Preparation method and device of graphite diacetylene powder material

Abstract

The application provides a preparation method and device of a graphdiyne powder material, and the method comprises the following steps: under the action of microwaves, the graphdiyne powder is prepared through a solution homogeneous system and in combination with a flow continuous growth process. The application realizes the large-batch continuous preparation of the graphdiyne powder under the condition of no substrate by using the microwave method, and overcomes the technical difficulty that the graphdiyne powder is difficult to continuously mass-produce in a homogeneous solution. The reaction time is short, the yield is high, the operation is simple, and the two-dimensional graphdiyne nanosheet with uniform sheet diameter is prepared.

Description

Technical Field

[0001] This invention belongs to the field of materials preparation, specifically relating to a method and apparatus for continuous batch preparation of graphite diacetylene powder materials. Background Technology

[0002] Graphitic bisyne is a type of graphitic bisyne composed of sp and sp 2 A novel two-dimensional carbon material composed of hybrid carbon atoms. Due to its unique diyne bond (-C≡CC≡C-), continuous π-conjugated system, and uniformly distributed pore structure, graphitic diyne has broad application potential in energy catalysis, gas separation, and biomedicine. Graphitic diyne is a two-dimensional semiconductor material with a direct band gap of 0.44–1.47 eV and high room-temperature carrier mobility. 4 -10 5 cm 2 ·V -1 ·s -1 This has led to its widespread attention in the fields of electronics, optics, and magnetism.

[0003] Since Academician Li Yuliang first proposed a method for preparing graphdiyne in 2010, scientists have developed many methods for preparing graphdiyne with different morphologies. For example, 1 nm thick graphdiyne films can be obtained through confinement methods, graphdiyne nanowalls can be grown on arbitrary substrates through the "copper envelope method," and graphdiyne nanoribbons and nanotubes can be obtained through template methods.

[0004] However, these methods have drawbacks such as long reaction times (24h-72h), low yields, and complex operations. Therefore, developing a rapid, continuous, and large-scale preparation method for graphitic diyne powder can provide a fundamental guarantee for the industrial application of graphitic diyne. Summary of the Invention

[0005] This invention provides a method and apparatus for the rapid, continuous, and large-scale preparation of graphitic diyne powder materials. The method includes preparing graphitic diyne powder under microwave irradiation via a homogeneous solution system combined with a continuous flow growth process.

[0006] One object of the present invention is to provide a method for continuous production of graphitic diacetylene, characterized in that the method includes the following steps:

[0007] S1. The graphitic diacetylene precursor and the catalyst are mixed with a soluble solvent in a certain proportion and uniformly dispersed to obtain a mixed solution;

[0008] S2. The mixed solution is fed into the pipeline of the microwave reactor for continuous production of graphitic diyne in a flowing state; under microwave conditions, the reaction is carried out at a certain temperature for a certain time to obtain the graphitic diyne powder dispersion.

[0009] S3. The obtained graphite diacetylene powder dispersion is washed and freeze-dried to obtain the graphite diacetylene powder.

[0010] The above method requires no substrate, has a short reaction time, and yields high output.

[0011] According to a specific embodiment of the present invention, the graphite diacetylene precursor is hexa(trimethylsilylethynyl)benzene (HEB-TMS).

[0012] According to a specific embodiment of the present invention, the concentration of the graphitic diacetylene precursor is 0.5-100 mg / mL.

[0013] According to a specific embodiment of the present invention, the catalyst is a copper catalyst; preferably one or more of copper chloride, copper acetate, copper nitrate, copper sulfate, cuprous chloride, and cuprous oxide; more preferably cuprous chloride.

[0014] According to a specific embodiment of the present invention, the concentration of the catalyst is 0.05-10 mg / mL.

[0015] According to a specific embodiment of the present invention, the soluble solvent is an organic solvent, preferably N,N-dimethylformamide (DMF).

[0016] According to a specific embodiment of the present invention, in step S1, the dispersion method is one or more of ultrasonic, high-speed dispersion disc, emulsifier, homogenizer, and centrifugal mill.

[0017] This invention removes TMS from the graphitic diyne precursor HEB-TMS in one step with the aid of a copper catalyst, without the need for separation, and allows for direct subsequent graphitic diyne growth reaction.

[0018] According to a specific embodiment of the present invention, step S2 further includes preheating the initial mixed solution with a certain power for a certain period of time before the continuous reaction begins, so as to bring it to the basic temperature required for the reaction.

[0019] According to a specific embodiment of the present invention, the initial solution is preheated at a temperature of 30-200°C.

[0020] According to a specific embodiment of the present invention, the power of the microwave reactor is 50-1500W, preferably 200-900W, specifically 200W, 400W, 700W, and 900W; the reaction time is 30s-30min, preferably 2min; and the reaction temperature is 130-155℃, preferably 130-140℃, and more preferably 135℃. The reaction time of the present invention is its transit time in the pipeline.

[0021] Another object of the present invention is to provide an apparatus for the above method, the apparatus comprising a microwave reactor, wherein the microwave reactor is provided with a pipeline for continuous growth of graphitic diyne.

[0022] One end of the pipeline is connected to an adjustable flow rate peristaltic pump, and the mixed solution is added to the pipeline at a certain rate through the peristaltic pump;

[0023] The other end of the pipeline is connected to a vacuum pump to enable the flow of the solution phase;

[0024] The device also includes a collection device;

[0025] Preferably, the pipeline is a quartz tube.

[0026] According to a specific embodiment of the present invention, the specific method of using the device is as follows: a peristaltic pump is used to pump the above mixed solution into a continuous growth pipeline, the vacuum pump and the peristaltic pump are turned on to continuously pump the mixed solution into the pipeline until it fills the entire pipeline, the microwave reactor is turned on and set to constant power operation, a black precipitate is observed to be generated, and the black precipitate graphitic diacetylene powder dispersion generated by the reaction is pumped into a collection bottle.

[0027] Beneficial effects:

[0028] This invention utilizes a microwave method to achieve large-scale continuous preparation of graphitic diacetylene powder under substrate-free conditions, overcoming the technical challenge of continuous mass production of graphitic diacetylene powder in homogeneous solutions. The method features short reaction time, high yield, simple operation, and the preparation of uniformly sized two-dimensional graphitic diacetylene nanosheets. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of the preparation device for rapid and continuous mass production of graphite diacetylene powder material according to the present invention.

[0030] Figure 2 This is a photograph of the DMF dispersion of graphite diacetylene powder prepared in Example 1.

[0031] Figure 3 This is a transmission electron microscope (TEM) image of the graphitic diacetylene powder material prepared in Example 1.

[0032] Figure 4 This is an atomic force microscopy characterization image of the graphitic diacetylene powder material prepared in Example 1;

[0033] Figure 5 This is a statistical chart of the flake size of the graphite diacetylene powder material prepared in Example 1;

[0034] Figure 6 The image shows the Raman spectrum of the graphitic diacetylene powder material prepared in Example 1.

[0035] Figure 7 The attached diagram shows the N2 adsorption and desorption of the graphite diacetylene powder material prepared in Example 1.

[0036] Figure 8 The images show the full XPS spectrum and high-resolution C1s spectrum of the graphitic diacetylene powder material prepared in Example 1.

[0037] Figure 9A , Figure 9B Transmission electron microscopy (TEM) images of the graphitic diacetylene powders obtained in Examples 2 and 3 are shown respectively.

[0038] Figure 10A , Figure 10B and Figure 10C Transmission electron microscopy (TEM) images of the graphitic diacetylene powders obtained in Examples 4, 5, and 6 are shown respectively.

[0039] Figure 11 The image shows a transmission electron microscope (TEM) image of the graphitic diacetylene powder obtained in Comparative Example 2. Detailed Implementation

[0040] Typical embodiments embodying the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various variations in different embodiments without departing from the scope of the present invention, and the descriptions and illustrations herein are for illustrative purposes only and not intended to limit the present invention.

[0041] The preparation of the graphite diacetylene powder material according to an embodiment of the present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0042] Example 1

[0043] 300 mg of hexa(trimethylsilylethynyl)benzene (HEB-TMS) and 25 mg of cuprous chloride (CuCl) catalyst were added to 100 mL of N,N-dimethylformamide solution and stirred magnetically at 500 rpm for 15 min to fully dissolve HEB-TMS and CuCl, thus preparing 100 mL of a mixed solution of the precursor and catalyst.

[0044] A solution mobile phase microwave reaction apparatus was constructed. The main body of the system consists of a microwave reactor capable of constant power operation and a custom-designed quartz growth tube with a total length of 35cm, allowing the flow of the mobile liquid phase. The central serpentine tube is 15cm long, with an outer diameter of 6mm and an inner diameter of 4mm. Figure 1As shown in the figure, the maximum reaction power is 900W, and the maximum experimental temperature can reach 155℃. In addition, the solution outside the microwave reaction device is pumped in by a peristaltic pump with adjustable flow rate, and the flow of the solution phase is realized by a vacuum pump at the tail end. The pipeline and the collection bottle are connected by a vacuum connector. The vacuum pump can be connected to the vacuum connector to extract the reaction solution in the system, thereby realizing the flow of the solution phase.

[0045] The above mixed solution was pumped into the continuous growth pipeline using a peristaltic pump. The vacuum pump and peristaltic pump were turned on, with the peristaltic pump flow rate set to 10 mL / min. The solution was continuously pumped into the pipeline. Then, the vacuum pump and peristaltic pump were turned off, and the microwave reactor was started to preheat the solution to 135°C. The vacuum pump and peristaltic pump were turned on again (flow rate 10 mL / min). The microwave reactor was set to constant power operation (900 W), with a reaction temperature of 135°C and an actual reaction time of approximately 2 minutes. The microwave reactor was continuously run, and a black precipitate was observed to form in the pipeline. This precipitate could be collected at the end of the pipeline. The resulting black precipitate, a dispersion of graphitic diacetylene powder, was pumped into a collection bottle (e.g., ...). Figure 2 (As shown).

[0046] After the reaction was stopped, the graphitic diacetylene powder dispersion in the collection flask was allowed to cool to room temperature. The dispersion was transferred to 50 mL centrifuge tubes and centrifuged at 8000 rpm for 10 min to remove the DMF solvent. The supernatant was poured off, and 30 mL of pyridine solvent was added to each centrifuge tube. The mixture was then ultrasonically dispersed for 15 min using an ultrasonic cleaner to ensure that the graphitic diacetylene powder was uniformly dispersed in the pyridine solution. The mixture was left to stand overnight.

[0047] The pyridine dispersion of graphitic diacetylene powder was washed three times with pyridine, acetone and water by vacuum filtration, and the aqueous dispersion of graphitic diacetylene powder was collected.

[0048] The graphdiyne aqueous dispersion was briefly frozen with liquid nitrogen, and then dried using a freeze dryer for 3 days until dry. This yielded a graphdiyne powder sample.

[0049] The testing methods involved in the examples are as follows: the field emission scanning electron microscope is a FEI Quattro S; the Raman characterization is performed using a LabRAM HR Evolution Raman spectrometer from Horiba Corporation, Japan; the transmission electron microscope is a FEI Tecnai F20; the X-ray photoelectron spectroscopy (XPS) is performed using a Kratos Analytical Axis-Ultraspectrometer; and the atomic force microscope (AFM) is performed using a Bruker Dimension Icon AFM.

[0050] Figure 3The image shown is a transmission electron microscope (TEM) image of the graphitic diacetylene powder obtained in Example 1. It can be seen that the graphitic diacetylene powder obtained under these conditions has a two-dimensional circular flake morphology with relatively uniform flake size and thickness distribution.

[0051] Figure 4 The image shows the atomic force microscopy characterization of the graphitic diacetylene powder material prepared in Example 1. It can be seen that the graphitic diacetylene powder material has a relatively regular circular shape, with a nucleation center in the center with a height of 11 nm and edge lamellar thickness of about 4 nm.

[0052] Figure 5 This is a statistical chart of the flake size of the graphitic diacetylene powder material prepared in Example 1. The statistical results show that the obtained graphitic diacetylene powder material has a uniform flake size distribution, mainly distributed in the range of 200-280 nm, with an average flake size of 246 nm.

[0053] Figure 6 The image shows the Raman spectrum of the graphitic diacetylene powder material prepared in Example 1. The characteristic peaks of the Raman spectrum originate from the stretching vibrations of the carbon-carbon single bonds connecting the carbon-carbon triple bond and the benzene ring. (1336.5 cm⁻¹) -1 1524.2cm -1 1563.6cm -1 The spectral peak at 2172 cm⁻¹ originates from the stretching vibration of the carbon-carbon bonds in the benzene ring, similar to that in graphene. However, compared to graphene, due to the introduction of the carbon-carbon triple bond, the peak position of this vibrational mode in the acetylene-rich two-dimensional material is red-shifted and its intensity is lower. -1 The characteristic spectral peaks at the location originate from the stretching vibrations of the diacetylene bond (-C≡CC≡C-), proving that a coupling reaction occurred in the precursor.

[0054] Figure 7 The attached figure shows the N2 adsorption / desorption of the graphitic diacetylene powder obtained in Example 1. Test results show that the BET specific surface area of ​​this graphitic diacetylene powder is 362.9358 m². 2 / g, average pore size 11.6nm.

[0055] Figure 8 The figures show the full XPS spectrum and high-resolution C1s spectrum of the graphitic diacetylene powder material prepared in Example 1. The C1s peak in the figure can be deconvolved into four subpeaks, corresponding to C1s(sp) peaks. 2 ), CC(sp), CO and C=O. According to the structural model of graphitic diyne, the benzene rings are connected by diyne bonds (-C≡CC≡C-), therefore sp and sp 2 The peak area ratio of hybrid carbon atoms is 2. A small amount of C=O may originate from O2 adsorbed on the sample surface, as well as minor impurities or defects.

[0056] Example 2

[0057] Except for the addition of 100 mg of the graphitic diyne precursor hexa(trimethylsilylethynyl)benzene (HEB-TMS) in the first stage, the other conditions were the same as in Example 1. The morphology of the obtained graphitic diyne powder is as follows. Figure 9A The TEM characterization diagram is shown.

[0058] Example 3

[0059] Except for the addition of 500 mg of the graphitic diyne precursor hexa(trimethylsilylethynyl)benzene (HEB-TMS) in the first stage, all other conditions were the same as in Example 1. The morphology of the obtained graphitic diyne powder is as follows. Figure 9B The TEM characterization diagram is shown.

[0060] Figure 9A , Figure 9B Transmission electron microscopy (TEM) images of the graphitic diacetylene powders obtained in Examples 2 and 3 are shown respectively. It can be seen that the graphitic diacetylene powders obtained under these conditions have a two-dimensional circular flake morphology with relatively uniform flake size and thickness distribution.

[0061] Example 4

[0062] Except for the microwave reactor power being 200W in the first stage, all other conditions were the same as in Example 1. The morphology of the obtained graphitic diacetylene powder is as follows. Figure 10A The TEM characterization diagram is shown.

[0063] Example 5

[0064] Except for the microwave reactor power being 400W in the first stage, all other conditions were the same as in Example 1. The morphology of the obtained graphitic diacetylene powder is as follows. Figure 10B The TEM characterization diagram is shown.

[0065] Example 6

[0066] Except for the microwave reactor power of 700W in the first stage, all other conditions were the same as in Example 1. The morphology of the obtained graphitic diacetylene powder is as follows. Figure 10C The TEM characterization diagram is shown.

[0067] Figure 10A , Figure 10B and Figure 10C Transmission electron microscopy (TEM) images of the graphitic diacetylene powders obtained in Examples 4, 5, and 6 are shown respectively. It can be seen that the graphitic diacetylene powders obtained under these conditions have a two-dimensional circular flake morphology with relatively uniform flake size and thickness distribution.

[0068] Comparative Example 1

[0069] 300 mg of hexa(trimethylsilylethynyl)benzene (HEB-TMS) and 25 mg of cuprous chloride (CuCl) catalyst were added to 100 mL of N,N-dimethylformamide solution and stirred magnetically at 500 rpm for 15 min to fully dissolve HEB-TMS and CuCl, thus preparing 100 mL of a mixed solution of the precursor and catalyst.

[0070] In a static reactor, SiO2 / Si-graphene substrate was reacted at 60°C for 24 hours.

[0071] The obtained sample is a graphdiyne film grown on a graphene substrate. The film has a structure of 3 nm thickness and a lateral dimension of approximately 1 × 1 cm, attached to a SiO2 / Si-graphene substrate. 2 The resulting film is of finite size, unlike the powder samples obtained in Examples 1-6. Furthermore, this sample cannot be separated from the graphene substrate, resulting in lower yield.

[0072] Comparative Example 2

[0073] 300 mg of hexa(trimethylsilylethynyl)benzene (HEB-TMS) and 25 mg of cuprous chloride (CuCl) catalyst were added to 100 mL of N,N-dimethylformamide solution and stirred magnetically at 500 rpm for 15 min to fully dissolve HEB-TMS and CuCl, thus preparing 100 mL of a mixed solution of the precursor and catalyst.

[0074] In a static reactor, without substrate, the reaction was carried out at 135°C for 24 hours.

[0075] The resulting powder has a three-dimensional structure (e.g. Figure 11 ).

[0076] Unless otherwise specified, the terms used in this invention have the meanings commonly understood by those skilled in the art.

[0077] The embodiments described in this invention are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Those skilled in the art can make various other substitutions, changes and improvements within the scope of this invention. Therefore, this invention is not limited to the above embodiments, but is only defined by the claims.

Claims

1. A method for continuous production of graphitic diacetylene, characterized in that, The method includes the following steps: S1. The graphitic diacetylene precursor and the catalyst are mixed with a soluble solvent in a certain proportion and uniformly dispersed to obtain a mixed solution; S2. The mixed solution is passed into a pipeline that allows for the continuous growth of graphitic diyne in a flowing state; under microwave conditions, it is reacted at a certain temperature for a certain time to obtain a graphitic diyne powder dispersion. S3. The obtained graphite diacetylene powder dispersion is washed and freeze-dried to obtain graphite diacetylene powder. The graphitic diacetylene precursor is hexa(trimethylsilylethynyl)benzene, the catalyst is a copper catalyst, and the soluble solvent is N,N-dimethylformamide.

2. The method according to claim 1, characterized in that, The catalyst is one or more of copper chloride, copper acetate, copper nitrate, copper sulfate, cuprous chloride, and cuprous oxide.

3. The method according to claim 1, characterized in that, Step S2 further includes preheating the mixed solution for a certain period of time to bring it to the basic temperature required for the reaction.

4. The method according to claim 1, characterized in that, The microwave power is 50-1500W; the reaction time is 30s-30min; and the reaction temperature is 130-155℃.

5. The method according to claim 4, characterized in that, The microwave power is 200-900W; the reaction time is 2min; and the reaction temperature is 130-140℃.

6. The method according to claim 1, characterized in that, The concentration of the graphitic diacetylene precursor is 0.5-100 mg / mL.

7. The method according to claim 1, characterized in that, The concentration of the catalyst is 0.05-10 mg / mL.

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