Method for preparing nano-pore carbon-based two-dimensional membrane material through ionization irradiation and product of nano-pore carbon-based two-dimensional membrane material

Abstract

The invention discloses a method for preparing a nano-pore carbon-based two-dimensional membrane material through ionization irradiation and a product thereof, the preparation method comprises the following steps: step 1, dispersing a two-dimensional carbon-based nano material in a dispersant to prepare a dispersion liquid, and preparing the dispersion liquid into a precursor membrane for later use; and 2, carrying out ionization irradiation treatment on the precursor film prepared in the step 1, and carrying out annealing treatment on the precursor film subjected to the ionization irradiation treatment to obtain the nano-pore carbon-based two-dimensional film material. Compared with a traditional method, due to the unique physicochemical properties of the high-energy rays, physical damage and chemical effects can be synchronously generated in the process of penetrating through the membrane material, and the porous preparation process can be simplified; by regulating and controlling the raw material ratio in the precursor and the ionization irradiation condition, the size and density of gas molecules between membrane material layers can be controlled, and the aperture and empty density of the surface of the membrane material can be regulated and controlled in the subsequent annealing process; therefore, the method provided by the invention has the advantages of rapidness, high efficiency, economy, energy conservation and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of nanomaterials, and in particular to a method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation and a product thereof. Background Art

[0002] With the rapid development of nanotechnology, nanomaterials have been widely studied and applied in the fields of energy, environmental protection, biomedicine, information and communication. Among them, two-dimensional nanomaterials have been widely studied and applied in energy storage, ion / molecule separation, high-efficiency catalysis, and sensing technology due to their unique physical and chemical properties. Especially in the application of ion / molecule separation, the corresponding pores can be designed on the two-dimensional nanomembrane material according to the size of the target ions or molecules to be separated, and then the edges of the pores can be modified to achieve accurate screening of ions or molecules.

[0003] Therefore, a lot of research has been conducted on the preparation of pores in two-dimensional nanomembrane materials. The stripping method, etching method, electrolysis method, self-assembly, template method and CVD method have been studied to prepare nanoporous two-dimensional nanomembrane materials. The stripping method mainly uses bulk materials. Through chemical stripping or mechanical stripping, a thin film of two-dimensional materials can be obtained, and pores are formed in the membrane through subsequent treatment. The etching method usually uses photolithography technology to pre-prepare a hollow structure on a substrate, and then removes part of the material by dry etching or wet etching to form pores in the two-dimensional membrane. The electrolysis method is usually used to prepare porous structures of metal oxides or sulfides. The size or spacing of the pore structure can be adjusted by controlling the electrolysis conditions. Some polymers can form nanostructures through self-assembly technology. These self-assembled membranes have natural pore structures and are suitable for separation and filtration. The template method uses a template material with a specific pore structure to obtain a template membrane through filling or deposition technology, and then removes the template to obtain a two-dimensional membrane with a predetermined pore. CVD is a method for preparing high-quality two-dimensional membrane materials, which can then be used to form pore structures through subsequent etching steps.

[0004] With the development of nanotechnology, people are also constantly studying new methods to achieve a simpler and more efficient preparation of nanoporous two-dimensional membrane materials. Therefore, the present invention proposes a method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation and its products. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation, which is intended to have the advantages of being fast, efficient, economical, energy-saving and having adjustable pore structure compared to existing methods.

[0006] In order to solve the above technical problems, the object of the present invention is achieved as follows: A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: dispersing the two-dimensional carbon-based nanomaterial in a dispersant to prepare a dispersion liquid, and preparing the dispersion liquid into a precursor film for standby use; Step 2: The precursor film prepared in step 1 is subjected to ionizing radiation treatment, and then the precursor film after ionizing radiation treatment is annealed to obtain a nanoporous carbon-based two-dimensional membrane material.

[0007] On the basis of the above scheme and as a preferred scheme of the above scheme: the two-dimensional carbon-based nanomaterial is one or a mixture of any proportion of two of graphene, graphene oxide, and MXene.

[0008] On the basis of the above scheme and as a preferred scheme of the above scheme: the dispersant is one of water, ethanol, and DMF or a mixture of any proportions of the above.

[0009] On the basis of the above scheme and as a preferred scheme of the above scheme: the preparation method of the precursor membrane is a suction filtration method or a membrane laying method.

[0010] On the basis of the above scheme and as a preferred scheme of the above scheme: the radiation source of the ionizing radiation treatment is an electron accelerator or a cobalt source, and the radiation energy is 0.2-10MeV.

[0011] On the basis of the above scheme and as a preferred scheme of the above scheme: the irradiation dose rate of the ionizing radiation is 0.1 kGy / circle-10 kGy / circle, and the irradiation dose is 10 kGy-100 kGy.

[0012] On the basis of the above scheme and as a preferred scheme of the above scheme: the temperature condition of the ionizing radiation is 18-30°C, and the gas atmosphere is one or a mixture of any proportion of air, nitrogen, inert gas, and vacuum.

[0013] On the basis of the above scheme and as a preferred scheme of the above scheme: the temperature of the annealing treatment is 50-200°C, and the temperature rising or falling speed is 1-10°C / min.

[0014] A nanoporous carbon-based two-dimensional membrane material is prepared using any of the above methods for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0015] The beneficial effects of the present invention are: based on the method of preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation of the present invention, compared with the traditional method, due to the unique physical and chemical properties of high-energy rays, they will simultaneously produce physical damage and chemical effects in the process of penetrating the membrane material, thereby simplifying the porous preparation process; by regulating the raw material ratio in the precursor and the ionizing radiation conditions, the size and density of the gas molecules between the membrane material layers can be controlled, so the pore size and void density on the surface of the membrane material can be controlled in the subsequent annealing process; therefore, the method proposed by the present invention has the advantages of being fast, efficient, economical, and energy-saving. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is an infrared spectrum characterization diagram of the nanoporous graphene film material before and after ionizing radiation involved in Example 1; Figure 2 The XRD characterization diagram of the nanoporous graphene membrane material before and after ionizing radiation involved in Example 1; Figure 3 This is a TEM characterization image of the nanoporous graphene film material before ionizing irradiation involved in Example 1; Figure 4 This is a first TEM characterization image of the nanoporous graphene film material after ionizing radiation involved in Example 1; Figure 5 This is a second TEM characterization image of the nanoporous graphene membrane material after ionizing irradiation involved in Example 1. DETAILED DESCRIPTION

[0017] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments.

[0018] Example 1

[0019] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 8kGy / circle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0020] The nanoporous graphene membrane materials before and after ionizing irradiation were characterized and analyzed by infrared spectroscopy, XRD and TEM.

[0021] Combination Figure 1-5 Analysis was carried out and the results of infrared spectroscopy characterization showed that the functional groups on the surface of the nanoporous graphene membrane material remained basically unchanged before and after irradiation. The curve shapes of the nanoporous graphene membrane material before and after irradiation in the XRD characterization results were basically the same, further proving that the structure of the nanoporous graphene membrane material did not change before and after irradiation. TEM characterization showed that there was a pore structure on the surface of the nanoporous graphene membrane material after irradiation, indicating that a porous structure was successfully formed on the surface of the precursor membrane after irradiation treatment, and the nanoporous graphene membrane material was successfully prepared.

[0022] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0023] Example 2

[0024] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 8kGy / circle and the irradiation dose to 40kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0025] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0026] Example 3

[0027] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 10kGy / circle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0028] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0029] Example 4

[0030] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 10kGy / circle and the irradiation dose to 40kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0031] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0032] Example 5

[0033] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.2 g of graphene oxide, dissolve it in 100 ml of water to prepare a 2 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 8kGy / circle and the irradiation dose to 40kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0034] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0035] Example 6

[0036] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.2 g of graphene oxide, dissolve it in 100 ml of water to prepare a 2 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 8kGy / circle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0037] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0038] Example 7

[0039] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 5MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 10kGy / circle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0040] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0041] Example 8

[0042] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 10kGy / circle and the irradiation dose to 20kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0043] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0044] Example 9

[0045] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 2kGy / circle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0046] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0047] Example 10

[0048] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of water to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 1MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 5kGy / cycle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0049] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0050] Embodiment 11

[0051] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of graphene oxide, dissolve it in 100 ml of DMF solution to prepare a 5 g / L dispersion, and prepare a precursor film from the dispersion by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 5kGy / cycle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 150°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous graphene film material.

[0052] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0053] Example 12

[0054] A method for preparing a nanoporous carbon-based two-dimensional membrane material by ionizing radiation comprises the following steps: Step 1: Weigh 0.5 g of MXene and dissolve it in 100 ml of water to prepare a 5 g / L dispersion. Prepare the dispersion into a precursor film by suction filtration for later use; Step 2: Use a 10MeV electron accelerator to treat the precursor film prepared in step 1 with ionizing radiation at a temperature of 18-30°C, that is, at room temperature. Set the irradiation dose rate to 5kGy / cycle and the irradiation dose to 80kGy; place the irradiated precursor film in a vacuum oven for annealing, set the temperature to 200°C, the heating rate to 10°C / min, and the cooling rate to 5°C / min to obtain a nanoporous MXene film material.

[0055] A nanoporous carbon-based two-dimensional membrane material is prepared using the above-mentioned method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation.

[0056] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation, characterized in that: The following steps are involved: Step 1: dispersing the two-dimensional carbon-based nanomaterial in a dispersant to prepare a dispersion liquid, and preparing the dispersion liquid into a precursor film for standby use; Step 2: The precursor film prepared in step 1 is subjected to ionizing radiation treatment, and then the precursor film after ionizing radiation treatment is annealed to obtain a nanoporous carbon-based two-dimensional membrane material.

2. The method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation according to claim 1, characterized in that: The two-dimensional carbon-based nanomaterial is one of graphene, graphene oxide, and MXene, or a mixture of two of them in any proportion.

3. The method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation according to claim 1, characterized in that: The dispersant is one of water, ethanol and DMF or a mixture of any proportions thereof.

4. The method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation according to claim 1, characterized in that: The precursor membrane is prepared by a suction filtration method or a membrane laying method.

5. The method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation according to claim 1, characterized in that: The radiation source of the ionizing radiation treatment is an electron accelerator or a cobalt source, and the radiation energy is 0.2-10 MeV.

6. The method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation according to claim 1, characterized in that: The ionizing radiation has an irradiation dose rate of 0.1 kGy / circle-10 kGy / circle, and an irradiation dose of 10 kGy-100 kGy.

7. The method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation according to claim 1, characterized in that: The temperature condition of the ionizing radiation is 18-30° C., and the gas atmosphere is one of air, nitrogen, inert gas, and vacuum, or a mixture of any proportions thereof.

8. The method for preparing nanoporous carbon-based two-dimensional membrane materials by ionizing radiation according to claim 1, characterized in that: The temperature of the annealing treatment is 50-200° C., and the heating or cooling speed is 1-10° C. / min.

9. A nanoporous carbon-based two-dimensional membrane material, characterized in that: The material is prepared by the method for preparing nanoporous carbon-based two-dimensional membrane material by ionizing radiation as described in any one of claims 1 to 8.

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