g (0.8 mmol) of CuI and 0.2096 g (0.8 mmol) of Ph 3 P were successively added to 80 mL of triethanolamine. The resulting mixture was stirred in a three - necked flask at 80 °C under a nitrogen atmosphere for a substitution reaction for 5 days.

[0134] Then, the solvent of the substitution reaction system was evaporated, and the residue was purified by column chromatography, eluted with a mixed solution of n - hexane and dichloromethane with a volume ratio of 5:1, (V 正己烷 :V 二氯甲烷 = 5:1), until no product was detected on the thin - layer chromatography plate, and white powdery 2,3,5,6 - tetra[(trimethylsilyl)ethynyl] - 1,4 - difluorobenzene was obtained.

[0135] To a 15 mL THF solution containing 56 mg (0.133 mmol) of 2,3,5,6 - tetra[(trimethylsilyl)ethynyl] - 1,4 - difluorobenzene, 0.4 mL of a 1 mol / L THF solution of TBAF was added. The resulting mixture was stirred at 6 °C for a deprotection reaction for 30 min. After the deprotection reaction system was diluted with CH 2 Cl 2 , it was washed with distilled water, dried with anhydrous Na 2 SO 4 , and the solvent was removed by rotary evaporation under vacuum to obtain 2,3,5,6 - tetraethynyl - 1,4 - difluorobenzene.

[0136] (2) Preparation of large - area two - dimensional polyyne - rich carbon material film The obtained 2,3,5,6 - tetraethynyl - 1,4 - difluorobenzene was diluted with pyridine to obtain a precursor solution with a concentration of 0.05 mg / mL. Then, the diluted solution was placed in a reaction cell, heated to 60 °C, and a copper foil was slowly pulled from the left end to the right end of the reaction cell within 1 h (the active surface area was 50 cm 2 ), with a moving speed of 1 cm / min, for a deposition polymerization reaction. After the reaction was completed, the copper foil was washed successively with acetone and N - methylpyrrolidone, and a pale yellow film with a thickness of 300 nm appeared on the copper foil, which was a two - dimensional polyyne - rich carbon material film with the structure shown in Formula VII - 1: Replace pyridine with pyridine + dimethyl sulfoxide, where the volume ratio of pyridine to dimethyl sulfoxide is 1:5, and a two-dimensional polyacetylene carbon material film with the structure shown in Formula VI-1 appears on the copper foil.

[0137] Formula VI-1; Formula VII-1.

[0138] The reaction equation of Example 6 is as shown below.

[0139] .

[0140] Example 7 (1) Preparation of reaction monomers Add 1.259 g (4 mmol) of 1,3,5-tribromobenzene, 5.64 mL (40 mmol) of (CH 3 ) 3 SiC≡CH, 0.2808 g (0.40 mmol) of PdCl 2 (PPh 3 ) 2 , 0.152 g (0.8 mmol) of CuI and 0.2096 g (0.8 mmol) of Ph 3 P to 80 mL of triethanolamine in turn. The resulting mixture is stirred in a three-necked flask at 80 °C under a nitrogen atmosphere for a substitution reaction for 5 days.

[0141] Then, evaporate the solvent from the substitution reaction system, and purify the residue by column chromatography, eluting with a mixed solution of n-hexane and dichloromethane with a volume ratio of 5:1, (V 正己烷 : V 二氯甲烷 = 5:1), until no product can be detected by thin-layer chromatography plate to obtain white powdery 1,3,5-tris[(trimethylsilyl)ethynyl]benzene.

[0142] Add 0.4 mL of a THF solution of TBAF with a concentration of 1 mol / L to a 15 mL THF solution containing 56 mg (0.133 mmol) of 1,3,5-tris[(trimethylsilyl)ethynyl]benzene, and stir the resulting mixture at 6 °C (deprotection) for 30 min. After the deprotection reaction system is diluted with CH 2 Cl 2 , wash it with distilled water, dry it with anhydrous Na 2 SO 4 , and remove the solvent by vacuum rotary evaporation to obtain 1,3,5-triethynylbenzene.

[0143] (2) Preparation of large-area two-dimensional polyacetylene carbon material film Dilute the obtained 1,3,5-triethynylbenzene with 250 mL of pyridine, then place the diluted solution in a reaction cell. Next, add 1,3,5-tribromobenzene to the reaction cell. The concentrations of 1,3,5-triethynylbenzene and 1,3,5-tribromobenzene are 0.12 mg / mL and 0.1 mg / mL, respectively. Heat the mixture to 60 °C, and then add 250 mL of water and 1.56 g of palladium acetate to the reaction cell. Slowly pull the copper foil from the cleaning cell and the left end of the reaction cell to the right end within 1 h (the active surface area is 1000 cm 2 ), with a moving speed of 1 cm / min, to carry out the deposition polymerization reaction. After the reaction is completed, wash the copper foil with acetone and N-methylpyrrolidone in sequence. A pale yellow film appears on the copper foil, with a thickness of 300 nm, which is the two-dimensional alkyne-rich carbon material film with the structure of Formula IX-1.

[0144] Formula IX-1.

[0145] The reaction equation of Example 7 is as follows.

[0146] .

[0147] Structure Characterization Figure 2 is the XPS survey spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1, Figure 2 indicating that the two-dimensional alkyne-rich carbon material is composed of carbon elements.

[0148] Figure 3 is the C-XPS spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1, Figure 3 indicating that the two-dimensional alkyne-rich carbon material is composed of two types of carbon atoms, sp-C and sp 2 -C.

[0149] Figure 4 is the infrared spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1, Figure 4 indicating that the two-dimensional alkyne-rich carbon material contains two functional groups, benzene rings and alkyne bonds.

[0150] Figure 5 is the Raman spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1, Figure 5 indicating that the molecular structure of this material contains aromatic rings and carbon-carbon triple bonds.

[0151] Figure 6 is the high-resolution transmission electron microscope image of the two-dimensional alkyne-rich carbon material obtained in Example 1, Figure 6 indicating that the two-dimensional alkyne-rich carbon material prepared by this method has high crystallinity.

[0152] Figure 7Scanning electron microscope images of the two-dimensional carbon-rich alkyne materials obtained by reacting for 2 min, 10 min, 30 min, and 1 h in a pyridine / acetone mixed solution in Example 2 on a copper foil. Figure 7 It shows that the two-dimensional carbon-rich alkyne materials can grow successfully on the copper foil.

[0153] Figure 8 Physical images of the two-dimensional carbon-rich alkyne materials obtained by reacting for 2 min, 10 min, 30 min, and 1 h in a pyridine / acetone mixed solution in Example 2 on a copper foil. Figure 8 It shows that the growth of the two-dimensional carbon-rich alkyne materials is manifested by the deepening of the color of the copper foil.

[0154] Figure 9 Scanning electron microscope images of the two-dimensional carbon-rich alkyne materials obtained by reacting for 2 min, 10 min, 30 min, and 1 h in a pyridine solution in Example 1 on a copper foil. Figure 9 It shows that in the pyridine solution, the two-dimensional carbon-rich alkyne materials can grow on the copper foil.

[0155] Figure 10 Physical images of the two-dimensional carbon-rich alkyne materials obtained by reacting for 2 min, 10 min, 30 min, and 1 h in a pyridine solution in Example 1 on a copper foil. Figure 10 It shows that in the pyridine solution, a small amount of the grown two-dimensional carbon-rich alkyne materials will not change the color of the copper foil.

[0156] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a large-area two-dimensional alkyne-rich carbon material film, characterized in that: The following steps are involved: The copper substrate moves in a directional manner through a precursor solution to perform a deposition polymerization reaction, thereby obtaining a two-dimensional acetylene-rich carbon material film on the surface of the copper substrate; The moving speed of the copper substrate is 0.01-10 cm / min; The components of the precursor solution include monomers for preparing two-dimensional alkyne-rich carbon materials and a polar organic solvent.

2. The preparation method according to claim 1, wherein the two-dimensional alkyne-rich carbon material has one or more structures shown in Formula I to Formula IX; Formula I; Formula II; Formula III; Formula IV; Formula V; Formula VI; Formula VII; Formula VIII; Formula IX; in, In formula II, X, Y, and Z are independently H, F, Cl, CH3, OCH3, CF3, CN, NH2, NO2, or COOCH3 groups; In formula III, W, X, Y, and Z are independently H, F, Cl, OCH3, CN, CF3, NH2, NO2, or COOCH3 groups; In formula IV, X is B or P; In formula V, X is C, Si, Ge, Sn, Pb, Ti, Zr, or ; In formula VI and formula VII, X and Y are independently H, F, Cl, OCH3, CF3, CN, NH2, NO2 or COOCH3 groups; In formula VIII, X is C or N, and Y is H, F, Cl, CH3, OCH3, CF3, CN, NH2, NO2 or COOCH3 group; In formula IX, W is C or N, and X, Y, and Z are independently H, F, Cl, OCH3, CF3, CN, NH2, NO2, or COOCH3 groups.

3. The preparation method according to claim 2, characterized in that: The monomer corresponding to the two-dimensional alkyne-rich carbon material with the structure shown in Formula I has the structure shown in Formula a; The monomer corresponding to the two-dimensional alkyne-rich carbon material with the structure shown in formula II has the structure shown in formula b; The monomer corresponding to the two-dimensional alkyne-rich carbon material with the structure shown in formula III has the structure shown in formula C; The monomer corresponding to the two-dimensional alkyne-rich carbon material with the structure shown in Formula IV has the structure shown in Formula d; The monomer corresponding to the two-dimensional alkyne-rich carbon material with the structure shown in formula V has the structure shown in formula e; The monomer corresponding to the two-dimensional alkyne-rich carbon material with the structure shown in Formula VI and Formula VII has the structure shown in Formula f; The monomer corresponding to the two-dimensional alkyne-rich carbon material of structure VIII has a structure shown in formula g; The monomers corresponding to the two-dimensional alkyne-rich carbon material of the structure shown in formula IX include a compound having a structure shown in formula h and tribromobenzene; Formula a; Formula b; Formula c; Formula d; Formula e; Formula f; Formula g; Formula h.

4. The preparation method according to claim 1 or 3, characterized in that: The concentration of the monomer in the precursor solution is 0.0001-5 mg / mL.

5. The preparation method according to claim 1, characterized in that: The precursor solution also includes a catalyst, and the mass concentration of the catalyst in the precursor solution is 0-5%.

6. The preparation method according to claim 1, characterized in that: The polar organic solvent includes essential components and non-essential components, wherein the essential component includes pyridine; the non-essential components include one or more of triethylamine, diethylamine, tetrahydrofuran, dichloromethane, chloroform, acetone, N, N-dimethylformamide, N-methylpyrrolidone, toluene, p-xylene, dimethyl sulfoxide, acetonitrile and N, N, N, N-tetramethylethylenediamine; The volume ratio of the essential ingredients to the non-essential ingredients is 1:0-20.

7. The preparation method according to claim 1, characterized in that: The thickness of the copper substrate is 10-100 μm; The temperature of the deposition polymerization reaction is 20-120°C; The thickness of the two-dimensional acetylene-rich carbon material film is 100 nm~200 μm.

8. The preparation method according to claim 1, characterized in that: The precursor solution is a flowing liquid, and the flow rate of the precursor solution is 1-20 mL / min.

9. A device for preparing a large-area two-dimensional acetylene-rich carbon material film, characterized in that: It includes a winder, a front cleaning tank, a reaction tank and a rear cleaning tank; The front cleaning tank, the reaction tank and the rear cleaning tank are connected in sequence; The winding machine comprises an unwinding part and a winding part, wherein the unwinding part is arranged at the inlet end of the front cleaning tank, and the winding part is arranged at the outlet end of the rear cleaning tank. The winding machine drives the copper substrate to pass through the front cleaning tank, the reaction tank and the rear cleaning tank in sequence.

10. The device according to claim 9, characterized in that An ultraviolet-visible spectrophotometer is also arranged above the reaction pool.

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