CN111483999A - Preparation method of nitrogen-doped carbon nanotube, nitrogen-doped carbon nanotube and application of nitrogen-doped carbon nanotube - Google Patents
Preparation method of nitrogen-doped carbon nanotube, nitrogen-doped carbon nanotube and application of nitrogen-doped carbon nanotube Download PDFInfo
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Abstract
The invention provides a preparation method of a nitrogen-doped carbon nanotube, which comprises the following steps: (1) adding ferric trichloride and calcium chloride into a first porcelain boat, adding a low-boiling-point alcohol solvent for dissolving, and evaporating the low-boiling-point alcohol solvent after uniformly mixing; (2) and putting melamine into a second porcelain boat, separately putting the first porcelain boat and the second porcelain boat into a tube furnace, driving air in the tube furnace by using inert gas, closing the air inlet end of the tube furnace, pricking the air outlet end into an air collecting container, heating for calcining, and pickling, washing and drying to obtain the nitrogen-doped carbon nanotube. The prepared nitrogen-doped carbon nano tube is bamboo-like, has thin tube wall, uniform shape, concentrated pore size distribution and high nitrogen content, and greatly improves the catalytic performance or the capacitance activity; the preparation method has the advantages of cheap and easily obtained raw materials, simple equipment, easy and controllable preparation process, no use of a large amount of corrosive gas, safety, energy conservation, environmental friendliness, lower production cost and high yield.
Description
Technical Field
The invention particularly relates to a preparation method of a nitrogen-doped carbon nanotube, the nitrogen-doped carbon nanotube and application thereof.
Background
Carbon Nanotubes (CNTs) have been widely studied in the fields of electronics, biological probes, field emission, heat conduction, specialty materials, particularly in the environmental and energy fields, due to their large long diameter and specific surface area, and excellent mechanical properties. Carbon nanotubes have excellent applications as candidate materials, such as electrode materials, exchange membranes, catalysts, sensors, microelectronic elements, fuel cells, and the like. Carbon nanotubes are the hot spot of current research and have considerable potential for commercial exploitation. The current method for preparing carbon nanotubes is: graphite arc process, floating catalyst process, laser vapor process, pyrolytic polymer process, chemical vapor deposition. Among these methods, the chemical vapor deposition method is widely used as a method for preparing carbon nanotubes because it can adjust experimental conditions such as a carbon source, a catalyst, and a synthesis atmosphere. However, the use of carrier gas in the method causes low yield of the carbon nano tube, high operation cost and complex tail gas treatment; at the same time, the differences between the solid phase catalyst particles make the morphology of the resulting carbon nanotubes somewhat uniform.
The homogeneous medium method is a green process for preparing controllable nano materials, the environment for elementary growth of the materials in the homogeneous medium is completely the same, and the method has the advantages of cheap and easily-obtained raw materials, simple preparation process and low cost.
In view of the above problems, it is necessary to develop a method that combines the homogeneous medium method with the chemical vapor deposition method, so as to solve the problem of non-uniform morphology of the carbon nanotubes.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a nitrogen-doped carbon nanotube by using an improved chemical vapor deposition method, a nitrogen-doped carbon nanotube and applications thereof, wherein the prepared nitrogen-doped carbon nanotube is in a bamboo knot shape and has characteristics of uniform shape and uniform pore size distribution.
The first purpose of the invention is to provide a preparation method of nitrogen-doped carbon nanotubes, which comprises the following steps:
(1) adding ferric trichloride and calcium chloride into a first porcelain boat, adding a low-boiling-point alcohol solvent for dissolving, and evaporating the low-boiling-point alcohol solvent after uniformly mixing;
(2) and putting melamine into a second porcelain boat, putting the first porcelain boat and the second porcelain boat into a tube furnace separately, introducing inert gas to remove air in the tube furnace, closing the air inlet end of the tube furnace, pricking the air outlet end into an air collecting container, heating for calcining, and pickling, washing and drying to obtain the nitrogen-doped carbon nanotube.
In the invention, ferric trichloride and calcium chloride are fully and uniformly mixed, and then a liquid-phase molten salt system is formed at high temperature in a tubular furnace and is used as a liquid medium in the chemical vapor deposition process, so that the uniformity of the growth environment in the formation process of the carbon nano tube is ensured, and the uniformity of the morphology of the generated carbon nano tube is improved.
In the invention, the gas inlet end and the gas outlet end are adjusted in the tubular furnace to create the static atmosphere in the chemical vapor deposition, thereby avoiding the use of carrier gas, saving the consumption of gas and avoiding a severe tail gas absorption device.
Specifically, in the step (1), the feeding molar ratio of the ferric trichloride to the calcium chloride is 0.5-2.5: 1.
Specifically, in the step (1), the low-boiling alcohol solvent is ethanol or propanol. In the invention, a low-boiling-point alcohol solvent is used as a solvent, a solution of ferric trichloride hexahydrate and calcium chloride of the low-boiling-point alcohol solvent is formed, and the shape and the area of a deposition area are changed by utilizing the liquidity of the solution.
Specifically, in the step (2), the temperature of the calcination is 600-1000 ℃.
Specifically, the molar ratio of the total feeding of the ferric trichloride and the calcium chloride to the feeding of the melamine is 1: 30-260.
The melamine can be used as a carbon source and a nitrogen source and can also be used as a synthetic atmosphere of chemical vapor deposition; the excess melamine can be recovered for reuse after carbonization.
Specifically, the nitrogen-doped carbon nanotube has a uniform structure, a length of 8-15 μm, a tube diameter of 60-100nm, and is a bamboo-like carbon nanotube with an open end.
The second objective of the present invention is to provide a nitrogen-doped carbon nanotube prepared by the method for preparing a nitrogen-doped carbon nanotube.
A third object of the present invention is to provide a use of the nitrogen-doped carbon nanotube as described above in fuel cells, electrolytic water and metal air cells.
Compared with the prior art, the prepared nitrogen-doped carbon nanotube is bamboo-like, has thin tube wall, uniform shape, concentrated pore size distribution and high nitrogen content, and greatly improves the catalytic performance or the capacitance activity; the preparation method has the advantages of cheap and easily obtained raw materials, simple equipment, easy and controllable preparation process, no use of a large amount of corrosive gas, safety, energy conservation, environmental friendliness, lower production cost and high yield.
Drawings
FIG. 1(a) schematic representation of example 1 before carbonization; (b) example 1 schematic representation after carbonization; (c) comparative example 1 schematic before carbonization; (d) comparative example 1 schematic after carbonization; (e) comparative example 2 schematic before carbonization; (f) comparative example 2 schematic after carbonization;
FIG. 2(a) SEM image of nitrogen-doped carbon nanotubes prepared in example 1; (b) TEM images of nitrogen-doped carbon nanotubes prepared in example 1; (c) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 1; (d) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 2;
FIG. 3(a) SEM image of nitrogen-doped carbon nanotubes prepared in example 2; (b) SEM image of nitrogen-doped carbon nanotubes prepared in example 3; (c) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 3; (d) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 4;
FIG. 4(a) SEM image of nitrogen-doped carbon nanotubes prepared in example 4; (b) SEM image of nitrogen-doped carbon nanotubes prepared in example 5; (c) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 5; (d) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 6;
FIG. 5(a) SEM image of N-doped carbon nanotubes prepared in example 6; (b) SEM image of nitrogen doped carbon nanotubes prepared in example 7; (c) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 7; (d) SEM image of nitrogen-doped carbon nanotubes prepared in comparative example 8;
FIG. 6 is a comparative BET test pattern of the N-doped carbon nanotubes prepared in example 1 and comparative examples 1-2;
FIG. 7 is a graph showing a comparison of pore size distributions of nitrogen-doped carbon nanotubes prepared in example 1 and comparative examples 1-2;
FIG. 8 shows the results of example 1 as a catalyst and a conventional Pt/C catalyst at 0.1mol L-1ORR test in KOH solution of (a);
FIG. 9 shows the catalyst prepared in example 1 at 1mol L-1OER test patterns in KOH solution;
FIG. 10 shows the catalyst prepared in example 1 and Pt/C + RuO2Power density contrast plots for tests of zinc-air cells assembled with the catalyst as an air cathode;
FIG. 11 is a full hydrolysis test chart of the catalyst prepared in example 1.
Detailed Description
The first purpose of the invention is to provide a preparation method of nitrogen-doped carbon nanotubes, which comprises the following steps:
(1) adding ferric trichloride and calcium chloride into a first porcelain boat, adding a low-boiling-point alcohol solvent (ethanol or propanol) for dissolving, and evaporating the low-boiling-point alcohol solvent after uniformly mixing; the feeding molar ratio of the ferric trichloride to the calcium chloride is 0.5-2.5: 1.
(2) Putting melamine into a second porcelain boat, putting the first porcelain boat and the second porcelain boat into a tube furnace separately, introducing inert gas to remove air in the tube furnace, pricking a gas container (selecting a balloon in the invention) at an air outlet end, closing the air inlet end of the tube furnace, heating for calcination, pickling, washing with water, and drying to obtain the nitrogen-doped carbon nanotube (the nitrogen-doped carbon nanotube has a uniform structure, a length of 8-15 μm, a tube diameter of 60-100nm, and is a bamboo-like carbon nanotube with an opening at the tail end). The temperature of calcination is 600-1000 ℃. The molar ratio of the total feeding of ferric trichloride and calcium chloride to the feeding of melamine is 1: 30-260.
The second objective of the present invention is to provide a nitrogen-doped carbon nanotube prepared by the above method.
The third purpose of the invention is to provide the application of the nitrogen-doped carbon nano tube in fuel cells and water electrolysis.
Applications are now listed as follows:
the application one is as follows: the catalyst can be directly used as an oxygen reduction catalyst of a fuel cell. The method comprises the following specific steps: the prepared bamboo-shaped nitrogen-doped carbon nano tube, Nafion solution and alcohol (methanol, ethanol or isopropanol) are mixed, ultrasonic treatment is carried out, and the obtained solution is sprayed on a proton exchange membrane of a fuel cell and is used as an oxygen reduction electrode of the fuel cell.
The bamboo-shaped nitrogen-doped carbon nano tube prepared by the invention contains a large number of defect sites, can be used as a carrier of a noble metal platinum catalyst and is applied to an oxygen reduction catalyst of a fuel cell, and the specific application steps comprise adding 100mg of sodium citrate into 20m L water, adjusting the pH value to 7 by using 3 mol/L ammonia water, slowly dropwise adding 3.3m L chloroplatinic acid and 100mg of Fe @ NCNTs powder (prepared by the invention), stirring uniformly, performing ultrasonic treatment for 0.5h, adjusting the pH value to 8-9 by using the ammonia water, and dropwise adding 80mg of NaBH to the solution4And 10m L of water, stirring for 0.5-16h, filtering the product until the filtrate becomes neutral, and vacuum drying the obtained sample.
The application is as follows: application of nitrogen-doped carbon nanotubes in electrolytic water.
The prepared nitrogen-doped carbon nanotube catalyst, polymer binder PTFE, acetylene black and carbon are dispersed in isopropanol to prepare uniform slurry to prepare the cathode of the metal-air battery. The slurry was prepared as a sheet, and after drying, the sheet was pressed against the nickel foam at a pressure of 20 MPa. The pressed pole piece can be used as an oxygen evolution reaction electrode (OER) in electrolytic water.
And application four: the nitrogen-doped carbon nanotube is applied to a metal-air battery.
The prepared nitrogen-doped carbon nanotube catalyst, polymer binder PTFE, acetylene black and carbon are dispersed in isopropanol to prepare uniform slurry to prepare the cathode of the metal-air battery. The slurry was prepared as a sheet, and after drying, the sheet was pressed against the nickel foam at a pressure of 20 MPa. The pressed pole piece can be used as an oxygen reduction reaction electrode (ORR) in a metal-air battery. The anode of the metal air electrode is made of zinc foil, and the electrolyte is KOH solution.
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry.
(1) 0.02705g of ferric chloride hexahydrate and 0.0058g of calcium chloride are added into a first porcelain boat, 5m of L of ethanol is added for dissolution, and the ethanol is evaporated after uniform mixing;
(2) 2.5g of melamine is put into a second porcelain boat, the first porcelain boat and the second porcelain boat are separately put into a tube furnace, inert gas is used for driving away air in the tube furnace, the air inlet end of the tube furnace is closed, the temperature is raised for calcination, and the temperature is increased for 2.5 ℃ min-1The heating rate of (3) is increased to 800 ℃ and maintained at this temperature for 120 min; subsequently, at 5 ℃ for min-1The cooling rate of (a) cools the temperature to 30 ℃. Then 1M HNO3And treating the solution for 24 hours to remove unstable Fe species, washing the solution to be neutral by water, and drying the solution for 12 hours at the temperature of 60 ℃ to obtain the nitrogen-doped carbon nanotube.
The N-doped carbon nanotube prepared in this example is labeled as Fe @ NCNTs-1.
Embodiment 4 this example provides a method for preparing nitrogen-doped carbon nanotubes, nitrogen-doped carbon nanotubes and applications thereof, which are substantially the same as those in embodiment 1, except that: in step (2), 1.25g of melamine was added.
Example 7 this example provides a method of fabricating nitrogen-doped carbon nanotubes, and applications thereof, which are substantially the same as in example 1, except that: in the step (2), the temperature of calcination was 1000 ℃.
Comparative example 1 this comparative example provides a method for preparing nitrogen-doped carbon nanotubes, nitrogen-doped carbon nanotubes and their use, which is substantially the same as in example 1 except that in step (1), 0.02705g of ferric chloride hexahydrate are added to a first porcelain boat, 5m of L ethanol is added for dissolution, the ethanol is evaporated after uniform mixing, and step (2) is the same as in example 1.
The nitrogen-doped carbon nanotube prepared in this comparative example was labeled as Fe @ NCNTs-2.
Comparative example 2 this comparative example provides a method for preparing a nitrogen-doped carbon nanotube, a nitrogen-doped carbon nanotube and applications thereof, comprising the steps of:
(1) 0.02705g of ferric chloride hexahydrate, 0.0058g of calcium chloride and 2.5g of melamine were added to a zirconium casserole and ball-milled at 550rpm for 6 hours;
(2) and (2) placing the solid powder obtained in the step (1) into a tube furnace, driving the air in the tube furnace with inert gas, and closing the air inlet end of the tube furnace to keep the tube furnace in a static atmosphere. At 2.5 ℃ for min-1The heating rate of (3) is increased to 800 ℃ and maintained at this temperature for 120 min; subsequently, at 5 ℃ for min-1The cooling rate of (a) cools the temperature to 30 ℃. Then 1M HNO3And treating the solution for 24 hours to remove unstable Fe species, washing the solution to be neutral by water, and drying the solution for 12 hours at the temperature of 60 ℃ to obtain the nitrogen-doped carbon nanotube.
The nitrogen-doped carbon nanotube prepared in this comparative example was labeled as Fe @ NCNTs-3.
Comparative example 3 this comparative example provides a method for preparing nitrogen-doped carbon nanotubes, nitrogen-doped carbon nanotubes and their use, which is substantially the same as in example 1 except that: 0.01g of ferric chloride hexahydrate was added.
Comparative example 4 this comparative example provides a method for preparing nitrogen-doped carbon nanotubes, nitrogen-doped carbon nanotubes and their use, which is substantially the same as in example 1 except that: 0.03g of ferric chloride hexahydrate was added.
Comparative example 5 this comparative example provides a method of preparing nitrogen-doped carbon nanotubes, which is substantially the same as in example 1 except that: in step (2), 0.625g of melamine was added.
Comparative example 6 this comparative example provides a method for preparing nitrogen-doped carbon nanotubes, nitrogen-doped carbon nanotubes and their use, which is substantially the same as in example 1 except that: in step (2), 5.0g of melamine was added.
Comparative example 7 this comparative example provides a method of preparing nitrogen-doped carbon nanotubes, nitrogen-doped carbon nanotubes and their use, which is substantially the same as in example 1 except that: in the step (2), the temperature of calcination was 500 ℃.
Comparative example 8 this comparative example provides a method for preparing nitrogen-doped carbon nanotubes, nitrogen-doped carbon nanotubes and their use, which is substantially the same as in example 1 except that: in the step (2), the temperature of calcination was 1100 ℃.
FIGS. 1(a) and (b) are schematic views before and after carbonization in example 1, respectively, FIGS. 1(c) and (d) are schematic views before and after carbonization in comparative example 1, respectively, and FIGS. 1(e) and (f) are schematic views before and after carbonization in comparative example 2, respectively. Through the explanation, the low-temperature molten salt acts as a liquid phase medium and has fluidity and regulation performance.
FIG. 2(a-b) shows that the Fe @ NCNT-1 prepared by the invention has a uniform structure, a length of 8-15 μm, a tube diameter of 60-100nm and a bamboo-like carbon nanotube with an open end.
FIGS. 3(a-d) are SEM images of samples prepared in examples 2-3 and comparative examples 3-4, respectively, at different amounts of ferric trichloride hexahydrate. The comparison shows that the carbon nano tube prepared under the appropriate Fe content has more uniform appearance and low impurity content of the sample.
FIGS. 4(a-d) are SEM images of samples prepared in examples 4-5 and comparative examples 5-6, respectively, at different amounts of melamine. The comparison shows that the proper amount of melamine can ensure the morphology of the formed carbon nano tube, reduce the content of amorphous carbon in the sample and reduce the consumption of the medicine.
FIGS. 5(a-d) are SEM images of samples prepared in examples 6-7 and comparative examples 7-8 at different calcination temperatures in this order. By contrast, temperature affects the formation of carbon nanotubes.
FIG. 6 is a comparative BET test pattern of the N-doped carbon nanotubes prepared in example 1 and comparative examples 1-2; as can be seen from the figure, the specific surface area of Fe @ NCNTs-1 prepared in example 1 is 137.5m2In terms of/g, the specific surface area of Fe @ NCNTs-2 prepared in comparative example 1 was 79.7m/g, and that of comparative example 2 was 58.08m2The BET test data results for example 1 are therefore much higher than for comparative examples 1-2.
FIG. 7 is a graph showing a comparison of pore size distributions of nitrogen-doped carbon nanotubes prepared in example 1 and comparative examples 1-2; the pore size distribution of the bamboo-like carbon nanotube in example 1 is mainly mesoporous, and is mainly distributed around 3-6nm, which indicates that the bamboo-like carbon nanotube has many active sites and many defect centers.
FIG. 8 shows the results of example 1 as a catalyst and a conventional Pt/C catalyst at 0.1mol L-1ORR test in KOH solution of (a); compared with a Pt/C catalyst, the Fe @ NCNTs-1 catalyst prepared by the invention has the advantages that the initial potential and the half-wave point position are respectively 0.95V and 0.81V, and the good oxygen reduction performance is shown.
FIG. 9 shows the catalyst prepared in example 1 at 1mol L-1OER test patterns in KOH solution; fe @ NCNTs-1 at 2mA cm-2～10mA cm-2All over-potentials of the current density of the standard material are less than RuO2The overpotential of (2) shows that Fe @ NCNTs-1 is excellent in oxygen evolution performance.
FIG. 10 is a graph of power density versus test for a zinc-air cell assembled with the catalyst prepared in example 1 and Pt/C + RuO2 catalyst as an air cathode; the invention is at 200mA cm-2The power can reach 160mW cm under the current density of-2。
FIG. 11 is a full hydrolysis test pattern of the catalyst prepared in example 1; indicating that full water splitting can be performed.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A preparation method of nitrogen-doped carbon nanotubes is characterized by comprising the following steps:
(1) adding ferric trichloride and calcium chloride into a first porcelain boat, adding a low-boiling-point alcohol solvent for dissolving, and evaporating the low-boiling-point alcohol solvent after uniformly mixing;
(2) and putting melamine into a second porcelain boat, putting the first porcelain boat and the second porcelain boat into a tube furnace separately, introducing inert gas to remove air in the tube furnace, closing the air inlet end of the tube furnace, pricking the air outlet end into an air collecting container, heating for calcining, and pickling, washing and drying to obtain the nitrogen-doped carbon nanotube.
2. The method of claim 1, wherein the nitrogen-doped carbon nanotube is prepared by: in the step (1), the feeding molar ratio of the ferric trichloride to the calcium chloride is 0.5-2.5: 1.
3. The method of claim 1, wherein the nitrogen-doped carbon nanotube is prepared by: in the step (1), the low-boiling-point alcohol solvent is ethanol or propanol.
4. The method of claim 1, wherein the nitrogen-doped carbon nanotube is prepared by: in the step (2), the calcination temperature is 600-1000 ℃.
5. The method of claim 1, wherein the nitrogen-doped carbon nanotube is prepared by: the molar ratio of the total feeding of the ferric trichloride hexahydrate and the calcium chloride to the feeding of the melamine is 1: 30-260.
6. The method of claim 1, wherein the nitrogen-doped carbon nanotube is prepared by: the nitrogen-doped carbon nano tube has a uniform structure, the length of 8-15 mu m and the tube diameter of 60-100nm, and is a bamboo-like carbon nano tube with an open end.
7. A nitrogen-doped carbon nanotube produced by the method for producing a nitrogen-doped carbon nanotube according to any one of claims 1 to 6.
8. Use of the nitrogen-doped carbon nanotubes of claim 7 in fuel cells, electrolytic water and metal air cells.
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| CN113066994A (en) * | 2021-03-17 | 2021-07-02 | 宁波材料所杭州湾研究院 | Carbon material/platinum composite material rich in topological defects, and preparation method and application thereof |
| CN114000164A (en) * | 2021-11-03 | 2022-02-01 | 深圳市橘井舒泉技术有限公司 | Novel oxygen evolution electrode and preparation method thereof |
| CN114005973A (en) * | 2021-11-02 | 2022-02-01 | 贵州梅岭电源有限公司 | Preparation method and application of heteroatom modified composite negative electrode material |
| CN114094125A (en) * | 2021-10-13 | 2022-02-25 | 江苏大学 | CoFe/CeO2Preparation method and application of-nitrogen-doped carbon nanotube composite electrode catalyst material |
| CN114318412A (en) * | 2022-01-27 | 2022-04-12 | 江西师范大学 | Limited-domain N-doped Fe nano-particles and preparation method and application thereof |
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