CN111994894B - Preparation method of nitrogen-doped aerogel carbon micro-tube - Google Patents
Preparation method of nitrogen-doped aerogel carbon micro-tube Download PDFInfo
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Abstract
The invention discloses a preparation method of nitrogen-doped aerogel carbon micro-tubes, which comprises the following steps of (1) mixing chitosan and ionic liquid, stirring, adding a catalyst, heating to 60-120 ℃ and stirring for 1-4h for dissolution; the ionic liquid is 1-ethyl-3-methylimidazole acetate, 1-allyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate and 1-ethyl-3-methylimidazole chloride; (2) And (3) heating to 900-1500 ℃ in an inert gas atmosphere, treating for 0.5-2h, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube. The method has simple process and low cost, the obtained carbon micro-tube macroscopically presents an aerogel tube shape to form an integral three-dimensional net structure, the tube diameter range is 0.5-2 mu m, and the biomass chitosan is used as the raw material and is easy to obtain and low in cost.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of a nitrogen-doped aerogel carbon micro-tube.
Background
Tubular carbon has been developed for nearly twenty years since the first preparation of carbon nanotubes by Iijima. The carbon nano tube has outstanding mechanical property, electrical property, thermal property and optical property, and is widely applied to various fields such as nano electronic devices, transparent displays, super-strong materials, polymer composite materials, coatings, printing ink, energy devices and the like. The carbon nanotube is also a unique carbon material, has very similar physical and chemical properties to those of the carbon nanotube, has larger difference in the pipe diameter, is an important member in a one-dimensional carbon material family, and overcomes the defect of limited application range caused by smaller dimension of the carbon nanotube. The biomass is used as a material with higher carbon content, is green and environment-friendly and accords with the strategy of sustainable development, and is an ideal carbon source for preparing the carbon micro-tubes. The advantages of the biomass structure and the diversity of the properties are fully utilized, so that the carbon micro-tube with better performance effect is efficiently and stably obtained. By exploring how a biomass carbon source influences the carbon micro-tube structure in the preparation of the biomass-based carbon micro-tube, and further improving the preparation method, the reaction flow process is further optimized by pushing the product reversely, the product optimization is realized, and meanwhile, the mechanism and effect mechanism of the biomass-based carbon micro-tube in the application fields of adsorption, catalysis, drug slow release, super-capacitor and the like are explored, so that the method is a necessary step for realizing the large-scale production of the biomass-based carbon micro-tube.
At present, most of the methods for preparing the carbon micro-tubes have the problems of more steps in the preparation process, high requirements on process conditions, low replicability of the final product and the like. Most of carbon sources for preparing the carbon micro-tube are expensive, toxic and harmful products are more in the preparation process, the raw materials have certain toxicity, and the defects also lead the development of the preparation of the carbon micro-tube to be hindered to a certain extent. In addition, many studies have been conducted on the utilization of a hollow tubular structure of biomass itself, further carbonization into a tube, and subsequent modification studies, and the product is limited to a raw material structure. Therefore, the dependence on the biomass structure is broken through, and the method becomes a great difficulty to be solved urgently. In addition, most of the current methods for preparing carbon nanotubes have the problems of complex preparation method and high raw material cost. The preparation method aims at solving the problems, simultaneously realizes the simplification of the preparation process, reduces the production cost, improves the product performance, and can be used for strongly promoting the research of the carbon micro-tube.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
Aiming at the problems of more process steps, high technological condition requirements, high raw material cost, certain toxicity, limited product structure due to the raw material structure and the like in the preparation of the carbon nano tube in the prior art, the invention provides a preparation method of the nitrogen-doped aerogel carbon micro tube, and aims to obtain the preparation method of the nitrogen-doped aerogel carbon micro tube with simple process, simple operation and low cost.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following operation steps:
(1) Mixing chitosan and ionic liquid, stirring, adding a catalyst, heating to 60-120 ℃, and stirring for 1-4h for dissolution; the ionic liquid is 1-ethyl-3-methylimidazole acetate, 1-allyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate and 1-ethyl-3-methylimidazole chloride;
(2) And (3) heating the substance obtained after the dissolution in the step (1) to 900-1500 ℃ under the condition of inert gas atmosphere, performing constant temperature treatment for 0.5-2h, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube.
Preferably, in the step (1), the chitosan and the ionic liquid are mixed in a mass ratio of 0.05:1.
Preferably, in step (1), stirring is performed at room temperature for 10 to 20 minutes.
Preferably, the catalyst in the step (1) is used in an amount of 5 to 100% of the mass of the chitosan.
Preferably, the catalyst in step (1) is used in an amount of 5% by mass of chitosan.
Preferably, the catalyst in step (1) is ferric nitrate or ferric chloride.
Preferably, the inert gas in step (2) is nitrogen or argon.
Preferably, in the step (2), the temperature is raised to 900-1500 ℃ at a temperature raising rate of 5-10 ℃/min.
Preferably, in the step (2), the temperature is raised to 1200-1500 ℃ under the inert gas atmosphere condition, and the constant temperature treatment is carried out for 0.5-2h.
Compared with the prior art, the invention has the following beneficial effects:
the method has the advantages of simple process, easy parameter control, simple operation, easy amplification and low cost; compared with the powdery carbon micro-tube, the carbon micro-tube obtained by the invention is macroscopic in an aerogel tube shape, forms an integral three-dimensional net structure, has the tube diameter range of 0.5-2 mu m, and is easy to obtain and low in cost by taking biomass chitosan as a raw material.
Drawings
FIG. 1 is an X-ray diffraction pattern of the resulting nitrogen-doped aerogel carbon nanotubes at 1200℃with varying amounts of catalyst.
FIG. 2 is an X-ray diffraction pattern of the resulting nitrogen-doped aerogel carbon nanotubes at different temperatures with the same catalyst dosage.
FIG. 3 is a scanning electron microscope image of the nitrogen-doped aerogel carbon nanotubes obtained at different temperatures with the same catalyst dosage; wherein, (a) is the morphology of the nitrogen-doped aerogel carbon micro-tube obtained at 1000 ℃ when the catalyst dosage is 5%, and the magnification is 10 mu m; (b) The morphology of the nitrogen-doped aerogel carbon micro-tube obtained at 1200 ℃ when the catalyst dosage is 5 percent, and the magnification is 10 mu m; (c) The morphology of the nitrogen-doped aerogel carbon micro-tube obtained at 1500 ℃ when the catalyst dosage is 5 percent, and the magnification is 10 mu m.
FIG. 4 is a transmission electron microscope image of the nitrogen-doped aerogel carbon nanotubes prepared in example 1 of the present invention; wherein, (a) is a transmission electron microscope image with a magnification of 5 μm, (b) is a transmission electron microscope image with a magnification of 1 μm, (c) is a transmission electron microscope image with a magnification of 20nm, (d) is a transmission electron microscope image with a magnification of 50nm, (e) is a transmission electron microscope image with a magnification of 5nm, and (f) is a transmission electron microscope image with a magnification of 20 nm.
FIG. 5 is a transmission electron micrograph of a cross section of a nitrogen-doped aerogel carbon nanotube prepared in example 1 of the present invention at a magnification of 2. Mu.m.
Detailed Description
The following detailed description, in conjunction with the accompanying drawings, describes in detail, but it is to be understood that the scope of the invention is not limited to the specific embodiments. The raw materials and reagents used in the examples were commercially available unless otherwise specified.
Example 1
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-ethyl-3-methylimidazole acetate, stirring at room temperature for 10min, adding 0.015g of catalyst ferric chloride, heating to 800 ℃, and stirring for 4h for dissolution;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 1200 ℃ at a heating rate of 5 ℃/min under the condition of nitrogen atmosphere, performing constant temperature treatment for 1h, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Example 2
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-ethyl-3-methylimidazole acetate, stirring at room temperature for 20min, adding 0.15g of catalyst ferric nitrate, heating to 120 ℃, and stirring for 2h to dissolve;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 1500 ℃ at a heating rate of 10 ℃/min under the condition of nitrogen atmosphere, performing constant temperature treatment for 0.5h, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Example 3
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-ethyl-3-methylimidazole acetate, stirring at room temperature for 15min, adding 0.3g of catalyst ferric chloride, heating to 120 ℃, and stirring for 1h to dissolve;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 900 ℃ at a heating rate of 7 ℃/min under an argon atmosphere condition, performing constant temperature treatment for 2 hours, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Example 4
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-allyl-3-methylimidazole chloride (AMiMCl), stirring at room temperature for 15min, adding 0.06g of catalyst ferric nitrate, heating to 120 ℃, and stirring for 1h to dissolve;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 1200 ℃ at a heating rate of 7 ℃/min under the condition of nitrogen atmosphere, performing constant temperature treatment for 2 hours, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Example 5
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-butyl-3-methylimidazole chloride (BMiMCl), stirring at room temperature for 15min, adding 0.09g of catalyst ferric nitrate, heating to 60 ℃, and stirring for 4h for dissolution;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 1200 ℃ at a heating rate of 7 ℃/min under an argon atmosphere condition, performing constant temperature treatment for 2 hours, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Example 6
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-ethyl-3-methylimidazole acetate (EMiMOAc), stirring at room temperature for 15min, adding 0.15g of catalyst ferric nitrate, heating to 120 ℃, and stirring for 1h for dissolution;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 1200 ℃ at a heating rate of 5 ℃/min under an argon atmosphere condition, performing constant temperature treatment for 2 hours, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Example 7
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-butyl-3-methylimidazole acetate (BMiMOAc), stirring at room temperature for 15min, adding 0.18g of catalyst ferric nitrate, heating to 120 ℃, and stirring for 1h for dissolution;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 1200 ℃ at a heating rate of 7 ℃/min under an argon atmosphere condition, performing constant temperature treatment for 2 hours, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Example 8
The preparation method of the nitrogen-doped aerogel carbon micro-tube comprises the following specific operation steps:
(1) Mixing 0.3g of chitosan with 6g of 1-ethyl-3-methylimidazole chloride (EMiMCl), stirring at room temperature for 15min, adding 0.21g of catalyst ferric nitrate, heating to 70 ℃, and stirring for 1h for dissolution;
(2) Placing the ionic liquid-chitosan-catalyst homogeneous system dissolved in the step (1) into a quartz boat, then placing the quartz boat into a constant temperature area of a tubular high-temperature furnace, heating to 1200 ℃ at a heating rate of 5 ℃/min under an argon atmosphere condition, performing constant temperature treatment for 2 hours, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube with the tube diameter range of 0.5-2 mu m.
Comparative example 1
The reaction was carried out in the same manner as in example 1 without adding a catalyst, and after the reaction, there was no tubular structure product and no product.
And (3) detection:
the catalyst amounts in step (1) were adjusted to 20%, 50% and 100%, respectively, and the rest was the same as in example 1, and the obtained nitrogen-doped aerogel carbon nanotube (including the results of example 1) had an X-ray diffraction pattern shown in fig. 1.
The reaction temperature of the inert gas in the step (2) is respectively adjusted to 1000 ℃ and 1500 ℃, the rest operation is the same as that of the embodiment 1, the X-ray diffraction diagram of the obtained nitrogen doped aerogel carbon nano tube (comprising the result of the embodiment 1) is shown in fig. 2, and the scanning electron microscope diagram is shown in fig. 3; in FIG. 2, 1000-5 represents 5% of catalyst at 1000℃and 1200-5 represents 5% of catalyst at 1200℃and 1500 represents 5% of catalyst at 1500 ℃.
As can be seen from fig. 1, fig. 2, fig. 3, fig. 4 and fig. 5, the nitrogen-doped aerogel carbon micro-tube obtained by the method can obtain the nitrogen-doped aerogel carbon micro-tube with good crystallinity under the conditions of low catalyst dosage and lower temperature, and the nitrogen-doped aerogel carbon micro-tube prepared by the method is in an aerogel tube shape, forms an integral three-dimensional network structure, and has the tube diameter range of 0.5-2 μm.
According to the preparation method of the nitrogen-doped aerogel carbon micro-tube, the solution system formed by dissolving the biomass raw material by adopting the ionic liquid is used as a carbon source to directly carbonize and prepare the carbon micro-tube, so that dependence on a biomass structure is broken, namely, the carbon micro-tube can be formed without the biomass itself having a tubular structure.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (7)
1. The preparation method of the nitrogen-doped aerogel carbon micro-tube is characterized by comprising the following operation steps:
(1) Mixing chitosan and ionic liquid according to the mass ratio of 0.05:1, stirring, adding a catalyst, heating to 60-120 ℃, and stirring for 1-4 hours for dissolution; the ionic liquid is one of 1-ethyl-3-methylimidazole acetate, 1-allyl-3-methylimidazole chloride, 1-butyl-3-methylimidazole chloride, 1-ethyl-3-methylimidazole acetate, 1-butyl-3-methylimidazole acetate or 1-ethyl-3-methylimidazole chloride;
(2) And (3) heating the substance obtained after the dissolution in the step (1) to 1200-1500 ℃ under the condition of inert gas atmosphere, performing constant temperature treatment for 0.5-2h, and cooling to room temperature to obtain the nitrogen-doped aerogel carbon micro-tube.
2. The method of manufacturing according to claim 1, characterized in that: stirring at room temperature for 10-20min in the step (1).
3. The method of manufacturing according to claim 1, characterized in that: the dosage of the catalyst in the step (1) is 5-100% of the mass of the chitosan.
4. The method of manufacturing according to claim 1, characterized in that: the catalyst in the step (1) is 5% of the mass of the chitosan.
5. The method of manufacturing according to claim 1, characterized in that: the catalyst in the step (1) is ferric nitrate or ferric chloride.
6. The method of manufacturing according to claim 1, characterized in that: the inert gas in the step (2) is nitrogen or argon.
7. The method of manufacturing according to claim 1, characterized in that: in the step (2), the temperature is raised to 1200-1500 ℃ at a temperature raising rate of 5-10 ℃/min.
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