CN109437156B - Preparation method of nitrogen-doped carbon nanotube - Google Patents
Preparation method of nitrogen-doped carbon nanotube Download PDFInfo
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Abstract
The invention relates to a preparation method of nitrogen-doped carbon nano-tubes, which is synthesized by adopting a hard template method and comprises the following steps: in a reaction medium of water and ethanol, cobalt nitrate hexahydrate is used as a cobalt source, and Co (OH) is synthesized by a hydrothermal method2A precursor; under certain conditions, Co (OH) is mixed by roasting2Conversion of precursor to Co3O4A nanowire; in trihydroxymethyl aminomethane buffer solution with certain pH value in Co3O4And coating a layer of polydopamine on the surface of the nanowire, then carbonizing the nanowire at high temperature in an inert atmosphere, finally etching the nanowire through HCl, washing the nanowire for multiple times through deionized water, and drying the nanowire to obtain the product. Compared with the prior art for preparing the carbon nano tube, the preparation process has the advantages of easily available raw materials, convenient operation and mild reaction conditions, and the prepared nitrogen-doped carbon nano tube has the characteristics of high nitrogen doping amount, large specific surface area and the like.
Description
Technical Field
The invention relates to the field of nano material preparation, in particular to a preparation method of a nitrogen-doped carbon nano tube.
Background
The nano material has a plurality of excellent physical and chemical properties, particularly, the porous carbon nano material is widely applied to the fields of catalysis, adsorption separation, sensing, electrochemistry and the like because of the controllable pore structure and surface chemical property, and the performance of the porous carbon material can be further improved by methods such as modification, doping and the like, so that the application value of the porous carbon material is improved.
Nitrogen is an ideal element for doping the carbon material, physical and chemical properties of the carbon material can be effectively improved through nitrogen doping, special optical, magnetic and electrical characteristics are generated, and the research on synthesis of the nitrogen is more and more interesting for scientists. The introduction of nitrogen atoms into the structure of the porous carbon material tends to increase the defect sites of the porous carbon material, so that the activity in electrochemical or electrocatalytic reactions is increased. The surface nitrogen-containing functional groups can improve the surface hydrophilic property of the porous carbon material, improve the biocompatibility of the porous carbon material, and enable the porous carbon material to be easily combined with metal ions, so that the metal catalyst can be uniformly dispersed on the surface of the carbon material. In a word, the nitrogen-doped porous carbon material has more excellent properties than a pure porous carbon material, and the application range of the carbon material in various fields is greatly expanded.
At present, the nitrogen-doped carbon nanotube preparation method has many publications. Chinese patent CN 107686105A discloses a method for preparing a nitrogen-doped carbon nanotube material, which comprises mixing carbon nanotubes and melamine solid at a mass ratio of 1:1-4, grinding with a mortar, roasting in nitrogen at high temperature, washing to neutrality, and drying. Chinese patent CN 108063056A discloses a porous nitrogen-doped carbon/carbon nanotube composite material and a preparation method thereof, wherein polypyrrole nanotubes are prepared by methyl orange, ferric chloride and pyrrole and used as a matrix, the polypyrrole nanotubes are subjected to in-situ reaction on the surfaces of the polypyrrole nanotubes to form a layer of metal organic framework material, and precursor powder is subjected to high-temperature carbonization in a nitrogen or argon protective atmosphere. Chinese patent CN 105084339A discloses a nitrogen-doped multi-walled carbon nanotube and a preparation method thereof, wherein a one-dimensional nanowire aqueous solution is mixed with tris (hydroxymethyl) aminomethane, the pH value of the mixture is adjusted to be alkaline, the mixture is reacted with dopamine hydrochloride, the reactant is reacted with tetraethyl silicate in the presence of a catalyst and a surfactant solution, tris (hydroxymethyl) aminomethane is mixed, the pH value of the mixture is adjusted to be alkaline, the reaction with dopamine hydrochloride is carried out, and finally the obtained reactant is sequentially subjected to freeze drying, carbonization treatment and etching treatment to obtain the nitrogen-doped multi-walled carbon nanotube. However, the reaction conditions of the above patents are harsh, the nitrogen doping amount of the prepared nitrogen-doped carbon nanotube is not high, the specific surface area does not meet the requirements, and the application in industrial production is difficult.
Disclosure of Invention
The invention aims to solve the problem that the existing preparation method of the carbon nanotube material has some harsh requirements, the preparation process of the carbon nanotube material provided by the invention has the characteristics of easily available raw materials, convenient operation and mild reaction conditions, and the prepared nitrogen-doped carbon nanotube has the characteristics of high nitrogen doping amount, large specific surface area and the like and can be applied to actual production activities.
The purpose of the invention is realized by the following technical scheme:
a preparation method of nitrogen-doped carbon nanotubes comprises the following steps:
(1) adding a cobalt source into a reaction medium of water and ethanol, and synthesizing to obtain Co (OH) by adopting a hydrothermal method2Precursor, calcining, and adding Co (OH)2Conversion of precursor to Co3O4A nanowire;
(2) mixing Co3O4Adding nano-wire into trihydroxymethyl aminomethane buffer solution, adding dopamine, adding into Co3O4Wrapping a layer of polydopamine on the surface of the nanowire, carrying out high-temperature carbonization in an inert atmosphere, and finally etching by acid liquor, washing and drying to obtain the product.
Further, the method comprises the following specific steps:
(1) mixing high-purity water and ethanol in equal volume, adding a cobalt source and urea, and performing ultrasonic dispersion to obtain a mixed solution;
(2) carrying out constant temperature reaction on the mixed solution at a set temperature, cooling the reaction solution to room temperature after the reaction is finished to obtain a solid product, and carrying out centrifugal separation, washing and drying to obtain Co (OH)2A precursor;
(3) mixing Co (OH)2The precursor is heated to a set temperature at a certain heating rate and is kept for a period of time to obtain Co3O4A nanowire;
(4) mixing Co3O4The nanowire is placed at pH8.5, completely performing ultrasonic treatment, putting dopamine in the buffer solution, stirring, centrifuging, and vacuum drying to obtain Co3O4@ polydopamine;
(5) mixing Co3O4@ polydopamine is subjected to two-stage heat treatment in nitrogen or argon atmosphere, each stage of heat treatment is increased to a set temperature at a certain heating rate and is kept for a period of time to obtain Co3O4@ nitrogen-doped carbon;
(6) mixing Co3O4And (3) putting the @ nitrogen-doped carbon into a hydrochloric acid solution, stirring, washing with deionized water, and drying to obtain the product.
Further, the cobalt source is cobalt nitrate hexahydrate.
Further, the volume ratio of the mass of the cobalt nitrate hexahydrate to the volume of the ethanol is 0.01-0.04g/ml, and preferably 0.02 g/ml.
Further, the mass ratio of the urea to the cobalt nitrate hexahydrate is 1: 1-1.3.
Further, the reaction temperature of the mixed solution in the step (2) is 60-120 ℃, the reaction time is 6-10 hours, preferably the reaction temperature is 90 ℃, and the reaction time is 8 hours.
Further, in the step (3), the temperature rising rate is 1-5 ℃/min, the set temperature is 200 ℃ and 400 ℃, and the holding time is 2-4 hours, preferably, the temperature rising rate is 2 ℃/min, the set temperature is 300 ℃, and the holding time is 3 hours.
Further, the dopamine and Co in the step (4)3O4The mass ratio of the nano wires is 0.2-2: 1, preferably 0.4 to 1 by mass.
Further, the heating rate of the first stage heat treatment in the step (5) is 1-5 ℃/min, the temperature is kept at 300 ℃ and 700 ℃, and the time is kept for 1-3 hours; the temperature rise rate of the second stage heat treatment is 1-10 ℃/min, the holding temperature is 400-; the temperature rise rate of the second-stage heat treatment is 5 ℃/min, the temperature is kept at 600 ℃ and 800 ℃, and the holding time is 2 hours.
Further, the concentration of the hydrochloric acid solution in the step (6) is 0.05-2mol/L, the stirring time is 12-36 hours, and preferably, the concentration of the hydrochloric acid solution is 1mol/L, and the stirring time is 24 hours.
Compared with the prior art, the invention has the advantages that: the synthesis is carried out by adopting a hard template method, the material synthesis mechanism is that rich nitrogen source and carbon source are provided by introducing dopamine, and Co3O4The nanowires do not simply act as hard templates, but also provide a large number of active sites for nitrogen-doped carbon nanotubes. The adopted process steps have the characteristics of easily obtained raw materials of the preparation process, convenient operation, mild reaction conditions, high nitrogen doping amount, large specific surface area and the like of the prepared nitrogen-doped carbon nano tube, and the used raw materials do not react with each other. In the process, the coating of dopamine is a more critical step, and how to skillfully coat and coat with proper thickness has a decisive effect on the finally synthesized material nitrogen-doped nanotube. In a word, the method has a wide application prospect, and provides a good scheme in the aspects of actual production activities, theoretical basic research and the like.
Drawings
FIG. 1 shows Co in example 13O4Transmission electron microscopy of nanowires;
FIG. 2 is a TEM photograph of N-doped carbon nanotubes in example 2;
FIG. 3 is a high-power transmission electron micrograph of nitrogen-doped carbon nanotubes of example 2;
FIG. 4 is a TEM photograph of N-doped carbon nanotubes in example 3;
FIG. 5 is a high-power transmission electron micrograph of nitrogen-doped carbon nanotubes of example 3;
FIG. 6 is a TEM photograph of N-doped carbon nanotubes obtained in example 4;
fig. 7 is a high power transmission electron micrograph of the nitrogen doped carbon nanotube of example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
0.87g of cobalt nitrate hexahydrate and 0.72g of urea were dissolved in 40mL of ultrapure water and 40mL of ethanol, and placed in a 100mL hydrothermal reaction kettle with polytetrafluoroethylene for 5 minutes with sonication. And screwing down and sealing the hydrothermal reaction kettle, and standing in a constant-temperature oven at 90 ℃ for 8 hours. Washing the generated solid product with deionized water for three times, and standing in a constant-temperature oven at 80 ℃ for 12 hours to obtain Co (OH)2And (3) precursor. Mixing Co (OH)2Placing the precursor in a tube furnace, heating to 300 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and keeping at 300 ℃ for 3 hours to obtain Co3O4A nanowire. FIG. 1 shows Co3O4Transmission electron microscopy of nanowires.
Example 2
500mg of Co obtained in example 1 were taken3O4The nanowires were placed in tris buffer at pH 8.5 and sonicated for 20 minutes. Adding 500mg of dopamine into the suspension, stirring for 24 hours, centrifuging, and drying in vacuum to obtain Co3O4@ Polydopamine-500. Mixing Co3O4@ poly dopamine-500 is heated to 500 ℃ at a heating rate of 2 ℃/min in an argon atmosphere and is kept at 500 ℃ for 2 hours; then, the temperature was raised to 600 ℃ at a rate of 5 ℃/min and maintained at 600 ℃ for 2 hours. And placing the obtained solid in 100mL hydrochloric acid solution with the concentration of 1mol/L, stirring for 24 hours, washing with deionized water, and drying to obtain the nitrogen-doped carbon nanotube product. Fig. 2 is a tem photograph of the n-doped carbon nanotube, and fig. 3 is a tem photograph of the n-doped carbon nanotube. The chemical element analysis results showed that the nitrogen content in the product was 8.2%.
Example 3
500mg of Co obtained in example 1 were taken3O4The nanowires were placed in tris buffer at pH 8.5 and sonicated for 20 minutes. Adding 500mg of dopamine into the suspension, stirring for 24 hours, centrifuging, and drying in vacuum to obtain Co3O4@ Polydopamine-500. Mixing Co3O4@ Polydopamine-500 at 2 deg.C/min in an argon atmosphereThe temperature rising rate of the clock is increased to 500 ℃, and the clock is kept at 500 ℃ for 2 hours; then the temperature is raised to 700 ℃ at a heating rate of 5 ℃/min and kept at 700 ℃ for 2 hours. And placing the obtained solid in 100mL hydrochloric acid solution with the concentration of 1mol/L, stirring for 24 hours, washing with deionized water, and drying to obtain the nitrogen-doped carbon nanotube product. Fig. 4 is a tem photograph of the n-doped carbon nanotube, and fig. 5 is a tem photograph of the n-doped carbon nanotube. The chemical element analysis results showed that the nitrogen content in the product was 7.6%.
Example 4
500mg of Co obtained in example 1 were taken3O4The nanowires were placed in tris buffer at pH 8.5 and sonicated for 20 minutes. Adding 500mg of dopamine into the suspension, stirring for 24 hours, centrifuging, and drying in vacuum to obtain Co3O4@ Polydopamine-500. Mixing Co3O4@ poly dopamine-500 is heated to 500 ℃ at a heating rate of 2 ℃/min in an argon atmosphere and is kept at 500 ℃ for 2 hours; then the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min and kept at 800 ℃ for 2 hours. And placing the obtained solid in 100mL hydrochloric acid solution with the concentration of 1mol/L, stirring for 24 hours, washing with deionized water, and drying to obtain the nitrogen-doped carbon nanotube product. Fig. 6 is a tem photograph of the n-doped carbon nanotube, and fig. 7 is a tem photograph of the n-doped carbon nanotube. The analysis result of chemical elements shows that the nitrogen content in the product is 6.5%.
Example 5
500mg of Co obtained in example 1 were taken3O4The nanowires were placed in tris buffer at pH 8.5 and sonicated for 20 minutes. Adding 200mg of dopamine into the suspension, stirring for 24 hours, centrifuging, and drying in vacuum to obtain Co3O4@ Polydopamine-200. Mixing Co3O4@ polydopamine-200 is heated to 500 ℃ at a heating rate of 2 ℃/min in an argon atmosphere and is kept at 500 ℃ for 2 hours; then, the temperature was raised to 600 ℃ at a rate of 5 ℃/min and maintained at 600 ℃ for 2 hours. The obtained solid was placed in 100mL of a 1mol/L hydrochloric acid solutionStirring for 24 hours, washing with deionized water, and drying to obtain the nitrogen-doped carbon nanotube product. The chemical element analysis results showed that the nitrogen content in the product was 5.2%.
Example 6
500mg of Co obtained in example 1 were taken3O4The nanowires were placed in tris buffer at pH 8.5 and sonicated for 20 minutes. Adding 300mg of dopamine into the suspension, stirring for 24 hours, centrifuging, and drying in vacuum to obtain Co3O4@ polydopamine-300. Mixing Co3O4@ polydopamine-300 is heated to 500 ℃ at a heating rate of 2 ℃/min in an argon atmosphere and is kept at 500 ℃ for 2 hours; then, the temperature was raised to 600 ℃ at a rate of 5 ℃/min and maintained at 600 ℃ for 2 hours. And placing the obtained solid in 100mL hydrochloric acid solution with the concentration of 1mol/L, stirring for 24 hours, washing with deionized water, and drying to obtain the nitrogen-doped carbon nanotube product. The chemical element analysis results showed that the nitrogen content in the product was 6.1%.
Example 7
500mg of Co obtained in example 1 were taken3O4The nanowires were placed in tris buffer at pH 8.5 and sonicated for 20 minutes. Adding 400mg of dopamine into the suspension, stirring for 24 hours, centrifuging, and drying in vacuum to obtain Co3O4@ Polydopamine-400. Mixing Co3O4@ polydopamine-400 is heated to 500 ℃ at a heating rate of 2 ℃/min in an argon atmosphere and is kept at 500 ℃ for 2 hours; then, the temperature was raised to 600 ℃ at a rate of 5 ℃/min and maintained at 600 ℃ for 2 hours. And placing the obtained solid in 100mL hydrochloric acid solution with the concentration of 1mol/L, stirring for 24 hours, washing with deionized water, and drying to obtain the nitrogen-doped carbon nanotube product. The chemical element analysis results showed that the nitrogen content in the product was 7.2%.
The above description is a preferred embodiment of the present invention, but the present invention should not be limited to the disclosure of this embodiment. Therefore, it is intended that all equivalents and modifications which do not depart from the spirit of the invention disclosed herein are deemed to be within the scope of the invention.
Claims (9)
1. A preparation method of nitrogen-doped carbon nanotubes is characterized by comprising the following steps:
(1) mixing high-purity water and ethanol in equal volume, adding a cobalt source and urea, and performing ultrasonic dispersion to obtain a mixed solution;
(2) carrying out constant temperature reaction on the mixed solution at a set temperature, cooling the reaction solution to room temperature after the reaction is finished to obtain a solid product, and carrying out centrifugal separation, washing and drying to obtain Co (OH)2A precursor;
(3) mixing Co (OH)2The precursor is heated to a set temperature at a certain heating rate and is kept for a period of time to obtain Co3O4A nanowire;
(4) mixing Co3O4Placing the nano-wire in a trihydroxymethyl aminomethane buffer solution with the pH value of 8.5, completely performing ultrasonic treatment, placing dopamine in the buffer solution, stirring, centrifuging, and vacuum drying to obtain Co3O4@ polydopamine;
(5) mixing Co3O4@ polydopamine is subjected to two-stage heat treatment in nitrogen or argon atmosphere, each stage of heat treatment is increased to a set temperature at a certain heating rate and is kept for a period of time to obtain Co3O4@ nitrogen-doped carbon;
(6) mixing Co3O4Putting the @ nitrogen-doped carbon into a hydrochloric acid solution, stirring, washing with deionized water, and drying to obtain a product;
the reaction temperature of the mixed solution in the step (2) is 60-120 ℃, and the reaction time is 6-10 hours;
in the step (3), the heating rate is 1-5 ℃/min, the set temperature is 200 ℃ and 400 ℃, and the holding time is 2-4 hours;
step (5), the heating rate of the first stage of heat treatment is 1-5 ℃/min, the temperature is kept at 300-; the temperature rise rate of the second-stage heat treatment is 1-10 ℃/min, the temperature is kept at 400-;
the concentration of the hydrochloric acid solution in the step (6) is 0.05-2mol/L, and the stirring time is 12-36 hours.
2. The method of claim 1, wherein the cobalt source is cobalt nitrate hexahydrate.
3. The method of claim 2, wherein the volume ratio of the cobalt nitrate hexahydrate to the ethanol is 0.01-0.04 g/ml.
4. The method of claim 2, wherein the mass ratio of the urea to the cobalt nitrate hexahydrate is 1: 1-1.3.
5. The method as claimed in claim 2, wherein the temperature of the mixed solution in step (2) is 90 ℃ and the reaction time is 8 hours.
6. The method as claimed in claim 1, wherein the temperature of step (3) is increased at a rate of 2 ℃/min, the temperature is set at 300 ℃, and the holding time is 3 hours.
7. The method of claim 1, wherein the dopamine and Co in step (4) are added to the carbon nanotubes3O4The mass ratio of the nano wires is 0.2-2: 1.
8. the method of claim 1, wherein the first heat treatment in the step (5) has a temperature rise rate of 2 ℃/min, a temperature of 500 ℃ and a holding time of 2 hours; the temperature rise rate of the second-stage heat treatment is 5 ℃/min, the temperature is kept at 600 ℃ and 800 ℃, and the holding time is 2 hours.
9. The method as claimed in claim 1, wherein the hydrochloric acid solution in step (6) has a concentration of 1mol/L and a stirring time of 24 hours.
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| CN110600712B (en) * | 2019-10-08 | 2021-06-04 | 西京学院 | Carbon and nitrogen Co-doped Co3O4Composite material, preparation method and application thereof |
| CN113479863B (en) * | 2021-06-03 | 2022-10-25 | 佛山市格瑞芬新能源有限公司 | Hierarchical porous carbon nanotube and preparation method and application thereof |
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| CN113526492A (en) * | 2021-07-29 | 2021-10-22 | 深圳齐锂纳米科技有限公司 | Preparation method of in-situ generated nitrogen-doped carbon nano tube |
| CN114276781B (en) * | 2021-12-07 | 2023-09-29 | 中国科学院宁波材料技术与工程研究所 | MO@NC core-shell structure type nano wave-absorbing material and preparation method thereof |
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