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

Abstract

The application 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. The application controls the directional movement of a copper substrate in a precursor solution, thereby controlling the residence time of the copper substrate per unit area in the precursor solution, so as to realize the growth of the two-dimensional acetylene-rich carbon material on the copper substrate per unit area with a fixed reaction time, and further obtain the two-dimensional acetylene-rich carbon material with uniform thickness and high crystallinity. In the deposition polymerization reaction process, the copper substrate in the precursor solution is constantly updated, so that the large-area and continuous preparation of the two-dimensional acetylene-rich carbon material can be realized, and the two-dimensional acetylene-rich carbon material is suitable for industrialization and batch production. Further, the application uses ultraviolet-visible spectroscopy to monitor the concentration of the precursor solution in real time, and through the constant flow and constant update of the precursor solution, the stability of the precursor concentration in the reaction process is ensured to be unchanged, so that the two-dimensional acetylene-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 in particular to a method and device for preparing a large-area two-dimensional acetylene-rich carbon material film. Background Art

[0002] Two-dimensional alkyne-rich carbon materials have broad application prospects in the fields of catalysis, energy storage, electronic devices and adsorption separation due to their unique structure and excellent performance. The copper template method for synthesizing two-dimensional alkyne-rich carbon materials can achieve gram-level preparation, but there are several problems: First, this method is an intermittent preparation. If large-scale preparation is required, the pre- and post-processing processes are relatively cumbersome, and errors are prone to occur during the preparation process. Second, the film thickness is uncontrollable. Depending on the placement of the copper sheet in the reaction vessel, there may be some areas where no two-dimensional alkyne-rich carbon material grows. Third, during the growth process of the two-dimensional alkyne-rich carbon material, a template replacement phenomenon occurs. The early two-dimensional alkyne-rich carbon material grows on a copper substrate. After the copper sheet is completely covered by the two-dimensional alkyne-rich carbon material, it continues to grow using the two-dimensional alkyne-rich carbon material as a template. This template replacement will cause a large number of defects in the two-dimensional alkyne-rich carbon material, thereby reducing the crystallinity of the two-dimensional alkyne-rich carbon material.

[0003] Currently, methods such as interfacial deposition, chemical vapor deposition, and van der Waals epitaxy have been developed to prepare two-dimensional (2D) alkyne-rich carbon materials. These methods significantly improve the crystallinity of these materials. Furthermore, they enable controllable film thickness, enabling the preparation of small-layer 2D alkyne-rich carbon materials. However, these methods can only achieve milligram or even microgram yields, making them unsuitable for large-scale production. Summary of the Invention

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

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a large-area two-dimensional alkyne-rich carbon material film, comprising the following steps:

[0007] The copper substrate moves in a directionally moving manner through the precursor solution to undergo a deposition polymerization reaction, thereby obtaining a two-dimensional alkyne-rich carbon material film on the surface of the copper substrate;

[0008] The movement rate of the copper substrate is 0.01-10 cm / min;

[0009] The components of the precursor solution include monomers for preparing two-dimensional alkyne-rich carbon materials and a polar organic solvent.

[0010] Preferably, the two-dimensional alkyne-rich carbon material has one or more structures shown in Formula I to Formula IX;

[0011] Formula I; Formula II; Formula III;

[0012] Formula IV; Formula V; Formula VI;

[0013] Formula VII; Formula VIII;

[0014] Formula IX;

[0015] Wherein, in Formula II, X, Y, and Z are independently H, F, Cl, CH3, OCH3, CF3, CN, NH2, NO2, or COOCH3 groups;

[0016] In formula III, W, X, Y, and Z are independently H, F, Cl, OCH3, CN, CF3, NH2, NO2, or COOCH3 groups;

[0017] In formula IV, X is B or P;

[0018] In formula V, X is C, Si, Ge, Sn, Pb, Ti, Zr, or ;

[0019] In formula VI and formula VII, X and Y are independently H, F, Cl, OCH3, CF3, CN, NH2, NO2 or COOCH3 groups;

[0020] In formula VIII, X is C or N, and Y is H, F, Cl, CH3, OCH3, CF3, CN, NH2, NO2 or COOCH3 group;

[0021] 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.

[0022] Preferably, the monomer corresponding to the two-dimensional alkyne-rich carbon material having the structure shown in Formula I has the structure shown in Formula a;

[0023] 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;

[0024] 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;

[0025] 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;

[0026] 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;

[0027] The monomer corresponding to the two-dimensional alkyne-rich carbon material of the structure represented by Formula VI or Formula VII has the structure represented by Formula f;

[0028] The monomer corresponding to the two-dimensional alkyne-rich carbon material of structure VIII has the structure shown in formula g;

[0029] The monomer corresponding to the two-dimensional alkyne-rich carbon material of the structure shown in IX includes a compound having the structure shown in formula h and tribromobenzene;

[0030] Formula a; Formula b; Formula c; Formula d;

[0031] Formula e; Formula f; Formula g; Formula h.

[0032] Preferably, the concentration of the monomer in the precursor solution is 0.0001-5 mg / mL.

[0033] Preferably, the precursor solution further comprises a catalyst, and the mass concentration of the catalyst in the precursor solution is 0-5%.

[0034] 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, chloroform, acetone, N, N-dimethylformamide, N-methylpyrrolidone, toluene, p-xylene, dimethyl sulfoxide, acetonitrile and N, N, N, N-tetramethylethylenediamine;

[0035] The volume ratio of the essential ingredients to the non-essential ingredients is 1:0-20.

[0036] Preferably, the thickness of the copper substrate is 10-100 μm;

[0037] The temperature of the deposition polymerization reaction is 20-120°C;

[0038] The thickness of the two-dimensional acetylene-rich carbon material film is 100 nm~200 μm.

[0039] Preferably, the precursor solution is a flowing liquid, and the flow rate of the precursor solution is 1-20 mL / min.

[0040] The present invention provides a large-area two-dimensional acetylene-rich carbon material film preparation device, comprising a winder, a front cleaning tank, a reaction tank and a rear cleaning tank;

[0041] The front cleaning tank, reaction tank and rear cleaning tank are connected in sequence;

[0042] The winding machine includes an unwinding part and a winding part. 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.

[0043] Preferably, an ultraviolet-visible spectrophotometer is further provided above the reaction pool.

[0044] The present invention provides a method for preparing a large-area two-dimensional, alkyne-rich carbon material film, comprising the following steps: passing a directionally moving copper substrate through a precursor solution to undergo a deposition polymerization reaction, thereby obtaining a two-dimensional, alkyne-rich carbon material film on the surface of the copper substrate; the copper substrate moving at a rate of 0.01 to 10 cm / min; and the precursor solution comprising monomers for preparing the two-dimensional, alkyne-rich carbon material and a polar organic solvent. By controlling the directionally moving copper substrate within the precursor solution, and thereby controlling the residence time per unit area of ​​the copper substrate in the precursor solution, the present invention enables the two-dimensional, alkyne-rich carbon material to grow on the copper substrate per unit area with a fixed reaction time, thereby obtaining a two-dimensional, alkyne-rich carbon material with uniform thickness and high crystallinity. During the deposition polymerization reaction, the copper substrate in the precursor solution is continuously renewed, thereby enabling large-scale, continuous preparation of the two-dimensional, alkyne-rich carbon material, suitable for industrialized, mass production of two-dimensional, alkyne-rich carbon materials.

[0045] Furthermore, the present invention utilizes ultraviolet-visible spectroscopy to monitor the concentration of the precursor solution in real time, and through the continuous flow and renewal of the precursor solution, ensures the stability of the precursor concentration during the reaction process, thereby achieving the growth of a two-dimensional acetylene-rich carbon material film at a certain reaction rate.

[0046] Furthermore, the present invention controls the growth thickness of the two-dimensional acetylene-rich carbon material film by controlling the precursor concentration and the reaction temperature.

[0047] The present invention provides a device for preparing large-area two-dimensional acetylene-rich carbon material films, comprising 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 sequentially connected; the winder includes a unwinding portion and a rewinding portion, the unwinding portion being disposed at the inlet end of the front-cleaning tank and the rewinding portion being disposed at the outlet end of the rear-cleaning tank; the winder drives a copper substrate through the front-cleaning tank, the reaction tank, and the rear-cleaning tank in sequence. In the present invention, the copper substrate is fixed to the winder, and the winder drives the copper substrate to move, thereby achieving large-area, continuous preparation of two-dimensional acetylene-rich carbon material films. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 Schematic diagram of the structure of the preparation device for large-area two-dimensional alkyne-rich carbon material films;

[0049] Figure 2 This is the XPS total spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1;

[0050] Figure 3 This is the C-XPS spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1;

[0051] Figure 4 This is the infrared spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1;

[0052] Figure 5 This is the Raman spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1;

[0053] Figure 6 This is a high-resolution transmission electron micrograph of the two-dimensional alkyne-rich carbon material obtained in Example 1;

[0054] Figure 7 The scanning electron microscope images of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in a pyridine / acetone mixed solution for 2 min, 10 min, 30 min, and 1 h in Example 2 are shown. Figure 7 In the figure, (a) is 2 min, (b) is 10 min, (c) is 30 min, and (d) is 1 h;

[0055] Figure 8 This is a physical picture of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in a pyridine / acetone mixed solution for 2 min, 10 min, 30 min, and 1 h in Example 2. Figure 8 In the figure, (a) is 2 min, (b) is 10 min, (c) is 30 min, and (d) is 1 h;

[0056] Figure 9 The scanning electron microscope images of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in pyridine solution for 2 min, 10 min, 30 min, and 1 h in Example 1 are shown. Figure 9 In the figure, (a) is 2 min, (b) is 10 min, (c) is 30 min, and (d) is 1 h;

[0057] Figure 10 This is a physical picture of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in pyridine solution for 2 min, 10 min, 30 min, and 1 h in Example 1. Figure 10 Among them, (a) is 2 min, (b) is 10 min, (c) is 30 min, and (d) is 1 h. DETAILED DESCRIPTION

[0058] The present invention provides a method for preparing a large-area two-dimensional alkyne-rich carbon material film, comprising the following steps:

[0059] The copper substrate moves in a directionally moving manner through the precursor solution to undergo a deposition polymerization reaction, thereby obtaining a two-dimensional alkyne-rich carbon material film on the surface of the copper substrate;

[0060] The movement rate of the copper substrate is 0.01-10 cm / min;

[0061] The components of the precursor solution include monomers for preparing two-dimensional alkyne-rich carbon materials and a polar organic solvent.

[0062] The present invention passes a directionally moving copper substrate 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. In the present invention, the copper substrate is preferably copper foil, and more preferably commercial copper foil.

[0063] 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 copper substrate is preferably cleaned, and the cleaning agent is preferably one or more of hydrochloric acid, water, and ethanol, and the concentration of the hydrochloric acid is preferably 1 mol / L.

[0064] In the present invention, the movement rate of the copper substrate is 0.01 to 10 cm / min, preferably 0.1 to 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, the residence time of the copper substrate from entering the reaction tank to leaving the reaction tank, measured from the position where the copper substrate begins to contact the precursor solution, is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, more preferably 3 to 6 hours, and specifically can be 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.

[0065] In the present invention, the precursor solution comprises monomers for preparing a two-dimensional alkyne-rich carbon material and a polar organic solvent. The concentration of the monomers in the precursor solution is preferably 0.0001 to 5 mg / mL, more preferably 0.001 to 4 mg / mL, further preferably 0.01 to 3 mg / mL, and even more preferably 0.1 to 1 mg / mL.

[0066] In the present invention, the polar organic solvent preferably includes essential components and non-essential components, and the essential component preferably includes pyridine; the non-essential components preferably 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 components to the non-essential components is preferably 1:0-20, more preferably 1:5-10, specifically 1:0, 1:1, 1:5, 1:8, 1:10, 1:15 or 1:20.

[0067] In the present invention, the precursor solution preferably further includes a catalyst, preferably palladium acetate. In the present invention, the mass concentration of the catalyst in the precursor solution is preferably 0-5%, specifically 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.

[0068] In the present invention, the deposition polymerization reaction is preferably carried out under a protective atmosphere, preferably nitrogen or argon. In the present invention, the deposition polymerization reaction temperature is preferably 20-120°C, more preferably 40-80°C, specifically 20°C, 40°C, 60°C, 80°C, 100°C, or 120°C.

[0069] In the present invention, the deposition polymerization reaction process further includes real-time monitoring of the precursor solution concentration by ultraviolet-visible spectroscopy.

[0070] 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, specifically 5 mL / min, 10 mL / min, 15 mL / min or 20 mL / min.

[0071] In the present invention, after the deposition polymerization reaction, the copper substrate and the two-dimensional acetylene-rich carbon material thin film on the surface of the copper substrate are preferably post-treated. The post-treatment preferably includes washing and drying in sequence. In the present invention, the reagent used for the washing is preferably acetone and / or N-methylpyrrolidone. The present invention has no particular requirements for the drying method, and any drying method well known in the art can be used.

[0072] After obtaining a two-dimensional acetylene-rich carbon material film on the surface of the copper substrate, the present invention preferably peels off the two-dimensional acetylene-rich carbon material film from the surface of the copper substrate. In the present invention, the peeling method preferably includes the following steps:

[0073] The copper substrate containing the two-dimensional alkyne-rich carbon material film is immersed in a hydrochloric acid solution or ammonia water to peel off the two-dimensional alkyne-rich carbon material from the copper substrate.

[0074] In the present invention, the concentration of the hydrochloric acid solution is preferably 1 mol / L hydrochloric acid; the ammonia solution is preferably commercial concentrated ammonia solution. In the present invention, the immersion time is preferably 10 to 600 minutes, more preferably 30 to 240 minutes, and specifically can be 10 minutes, 30 minutes, 60 minutes, 120 minutes, 180 minutes, 240 minutes, 300 minutes, 400 minutes, 500 minutes, or 600 minutes.

[0075] In the present invention, the thickness of the two-dimensional acetylene-rich carbon material film is 100 nm~200 μm, more preferably 500 nm~20 μm, specifically 100 nm, 500 nm, 1 μm, 5 μm, 10 μm, 50 μm, 100 μm, 150 μm or 200 μm.

[0076] In the present invention, the two-dimensional alkyne-rich carbon material preferably has one or more structures shown in Formula I to Formula IX;

[0077] Formula I; Formula II; Formula III;

[0078] Formula IV; Formula V; Formula VI;

[0079] Formula VII; Formula VIII;

[0080] Formula IX;

[0081] Wherein, in Formula II, X, Y, and Z are independently H, F, Cl, CH3, OCH3, CF3, CN, NH2, NO2, or COOCH3 groups, and X, Y, and Z can be the same group at the same time;

[0082] In formula III, W, X, Y, and Z are independently H, F, Cl, OCH3, CN, CF3, NH2, NO2, or COOCH3 groups, and W, X, Y, and Z can be the same group at the same time;

[0083] In formula IV, X is B or P;

[0084] In formula V, X is C, Si, Ge, Sn, Pb, Ti, Zr, (tetraphenylmethane) or (tetraphenylsilane);

[0085] In Formula VI and Formula VII, X and Y are independently H, F, Cl, OCH3, CF3, CN, NH2, NO2 or COOCH3 groups, and X and Y can be the same group at the same time;

[0086] In formula VIII, X is C or N, and Y is H, F, Cl, CH3, OCH3, CF3, CN, NH2, NO2 or COOCH3 group;

[0087] In formula IX, W can be C or N, X, Y, and Z are independently H, F, Cl, OCH3, CF3, CN, NH2, NO2, or COOCH3 groups, and X, Y, and Z can be the same group at the same time.

[0088] In the present invention, in the above structural formula, “ ” indicates the attachment site.

[0089] In the present invention, the source of the monomers for preparing the two-dimensional alkyne-rich carbon material is preferably commercially available or self-prepared. In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material of the structure shown in Formula I has the structure shown in Formula a.

[0090] Formula a.

[0091] In the present invention, the method for preparing the monomer having the structure shown in formula a preferably comprises the following steps:

[0092] The six-bromobenzene, ethynyltrimethylsilane and catalyst are sequentially added into triethylamine, and a substitution reaction is performed under a nitrogen environment to obtain hexakis[(trimethylsilyl)ethynyl]benzene;

[0093] A tetrahydrofuran solution of the hexakis[(trimethylsilyl)ethynyl]benzene and a tetrahydrofuran solution of a deprotection reagent are mixed to perform a deprotection reaction to obtain hexaethynylbenzene, i.e., a monomer having a structure shown in formula a.

[0094] In the present application, the catalyst preferably comprises PdCl2(PPh3)2, CuI and Ph3P; the molar ratio of PdCl2(PPh3)2, CuI and Ph3P in the catalyst is preferably 1:8:8.

[0095] In the present application, the molar ratio of the six-bromobenzene to ethynyltrimethylsilane is preferably 1:4; the ratio of the sum of the molar amounts of the six-bromobenzene and the catalyst is preferably 10:1; and the ratio of the amount of the six-bromobenzene to triethylamine is preferably 10 mmol: 20-80 mL, and more preferably 4 mmol: 50 mL.

[0096] In the present application, the temperature of the substitution reaction is preferably 80°C, and the time is preferably 3-5 days. In the present application, after the substitution reaction, the system obtained by the substitution reaction is preferably sequentially concentrated, purified by column chromatography and desolvated, and the eluent for the column chromatography is preferably a mixture of n-hexane and dichloromethane in a volume ratio of 5:1.

[0097] In the present application, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present application, the molar ratio of the hexakis[(trimethylsilyl)ethynyl]benzene to the deprotection reagent is preferably 0.1-0.15:0.4, and more preferably 0.1-0.12:0.4.

[0098] In the present application, the concentration of the tetrahydrofuran solution of the hexakis[(trimethylsilyl)ethynyl]benzene is preferably 0.008-0.015 mol / L, and more preferably 0.01-0.012 mol / L; and the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L. In the present application, the temperature of the deprotection reaction is preferably 0°C, and the time is preferably 30 min. In the present application, the deprotection reaction is preferably performed under stirring. In the present application, after the deprotection reaction, the system after the deprotection reaction is preferably sequentially diluted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, and vacuum rotary evaporated to remove the solvent to obtain hexaethynylbenzene, i.e., a monomer having a structure shown in formula a.

[0099] In the present application, the monomer corresponding to the two-dimensional rich-alkyne carbon material having a structure shown in formula II has a structure shown in formula b.

[0100] Formula b.

[0101] In the present application, the preparation method of the monomer with the structure shown in Formula b preferably comprises the following steps:

[0102] The tribromo derivative with the structure shown in Formula 1-1, ethynyltrimethylsilane and a catalyst are sequentially added into a polar solvent to perform a substitution reaction under a nitrogen environment to obtain an intermediate with the structure shown in Formula 1-2.

[0103] A tetrahydrofuran solution of the intermediate with the structure shown in Formula 1-2 and a tetrahydrofuran solution of a deprotection reagent are mixed to perform a deprotection reaction to obtain the monomer with the structure shown in Formula b.

[0104] Formula 1-1; Formula 1-2.

[0105] In the present application, the catalyst preferably comprises PdCl2(PPh3)2, CuI and Ph3P; the molar ratio of PdCl2(PPh3)2, CuI and Ph3P in the catalyst is preferably 1:2:2.

[0106] In the present application, the molar ratio of the tribromo derivative with the structure shown in Formula 1-1 to ethynyltrimethylsilane is preferably 1:10; the ratio of the sum of the molar amounts of the tribromo derivative with the structure shown in Formula 1-1 and the catalyst is preferably 2:1; in the present application, the polar solvent is preferably tetrahydrofuran, and the usage ratio of the tribromo derivative with the structure shown in Formula 1-1 to the polar solvent is preferably 4 mmol: 20-80 mL, more preferably 4 mmol: 50 mL.

[0107] In the present application, the temperature of the substitution reaction is preferably 80°C, and the time is preferably 3-5 days. In the present application, after the substitution reaction, the obtained system is preferably sequentially concentrated, purified by column chromatography and desolvated, and the eluent of the column chromatography purification is preferably a mixture of n-hexane and dichloromethane in a volume ratio of 5:1.

[0108] In the present application, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present application, the molar ratio of the intermediate with 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.

[0109] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate having the structure shown in Formula 1-2 is preferably 0.008~0.015 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. In the present invention, after the deprotection reaction, it is preferred to further dilute the system after the deprotection reaction with dichloromethane, wash it with distilled water, dry it with anhydrous sodium sulfate, and remove the solvent by vacuum rotary evaporation to obtain a monomer having the structure shown in Formula b.

[0110] In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material having the structure shown in Formula III has the structure shown in Formula C.

[0111] Formula c.

[0112] In the present invention, the method for preparing the monomer having the structure shown in formula C preferably comprises the following steps:

[0113] A compound having a structure shown in Formula 2-1, ethynyltrimethylsilane, and a catalyst are sequentially added to triethylamine, and a substitution reaction is carried out under a nitrogen environment to obtain an intermediate having a structure shown in Formula 2-2;

[0114] A tetrahydrofuran solution of the intermediate having the structure shown in Formula 2-2 and a tetrahydrofuran solution of a deprotection reagent are mixed and deprotection reaction is carried out to obtain a monomer having the structure shown in Formula C.

[0115] Formula 2-1; Formula 2-2.

[0116] In the present invention, the preparation process of the monomer having the structure represented by Formula C is substantially the same as that of the monomer having the structure represented by Formula B, with the only difference being the starting materials. The optional ranges of the amounts of raw materials and reaction conditions in the preparation process of the monomer having the structure represented by Formula C are referenced to the preparation process of the monomer having the structure represented by Formula B, and are not further described here.

[0117] In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material having the structure shown in Formula IV has the structure shown in Formula d.

[0118] Formula d.

[0119] In the present invention, the method for preparing the monomer having the structure shown in formula d preferably comprises the following steps:

[0120] The chloride with the structure shown in formula 3-1, n-butyl lithium and ethynyltrimethylsilane are sequentially added into tetrahydrofuran to perform a substitution reaction under a nitrogen atmosphere to obtain an intermediate with the structure shown in formula 3-2;

[0121] Formula 3-1; Formula 3-2;

[0122] A tetrahydrofuran solution of the intermediate with the structure shown in formula 3-2 and a tetrahydrofuran solution of a deprotection reagent are mixed to perform a deprotection reaction to obtain a monomer with the structure shown in formula d.

[0123] In the present application, the chloride with the structure shown in formula 3-1 and the ethynyltrimethylsilane preferably have a molar ratio of 1:5-15; the chloride with the structure shown in formula 3-1 and the n-butyl lithium preferably have a molar ratio of 1:2.4-3; and the chloride with the structure shown in formula 3-1 and the tetrahydrofuran preferably have a ratio of 1-3 mmol: 20-100 mL, more preferably 2 mmol: 50 mL.

[0124] In the present application, the temperature of the substitution reaction is preferably -80 ℃, and the time is preferably 2-4 h. In the present application, after the substitution reaction, the system obtained by the substitution reaction is preferably sequentially concentrated, purified by column chromatography and desolvated, and the eluent of the column chromatography is preferably a mixture of n-hexane and dichloromethane in a volume ratio of 5-10:1.

[0125] In the present application, the deprotection reagent is preferably tetrabutylammonium fluoride. In the present application, the intermediate with the structure shown in formula 3-2 and the deprotection reagent preferably have a molar ratio of 1:1-1:8, more preferably 1:4.

[0126] In the present application, the concentration of the tetrahydrofuran solution of the intermediate with the structure shown in formula 3-2 is preferably 8-15 mmol / L, more preferably 10-12 mmol / L; and the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L.

[0127] In the present application, the temperature of the deprotection reaction is preferably 0 ℃, and the time is preferably 30 min. In the present application, the deprotection reaction is preferably performed under stirring. In the present application, after the deprotection reaction, the system after the deprotection reaction is preferably sequentially diluted with distilled water, washed with distilled water, dried with anhydrous sodium sulfate, and vacuum distilled to remove the solvent to obtain a monomer with the structure shown in formula d.

[0128] In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material having the structure shown in Formula V has the structure shown in Formula e;

[0129] Formula e.

[0130] In the present invention, the method for preparing the monomer having the structure shown in formula e preferably comprises the following steps:

[0131] Chloride having the structure shown in Formula 4-1, n-butyl lithium, and ethynyltrimethylsilane are sequentially added to tetrahydrofuran, and a substitution reaction is carried out under a nitrogen atmosphere to obtain an intermediate having the structure shown in Formula 4-2;

[0132] Formula 4-1; Formula 4-2;

[0133] A tetrahydrofuran solution of the intermediate having the structure shown in Formula 4-2 and a tetrahydrofuran solution of a deprotection reagent are mixed and deprotection reaction is carried out to obtain a monomer having the structure shown in Formula e.

[0134] In the present invention, the molar ratio of the chloride having the structure represented by Formula 4-1 to ethynyltrimethylsilane is preferably 1:5~20; the sum of the molar amounts of the chloride having the structure represented by Formula 4-1 and n-butyllithium is preferably 1:3~4.8; the amount ratio of the chloride having the structure represented by Formula 4-1 to tetrahydrofuran is preferably 1~3mmol:20~100mL, more preferably 2mmol:50mL.

[0135] In the present invention, the temperature of the substitution reaction is preferably -80°C, and the time is preferably 2 to 4 hours. In the present invention, after the substitution reaction, the system obtained by the substitution reaction is preferably concentrated, purified by column chromatography, and desolvated in sequence. The eluent for the column chromatography purification is preferably a mixture of n-hexane and dichloromethane in a volume ratio of 5 to 10:1.

[0136] 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.

[0137] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate having the structure shown in Formula 4-2 is preferably 8~15mmol / L, more preferably 10~12mmol / L; the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1mol / L.

[0138] In the present invention, the temperature of the deprotection reaction is preferably 0°C, and the time is preferably 30 minutes. In the present invention, the deprotection reaction is preferably carried out under stirring. In the present invention, after the deprotection reaction, the system after the deprotection reaction is preferably diluted with CH2Cl2, washed with distilled water, dried with anhydrous Na2SO4, and vacuum rotary evaporation to remove the solvent to obtain a monomer having the structure shown in Formula e.

[0139] In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material having the structure shown in Formula VI or Formula VII has the structure shown in Formula f;

[0140] Formula f.

[0141] In the present invention, the method for preparing the monomer having the structure shown in formula f preferably comprises the following steps:

[0142] A tetrabromo derivative having a structure shown in Formula 5-1, ethynyltrimethylsilane, and a catalyst are sequentially added to triethylamine, and a substitution reaction is carried out under a nitrogen environment to obtain an intermediate having a structure shown in Formula 5-2;

[0143] Formula 5-1; Formula 5-2;

[0144] A tetrahydrofuran solution of the intermediate having the structure shown in Formula 5-2 and a tetrahydrofuran solution of a deprotection reagent are mixed and deprotection reaction is carried out to obtain a monomer having the structure shown in Formula f.

[0145] In the present invention, the catalyst preferably comprises PdCl2(PPh3)2, CuI and Ph3P; the molar ratio of PdCl2(PPh3)2, CuI and Ph3P in the catalyst is preferably 1:2:2.

[0146] In the present invention, the molar ratio of the tetrabromo derivative having the structure represented by Formula 5-1 and ethynyltrimethylsilane is preferably 1:10; the sum of the molar amounts of the tetrabromo derivative having the structure represented by Formula 5-1 and the catalyst is preferably 2:1; the amount ratio of the tetrabromo derivative having the structure represented by Formula 5-1 and triethylamine is preferably 4 mmol:20~80 mL, more preferably 4 mmol:50 mL.

[0147] 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, the system obtained by the substitution reaction is preferably concentrated, purified by column chromatography, and desolvated in sequence. The eluent for the column chromatography purification is preferably a mixture of n-hexane and dichloromethane in a volume ratio of 5:1.

[0148] In the present invention, the deprotecting agent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure represented by Formula 5-2 to the deprotecting agent is preferably 0.1-0.15:0.4, more preferably 0.1-0.12:0.4.

[0149] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate or the intermediate having the structure shown in Formula 5-2 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.

[0150] In the present invention, the temperature of the deprotection reaction is preferably 0-6°C, and the time is preferably 30 minutes. In the present invention, the deprotection reaction is preferably carried out under stirring. In the present invention, after the deprotection reaction, the system after the deprotection reaction is preferably diluted with dichloromethane, washed with distilled water, dried over anhydrous sodium sulfate, and vacuum rotary evaporation to remove the solvent to obtain a monomer having the structure shown in Formula f.

[0151] In the present invention, when a monomer having a structure shown in formula f is used to prepare a two-dimensional alkyne-rich carbon material having a 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 a monomer having a structure shown in formula f is used to prepare a two-dimensional alkyne-rich carbon material having a 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.

[0152] In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material of structure VIII has a structure shown in formula g;

[0153] Formula g.

[0154] In the present invention, the method for preparing the monomer having the structure shown in formula g preferably comprises the following steps:

[0155] A pentabromo derivative having a structure shown in Formula 6-1, ethynyltrimethylsilane, and a catalyst are sequentially added to triethylamine, and a substitution reaction is carried out under a nitrogen atmosphere to obtain an intermediate having a structure shown in Formula 6-2:

[0156] Formula 6-1; Formula 6-2;

[0157] A tetrahydrofuran solution of the intermediate having the structure represented by Formula 6-2 and a tetrahydrofuran solution of a deprotection reagent are mixed and subjected to a deprotection reaction to obtain a monomer having the structure represented by Formula g.

[0158] In the present invention, the catalyst preferably comprises PdCl2(PPh3)2, CuI and Ph3P; the molar ratio of PdCl2(PPh3)2, CuI and Ph3P in the catalyst is preferably 1:2:2.

[0159] In the present invention, the molar ratio of the pentabromo derivative having the structure represented by Formula 6-1 and ethynyltrimethylsilane is preferably 1:10; the sum of the molar amounts of the pentabromo derivative having the structure represented by Formula 6-1 and the catalyst is preferably 2:1; the amount ratio of the pentabromo derivative having the structure represented by Formula 6-1 and triethylamine is preferably 4 mmol:20~80 mL, more preferably 4 mmol:50 mL.

[0160] 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, the system obtained by the substitution reaction is preferably concentrated, purified by column chromatography, and desolvated in sequence. The eluent for the column chromatography purification is preferably a mixture of n-hexane and dichloromethane in a volume ratio of 5:1.

[0161] In the present invention, the deprotecting agent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure represented by Formula 6-2 to the deprotecting agent is preferably 0.1-0.15:0.4, more preferably 0.1-0.12:0.4.

[0162] In the present invention, the concentration of the tetrahydrofuran solution of the intermediate having the structure represented by 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.

[0163] In the present invention, the temperature of the deprotection reaction is preferably 0°C, and the time is preferably 30 minutes. In the present invention, the deprotection reaction is preferably carried out under stirring. In the present invention, after the deprotection reaction, the system after the deprotection reaction is preferably diluted with dichloromethane, washed with distilled water, dried over anhydrous sodium sulfate, and vacuum rotary evaporation to remove the solvent to obtain a monomer having the structure shown in formula g.

[0164] In the present invention, the monomer corresponding to the two-dimensional alkyne-rich carbon material of the structure shown in IX includes a compound having the structure shown in formula h and tribromobenzene; in the present invention, the molar ratio of the compound having the structure shown in formula h to tribromobenzene is preferably 3:1~1:3, more preferably 1:1.

[0165] Formula h.

[0166] In the present invention, the method for preparing the monomer having the structure shown in formula h preferably comprises the following steps:

[0167] A tribromo derivative having a structure shown in Formula 7-1, ethynyltrimethylsilane, and a catalyst are sequentially added to triethylamine, and a substitution reaction is carried out under a nitrogen atmosphere to obtain an intermediate having a structure shown in Formula 7-2:

[0168] Formula 7-1; Formula 7-2;

[0169] A tetrahydrofuran solution of the intermediate having the structure shown in Formula 7-2 and a tetrahydrofuran solution of a deprotection reagent are mixed and deprotection reaction is carried out to obtain a monomer having the structure shown in Formula g.

[0170] In the present invention, the catalyst preferably comprises PdCl2(PPh3)2, CuI and Ph3P; the molar ratio of PdCl2(PPh3)2, CuI and Ph3P in the catalyst is preferably 1:2:2.

[0171] In the present invention, the molar ratio of the tribromo derivative having the structure shown in Formula 7-1 and ethynyltrimethylsilane is preferably 1:10; the sum of the molar amounts of the tribromo derivative having the structure shown in Formula 7-1 and the catalyst is preferably 2:1; the amount ratio of the tribromo derivative having the structure shown in Formula 7-1 and triethylamine is preferably 4 mmol:20~80 mL, more preferably 4 mmol:50 mL.

[0172] 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, the system obtained by the substitution reaction is preferably concentrated, purified by column chromatography, and desolvated in sequence. The eluent for the column chromatography purification is preferably a mixture of n-hexane and dichloromethane in a volume ratio of 5:1.

[0173] In the present invention, the deprotecting agent is preferably tetrabutylammonium fluoride. In the present invention, the molar ratio of the intermediate having the structure represented by Formula 7-2 to the deprotecting agent is preferably 0.1-0.15:0.4, more preferably 0.1-0.12:0.4.

[0174] In the present application, the concentration of the tetrahydrofuran solution of the intermediate having the structure shown in formula 7-2 is preferably 0.008-0.015 mol / L, and more preferably 0.01-0.012 mol / L; and the concentration of the deprotection reagent in the tetrahydrofuran solution of the deprotection reagent is preferably 1 mol / L.

[0175] In the present application, the temperature of the deprotection reaction is preferably 0-6 ℃, and the time is preferably 30 min. In the present application, the deprotection reaction is preferably carried out under stirring. After the deprotection reaction in the present application, the system after the deprotection reaction is preferably diluted with dichloromethane, washed with distilled water in sequence, dried with anhydrous sodium sulfate, and the solvent is removed by vacuum rotary evaporation to obtain a monomer having the structure shown in formula h.

[0176] The present application provides a device for preparing large-area two-dimensional alkyne-rich carbon material film, comprising a winding machine, a front cleaning pool, a reaction pool and a back cleaning pool.

[0177] The front cleaning pool, the reaction pool and the back cleaning pool are connected in sequence.

[0178] The winding machine comprises an unwinding part and a winding part, the unwinding part is arranged at the inlet end of the front cleaning pool, and the winding part is arranged at the outlet end of the back cleaning pool, the winding machine drives the copper substrate to pass through the front cleaning pool, the reaction pool and the back cleaning pool in sequence.

[0179] In the present application, the front cleaning pool is used to hold the front cleaning reagent, and the front cleaning reagent is preferably one or more of hydrochloric acid, water and ethanol, which is used to clean the copper substrate. In the present application, the concentration of the hydrochloric acid is preferably 1 mol / L. In the present application, the number of front cleaning pools is preferably 3, which respectively holds hydrochloric acid, water and ethanol. In the present application, the width of a single front cleaning pool is preferably 1-50 cm, and more preferably 10-40 cm, and the length is preferably 20-480 cm, and more preferably 100-400 cm.

[0180] In the present application, the reaction pool is used to hold the precursor solution, and the width of the reaction pool is preferably 1-50 cm, and more preferably 10-40 cm, and the length is preferably 20-480 cm, and more preferably 100-400 cm. As a specific embodiment of the present application, the size of the reaction pool is preferably 25x60 cm.

[0181] In the present invention, the post-cleaning tank is used to hold a post-cleaning reagent, which is preferably one or more of ethanol, acetone, and N-methylpyrrolidone. In the present invention, the post-cleaning tank is preferably 1 to 50 cm wide, more preferably 10 to 40 cm long, and preferably 20 to 480 cm long, more preferably 100 to 400 cm long.

[0182] In the present invention, a UV-visible spectrophotometer is preferably provided above the reaction pool.

[0183] In the present invention, the structural diagram of the large-area two-dimensional acetylene-rich carbon material film preparation device is as follows Figure 1 The equipment from left to right includes an unwinder, three cleaning tanks, a reaction tank, a cleaning tank and a winder.

[0184] The copper substrate comes out of the unwinder and enters three cleaning tanks respectively. The three cleaning tanks can be filled with 1 mol / L hydrochloric acid, water, and ethanol to clean the copper substrate. Then the copper substrate enters the reaction tank for reaction, and then enters the post-cleaning tank to clean the obtained product. The post-cleaning tank is filled with one or more of ethanol, acetone and N-methylpyrrolidone. Finally, the reel collects the copper substrate and the product.

[0185] The method and apparatus for preparing a large-area two-dimensional acetylene-rich carbon material film provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0186] In the following examples, the size of the reaction cell is 25×60 cm, and the length of the copper substrate immersed in the precursor solution is 50 cm.

[0187] Example 1

[0188] (1) Preparation of reaction monomers

[0189] 5.515 g (10 mmol) of hexabromobenzene, 11.28 mL (40 mmol) of ethynyltrimethylsilane ((CH3)3SiC≡CH), 0.702 g (0.10 mmol) of PdCl2(PPh3)2, 0.152 g (0.8 mmol) of CuI, and 0.2096 g (0.8 mmol) of Ph3P were added sequentially to 80 mL of triethylamine, and the resulting mixture was stirred in a three-necked flask at 80°C under a nitrogen atmosphere for substitution reaction for 3 days.

[0190] The solvent of the system obtained by the substitution reaction was evaporated, and the residue was purified by column chromatography and eluted with a mixture of n-hexane and dichloromethane in a volume ratio of 5:1 (V 正己烷 :V 二氯甲烷=5:1), eluted to thin layer chromatography plate to detect no product, to obtain white powder of hexa[(trimethylsilyl)ethynyl]benzene.

[0191] To 15 mL solution of hexa[(trimethylsilyl)ethynyl]benzene containing 48.7 mg (0.133 mmoL) in THF, 0.4 mL of tetrabutylammonium fluoride solution with concentration of 1 mol / L in THF was added, the resulting mixture was stirred at 0 ℃, and the deprotection reaction was carried out for 30 min. The deprotection reaction system was diluted with dichloromethane, washed with distilled water, dried with anhydrous sodium sulfate, and the solvent was removed by vacuum evaporation to obtain hexa-ethynylbenzene.

[0192] (2) Preparation of large-area two-dimensional rich-alkyne carbon material film

[0193] The obtained hexa-ethynylbenzene was diluted with pyridine to obtain a precursor solution with a concentration of 0.02 mg / mL, which was added to the reaction cell and heated to 60 ℃. A copper foil was slowly pulled from the left end to the right end of the reaction cell (active surface area of 1000 cm 2 ) within 1 h, and the deposition polymerization reaction was carried out at a moving speed of 1 cm / min. After the reaction was completed, the copper foil was washed with acetone and N-methyl pyrrolidone in turn, and a layer of light yellow film with a thickness of 500 nm, i.e. a two-dimensional rich-alkyne carbon material film with the structure of formula I, appeared on the copper foil.

[0194] The reaction equation of Example 1 is shown below:

[0195] .

[0196] Example 2

[0197] The difference from Example 1 is only that:

[0198] The solvent in the precursor solution in the reaction cell was replaced with a mixed solvent of acetone and pyridine, and the volume ratio of acetone to pyridine was 20:1. The deposition polymerization reaction temperature was changed to 40 ℃.

[0199] After the deposition polymerization reaction was completed, a layer of light yellow film with a thickness of 400 nm, i.e. a two-dimensional rich-alkyne carbon material film with the structure of formula I, appeared on the copper foil.

[0200] Example 3

[0201] (1) Preparation of reaction monomer

[0202] Into 80 mL of tetrahydrofuran, 1.476 g (4 mmol) of 2,4,6-tribromo-1,3,5-trimethylbenzene, 5.64 mL (40 mmol) of (CH3)3SiC≡CH, 0.2808 g (0.40 mmol) of PdCl2(PPh3)2, 0.152 g (0.8 mmol) of CuI and 0.2096 g (0.8 mmol) of Ph3P were sequentially added, and the mixture was stirred in a three-neck flask at 80°C under nitrogen for 5 days to perform the substitution reaction.

[0203] Then, the solvent of the system after the substitution reaction was evaporated, and the residue was purified by column chromatography, eluted with a mixture of n-hexane and dichloromethane (volume ratio 5:1) until no product was detected on a thin layer chromatography plate (V 正己烷 :V 二氯甲烷 =5:1), and 1,3,5-tri[(trimethylsilyl)ethynyl]-2,4,6-trimethylbenzene was obtained in the form of white powder.

[0204] Into 15 mL of a THF solution containing 56 mg (0.133 mmol) of 1,3,5-(trimethylsilyl)ethynyl-2,4,6-trimethylbenzene, 0.4 mL of a THF solution of TBAF with a concentration of 1 mol / L was added, and the mixture was stirred at 6°C for 30 min to perform the deprotection reaction. After the deprotection reaction system was diluted with CH2Cl2, washed with distilled water, dried over anhydrous Na2SO4, and the solvent was removed by vacuum rotary evaporation to obtain 1,3,5-triethynyl-2,4,6-trimethylbenzene.

[0205] (2) Preparation of a large-area two-dimensional rich-ethynyl carbon material film

[0206] 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, and then the precursor solution was placed in a reaction cell and heated to 60°C. A copper foil was slowly pulled from the left end to the right end of the reaction cell (the active surface area was 1000 cm 2 ) within 1 h at a moving speed of 1 cm / min to perform the deposition polymerization reaction. After the reaction was completed, the copper foil was washed with acetone and N-methylpyrrolidone in sequence, and a layer of light yellow film with a thickness of 300 nm appeared on the copper foil, which was a two-dimensional rich-ethynyl carbon material film with the structure shown in formula II-1.

[0207] Formula II-1.

[0208] The reaction equation of Example 3 is shown below:

[0209] .

[0210] Example 4

[0211] (1) Preparation of the reaction monomer

[0212] 0.117 g (1 mmol) of boron trichloride, 50 mL of tetrahydrofuran, 1 mL (2.4 mmol) of 2.4 M n-butyllithium were mixed and stirred at -80 ℃ under nitrogen for 2 h. Then 2.12 mL (15 mmol) of (CH3)3SiC≡CH was added, and the substitution reaction was continued for 2 h.

[0213] After the solvent of the system obtained by the substitution reaction was evaporated, the residue was purified by column chromatography, eluted with a mixture of n-hexane and dichloromethane (volume ratio 5:1) (V 正己烷 :V 二氯甲烷 =5:1), until no product was detected on the thin layer chromatography plate, to obtain a yellow solid, i.e. tris[ (trimethylsilyl) ethynyl] boron.

[0214] To a 25 mL THF solution containing 0.12 mg (0.3 mmol) of tris[ (trimethylsilyl) ethynyl] boron, 1.2 mL of 1 mol / L TBAF THF solution was added, and the resulting mixture was stirred at 0 ℃ for deprotection reaction for 30 min. The deprotection reaction system was diluted with ethyl acetate, washed with distilled water, dried with anhydrous Na2SO4, and the solvent was removed by vacuum evaporation to obtain a white powdery solid, i.e. triethynyl boron.

[0215] (2) Preparation of large-area two-dimensional rich-alkyne carbon material film

[0216] The obtained triethynyl boron was diluted with 40 mL of pyridine to obtain a precursor solution with a concentration of 0.1 mg / mL, and then the precursor solution was placed in a reaction tank and heated to 60 ℃. The copper foil was slowly pulled from the left end to the right end of the reaction tank (the active surface area was 1000 cm 2 ) within 1 h at a moving speed of 1 cm / min to perform deposition polymerization reaction. After the reaction was completed, the copper foil was washed with acetone and N-methyl pyrrolidone in sequence, and a layer of light yellow film (thickness 400 nm) appeared on the copper foil, i.e. two-dimensional rich-alkyne carbon material film with the structure of formula IV-1.

[0217] Formula IV-1.

[0218] The reaction equation of Example 4 is shown as follows:

[0219] .

[0220] Example 5

[0221] (1) Preparation of the reaction monomer

[0222] Mix 0.167 g (1 mmol) of silicon tetrachloride, 50 mL of tetrahydrofuran, and 2 mL (4.8 mmol) of 2.4 M n-butyl lithium under nitrogen at -80 °C and stir for 2 h. Then add 2.83 mL (20 mmol) of (CH3)3SiC≡CH3 and continue stirring for 2 h to carry out the substitution reaction.

[0223] After evaporation of the solvent from the system obtained by the substitution reaction, the residue was purified by column chromatography using a mixture of n-hexane and dichloromethane in a volume ratio of 5:1 as eluent (V 正己烷 :V 二氯甲烷 =5:1), eluted until no product could be detected on the thin layer chromatography plate to obtain a yellow solid substance, namely tetrakis[(trimethylsilyl)ethynyl]silane.

[0224] To a 25 mL THF solution containing 12 mg (0.3 mmol) of tetrakis(trimethylsilyl)ethynyl]silane was added 1.6 mL of a 1 mol / L TBAF solution in THF. The resulting mixture was stirred at 0°C for 30 minutes for deprotection. The deprotection reaction system was diluted with ethyl acetate, washed with distilled water, dried over anhydrous Na₂SO₄, and the solvent removed by vacuum rotary evaporation to obtain a white powdery solid, triethynylsilane.

[0225] (2) Preparation of large-area two-dimensional alkyne-rich carbon material films

[0226] The obtained triethynyl silicon was diluted with pyridine to obtain a precursor solution with a concentration of 0.08 mg / mL. The precursor solution was then placed in a reaction cell and heated to 60°C. 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 ), moving at a speed of 1 cm / min, to carry out deposition polymerization. After the reaction was completed, the copper foil was washed with acetone and then N-methylpyrrolidone. A light yellow film with a thickness of 400 nm appeared on the copper foil, which is the two-dimensional acetylenic carbon material film with structure V-1:

[0227] Formula V-1.

[0228] The reaction formula of Example 5 is shown below.

[0229] .

[0230] Example 6

[0231] (1) Preparation of reaction monomers

[0232] 1.719 g (4 mmol) of 2,3,5,6-tetrabromo-1,4-difluorobenzene, 5.64 mL (40 mmol) of (CH3)3SiC≡CH, 0.2808 g (0.40 mmol) of PdCl2(PPh3)2, 0.152 g (0.8 mmol) of CuI and 0.2096 g (0.8 mmol) of Ph3P were added to 80 mL of triethanolamine in sequence, and the resulting mixture was stirred in a three-necked flask at 80°C under a nitrogen environment for a substitution reaction for 5 days.

[0233] Then, the solvent of the system obtained by the substitution reaction was evaporated, and the residue was purified by column chromatography, eluting with a mixture of n-hexane and dichloromethane in a volume ratio of 5:1. (V 正己烷 :V 二氯甲烷 =5:1) and eluted until no product could be detected on the thin layer chromatography plate to obtain 2,3,5,6-tetrakis[(trimethylsilyl)ethynyl]-1,4-difluorobenzene as a white powder.

[0234] To a 15 mL THF solution containing 56 mg (0.133 mmol) of 2,3,5,6-tetrakis[(trimethylsilyl)ethynyl]-1,4-difluorobenzene, 0.4 mL of a 1 mol / L TBAF solution in THF was added. The resulting mixture was stirred at 6°C for 30 minutes for deprotection. The deprotection reaction system was diluted with CH2Cl2, washed with distilled water, dried over anhydrous Na2SO4, and the solvent removed by vacuum rotary evaporation to yield 2,3,5,6-tetraethynyl-1,4-difluorobenzene.

[0235] (2) Preparation of large-area two-dimensional alkyne-rich carbon material films

[0236] 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. The diluted solution was then placed in a reaction cell and heated to 60 °C. A copper foil was slowly pulled from the left end to the right end of the reaction cell (active surface area 50 cm) within 1 h. 2 ), moving at a speed of 1 cm / min, to carry out deposition polymerization. After the reaction was complete, the copper foil was washed with acetone and then N-methylpyrrolidone. A pale yellow film with a thickness of 300 nm appeared on the copper foil, representing the two-dimensional acetylene-rich carbon material film with the structure shown in Formula VII-1:

[0237] If pyridine is replaced by pyridine + dimethyl sulfoxide, where the volume ratio of pyridine to dimethyl sulfoxide is 1:5, a two-dimensional acetylene-rich carbon material film with the structure shown in Formula VI-1 will appear on the copper foil.

[0238] Formula VI-1; Formula VII-1.

[0239] The reaction equation of Example 6 is shown below.

[0240] .

[0241] Example 7

[0242] (1) Preparation of reaction monomers

[0243] 1.259 g (4 mmol) of 1,3,5-tribromobenzene, 5.64 mL (40 mmol) of (CH3)3SiC≡CH, 0.2808 g (0.40 mmol) of PdCl2(PPh3)2, 0.152 g (0.8 mmol) of CuI and 0.2096 g (0.8 mmol) of Ph3P were added to 80 mL of triethanolamine in sequence, and the resulting mixture was stirred in a three-necked flask at 80°C under a nitrogen environment for a substitution reaction for 5 days.

[0244] Then, the solvent of the system obtained by the substitution reaction was evaporated, and the residue was purified by column chromatography, eluting with a mixture of n-hexane and dichloromethane in a volume ratio of 5:1. (V 正己烷 :V 二氯甲烷 =5:1) and eluted until no product could be detected on the thin layer chromatography plate to obtain 1,3,5-tris[(trimethylsilyl)ethynyl]benzene as a white powder.

[0245] To a 15 mL THF solution containing 56 mg (0.133 mmol) of 1,3,5-tris[(trimethylsilyl)ethynyl]benzene, 0.4 mL of a 1 mol / L TBAF solution in THF was added. The resulting mixture was stirred (deprotection) at 6°C for 30 minutes. The deprotection reaction system was diluted with CH2Cl2, washed with distilled water, dried over anhydrous Na2SO4, and the solvent was removed by vacuum rotary evaporation to yield 1,3,5-triethynylbenzene.

[0246] (2) Preparation of large-area two-dimensional alkyne-rich carbon material films

[0247] The obtained 1,3,5-triethynylbenzene was diluted with 250 mL of pyridine, and then the dilution was placed in the reaction cell. 1,3,5-tribromobenzene was then added to the reaction cell. The concentrations of 1,3,5-triethynylbenzene and 1,3,5-tribromobenzene were 0.12 mg / mL and 0.1 mg / mL, respectively. The temperature was raised to 60 °C, and 250 mL of water and 1.56 g of palladium acetate were added to the reaction cell. Within 1 h, the copper foil was slowly pulled from the left end to the right end of the cleaning cell and the reaction cell (active surface area 1000 cm 2), moving at a speed of 1 cm / min, to carry out deposition polymerization. After the reaction, the copper foil was washed with acetone and then N-methylpyrrolidone. A pale yellow film with a thickness of 300 nm appeared on the copper foil, representing the two-dimensional acetylenic-rich carbon material with the structure of Formula IX-1.

[0248] Formula IX-1.

[0249] The reaction formula of Example 7 is shown below.

[0250] .

[0251] Structural characterization

[0252] Figure 2 This is the XPS spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1. Figure 2 It shows that the two-dimensional alkyne-rich carbon material is composed of carbon elements.

[0253] Figure 3 This is the C-XPS spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1. Figure 3 It shows that the two-dimensional alkyne-rich carbon material is composed of sp-C and sp 2 -C is composed of two carbon atoms.

[0254] Figure 4 This is the infrared spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1. Figure 4 It shows that the two-dimensional alkyne-rich carbon material contains two functional groups: benzene ring and alkyne bond.

[0255] Figure 5 This is the Raman spectrum of the two-dimensional alkyne-rich carbon material obtained in Example 1. Figure 5 This indicates that the molecular structure of this material contains aromatic rings and carbon-carbon triple bonds.

[0256] Figure 6 This is a high-resolution transmission electron micrograph of the two-dimensional alkyne-rich carbon material obtained in Example 1. Figure 6 It shows that the two-dimensional alkyne-rich carbon material prepared by this method has high crystallinity.

[0257] Figure 7 The scanning electron microscope images of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in a pyridine / acetone mixed solution for 2 min, 10 min, 30 min, and 1 h in Example 2 are shown. Figure 7 It shows that two-dimensional alkyne-rich carbon materials can be successfully grown on copper foil.

[0258] Figure 8 This is a physical picture of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in a pyridine / acetone mixed solution for 2 min, 10 min, 30 min, and 1 h in Example 2. Figure 8The growth of two-dimensional alkyne-rich carbon material is manifested in the darkening of the color of the copper foil.

[0259] Figure 9 The scanning electron microscope images of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in pyridine solution for 2 min, 10 min, 30 min, and 1 h in Example 1 are shown. Figure 9 It shows that two-dimensional alkyne-rich carbon materials can be grown on copper foil in pyridine solution.

[0260] Figure 10 This is a physical picture of the two-dimensional alkyne-rich carbon material on copper foil obtained by reacting in pyridine solution for 2 min, 10 min, 30 min, and 1 h in Example 1. Figure 10 It shows that growing a small amount of two-dimensional alkyne-rich carbon material in pyridine solution will not change the color of copper foil.

[0261] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection 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 directionally moving manner through the precursor solution to undergo a deposition polymerization reaction, thereby obtaining a two-dimensional alkyne-rich carbon material film on the surface of the copper substrate; The movement rate of the copper substrate is 0.01-10 cm / min; The residence time of the copper substrate from entering the reaction tank to leaving the reaction tank is 0.5 to 10 h; The components of the precursor solution include monomers for preparing two-dimensional alkyne-rich carbon materials and a polar organic solvent; The two-dimensional alkyne-rich carbon material has one or more structures shown in Formula II to Formula IX; Wherein, 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.

2. The preparation method according to claim 1, characterized in that 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 of the structure represented by Formula VI or Formula VII has the structure represented by Formula f; The monomer corresponding to the two-dimensional alkyne-rich carbon material of structure VIII has the structure shown in formula g; The monomer corresponding to the two-dimensional alkyne-rich carbon material of the structure shown in IX includes a compound having the structure shown in formula h and tribromobenzene; 3. The preparation method according to claim 1 or 2, characterized in that The concentration of the monomer in the precursor solution is 0.0001-5 mg / mL.

4. 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%.

5. 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.

6. 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.

7. 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.

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