CN108821266B - Preparation method of nitrogen-doped graphene - Google Patents
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Abstract
Adding metered lime nitrogen, a carbon source and deionized water into a beaker respectively, controlling the temperature of a water bath at 60-80 ℃, stirring, adjusting the pH of a reaction material to 9-12, reacting for 3-5 h, uniformly spreading the reaction material into an enamel tray, drying, and uniformly grinding the material to obtain solid powder; transferring the solid powder into a porcelain boat, putting the porcelain boat into a tubular furnace for pyrolysis, introducing nitrogen into the furnace for protection, heating the tubular furnace to 540-580 ℃ at a speed of 1-3 ℃/min, preserving heat for 2-3 h, heating to 750-950 ℃ at a speed of 3-8 ℃/min, preserving heat for 1-2 h, then naturally cooling to room temperature, soaking the product with dilute hydrochloric acid, washing with water for multiple times until the product is neutral, and drying to obtain the nitrogen-doped graphene. The method uses cheap lime nitrogen as a raw material, and does not need to use a metal catalyst in the preparation process, thereby reducing the production cost and simplifying the production process.
Description
Technical Field
The invention belongs to the technical field of preparation and application of carbon materials, and particularly relates to a preparation method of nitrogen-doped graphene.
Background
The graphene is a two-dimensional periodic honeycomb lattice structure consisting of carbon six-membered rings, has the advantages of high conductivity, high thermal conductivity, high mechanical strength and the like, and the composite material of the graphene also has excellent performance. However, since graphene has no band gap, its conductivity cannot be completely controlled as in a conventional semiconductor, and graphene has a smooth and inert surface and weak interaction with other media, and in addition, graphene sheets have strong acting force and are easy to aggregate, so that graphene is not easily compounded with other materials, thereby hindering its application. At present, the electronic structure of graphene is changed and the active sites of metal particles adsorbed on the surface of the graphene are increased mainly by doping nitrogen elements into the graphene, so that the conductivity and stability of the graphene are improved, the interaction between the graphene and the metal particles is enhanced, and the application range of the graphene is further expanded.
The currently common methods for preparing nitrogen-doped graphene mainly comprise: (1) chemical Vapor Deposition (CVD) is a process in which gaseous precursors are reacted on a substrate to form a thin film. The method is characterized in that pentachloropyridine is used as a precursor for Cui P, Choi J-H and the like, nitrogen-doped graphene (Cui P, Choi J-H, Zeng C, Li Z, Wang J, Zhang Z.J.Am.chem.Soc.,2017,139:7196-7202.) is prepared on the surface of copper, a metal catalyst is needed in the method, and the separation of the metal catalyst and the nitrogen-doped graphene is difficult and the process is complex; (2) the nitrogen doping method of graphene oxide is characterized in that graphene oxide is used as a raw material, a nitrogen-containing substance is used as a nitrogen source, and nitrogen is doped under the high-temperature or hydrothermal condition. Taking graphene oxide as a raw material, taking acetonitrile or ammonia water as a nitrogen source, and carrying out nitrogen doping at high temperature by Tang P, GaoY J and the like to obtain nitrogen-doped graphene oxide (Tang P, Gao Y J, Yang J H, Li W J, ZHaoH Z, Ma D.Chin.J.Catal.,2014,35(6): 922-928); the patent with publication number CN104465113 discloses a method for preparing nitrogen-doped graphene by a hydrothermal method, which is to mix graphene oxide serving as a raw material with urea and sulfuric acid, and then perform hydrothermal reaction for 2 hours at 180 ℃ to obtain the nitrogen-doped graphene. Because graphene oxide is not easily available, the cost is high, and the method is limited; (3) a nitrogen-containing precursor conversion method comprises the steps of mixing a nitrogen-containing substance with a transition metal compound catalyst (such as iron salt, cobalt salt and nickel salt), reacting at a high temperature, and removing a metal compound to obtain the nitrogen-doped graphene. Glucose, ferric chloride and urea are dissolved in water by Wang C, Kang J and the like, the water is dried for 24 hours at 80 ℃, pyrolysis is carried out at 700 ℃, and iron is removed by hydrochloric acid to obtain nitrogen-doped graphene (Wang C, Kang J, Sun H, Ang H M, Tade M O, Wang S.Carbon,2016,102: 279-287.), and a metal catalyst used in the method can generate metal carbide and is difficult to completely remove, so that later-stage use is influenced. Because the method has a plurality of problems, the preparation method which has simple process, easily obtained raw materials, lower cost and no need of using metal catalyst is very important to find.
Disclosure of Invention
The invention aims to provide a preparation method of nitrogen-doped graphene, which does not need to use a metal catalyst, thereby omitting the step of separating the metal catalyst and the nitrogen-doped graphene, avoiding the generation of metal carbide in the manufacturing process and simplifying the process; in addition, the invention uses cheap lime nitrogen as raw material, which can reduce production cost.
In order to achieve the purpose, the preparation method of the nitrogen-doped graphene comprises the following steps:
(1) respectively adding the measured lime nitrogen, carbon source and deionized water into a beaker, heating in a water bath while stirring to obtain a reaction material, controlling the temperature of the water bath to be 60-80 ℃, introducing carbon dioxide gas into the beaker until the pH of the reaction material is 9-12, uniformly spreading the reaction material into an enamel plate after reacting for 3-5 h, then placing the enamel plate in a blast drying oven at 45-55 ℃ for drying for 3.5-4.5 h, and finally transferring the dried material in the enamel plate into a mortar for uniformly grinding to obtain solid powder; the mass ratio of the lime nitrogen to the carbon source to the deionized water is (1-4): 1: (2-20);
(2) transferring the solid powder obtained in the step (1) into a porcelain boat, putting the porcelain boat and the solid powder into a tubular furnace for pyrolysis, introducing nitrogen into the tubular furnace for protection, heating the tubular furnace to 540-580 ℃ in a furnace cavity at the speed of 1-3 ℃/min, preserving heat for 2-3 h, heating to 750-950 ℃ in the furnace cavity at the speed of 3-8 ℃/min, preserving heat for 1-2 h, taking out a product after the temperature in the furnace cavity is naturally cooled to room temperature, soaking the product in dilute hydrochloric acid, washing and filtering, washing with distilled water to be neutral, and drying the product at 75-85 ℃ for 3.5-4.5 h to obtain the nitrogen-doped graphene.
Preferably, the temperature of the water bath in the step (1) is 70 ℃, the pH of the reaction mass is controlled to be 10, and the reaction is carried out for 4 hours.
Preferably, in the step (2), the temperature of the tubular furnace is firstly increased to 550 ℃ at the speed of 2 ℃/min, and the temperature is kept for 2.5 hours.
Preferably, the temperature of the tubular furnace in the step (2) is raised to 850 ℃ at the speed of 5 ℃/min, and the temperature is kept for 1.5 h.
Preferably, the mass ratio of the lime nitrogen to the carbon source and the deionized water in the step (1) is 2.5: 1: 10.
preferably, the carbon source is one or more of citric acid, tartaric acid, malic acid, glucose, sucrose and fructose.
Preferably, in the step (1), the enamel plate is placed in an air drying oven at 50 ℃ for drying for 4 hours; and (3) finally, drying the product at 80 ℃ for 4h to obtain the nitrogen-doped graphene.
The method takes cheap lime nitrogen as a nitrogen source, obtains a mixture of dicyandiamide and calcium carbonate after hydrolysis and polymerization, carries out high-temperature pyrolysis on dicyandiamide, calcium carbonate and a carbon source, polymerizes dicyandiamide to generate graphite-phase carbon nitride in the pyrolysis process, and carbonizes the surface of the carbon source by taking the graphite-phase carbon nitride and the calcium carbonate as template agents. With the continuous rise of the temperature, the pyrolysis reaction is continuously carried out, the graphite-phase carbon nitride is further decomposed into small-molecular nitrogen-containing compounds, and the compounds are used as nitrogen dopants to carry out nitrogen doping on the carbonized product, so that the nitrogen-doped graphene is finally obtained.
Compared with the prior art, the method obtains the nitrogen-doped graphene through the pyrolysis method at high temperature and normal pressure, has simple process, does not need to use complex and expensive instruments and equipment, and is easy for industrial production; the raw materials in the invention are cheap and easy to obtain, and no special treatment is needed, the hydrolysate of lime nitrogen is used as a template agent and a nitrogen doping agent, and no additional metal or metal compound is needed in the preparation process, so that the production process is effectively simplified and the production cost is reduced; the nitrogen-doped graphene obtained by the preparation method is used as a catalyst for reducing p-nitrophenol by sodium borohydride, has high catalytic activity and has potential utilization value in the aspect of sewage treatment.
Drawings
Fig. 1 is a transmission electron microscope image of nitrogen-doped graphene prepared in example two of the present invention;
FIG. 2 is an X-ray diffraction pattern of nitrogen-doped graphene prepared according to example two of the present invention;
FIG. 3 is an X-ray photoelectron spectrum of nitrogen-doped graphene prepared according to example two of the present invention;
fig. 4 is a pore size distribution curve of nitrogen-doped graphene prepared in example two of the present invention;
fig. 5 is an isothermal adsorption-desorption curve of nitrogen-doped graphene prepared in example two of the present invention;
FIG. 6 is a diagram of an ultraviolet-visible spectrum of a nitrogen-doped graphene catalyzed sodium borohydride reduced p-nitrophenol prepared in example two of the present invention;
fig. 7 is a repetitive histogram of the reduction of p-nitrophenol by nitrogen-doped graphene catalyzed sodium borohydride prepared in the second embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples.
Example one
A preparation method of nitrogen-doped graphene comprises the following steps:
(1) adding the metered lime nitrogen, carbon source and deionized water into a beaker, heating in a water bath while stirring to obtain a reaction material, controlling the temperature of the water bath to be 60 ℃, introducing carbon dioxide gas into the beaker until the pH of the reaction material is 9, uniformly spreading the reaction material into an enamel plate after reacting for 5 hours, then placing the enamel plate in a 45 ℃ blast drying oven for drying for 4.5 hours, and finally transferring the dried material in the enamel plate to a grinding machine for uniformly grinding to obtain solid powder; the mass ratio of the lime nitrogen to the carbon source to the deionized water is 1: 1: 2; the carbon source is one or more of citric acid, tartaric acid, malic acid, glucose, sucrose and fructose;
(2) transferring the solid powder obtained in the step (1) into a porcelain boat, putting the porcelain boat and the solid powder into a tubular furnace together for pyrolysis, introducing nitrogen into the tubular furnace for protection, heating the tubular furnace to 540 ℃ at the speed of 1 ℃/min, preserving the heat for 3h, heating to 750 ℃ at the speed of 3 ℃/min, preserving the heat for 2h, naturally cooling the temperature in the furnace to room temperature, taking out the product, soaking the product in dilute hydrochloric acid, washing and filtering the product, washing the product with distilled water to be neutral, and finally drying the product at 75 ℃ for 4.5h to obtain the nitrogen-doped graphene.
The prepared sample is characterized by a transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, pore size distribution, isothermal adsorption-desorption curve and the like, and the result shows that the prepared sample is nitrogen-doped graphene, the pore size is mainly micropores, and the specific surface area is 181.5m2The nitrogen content (atomic%) was 10.89%.
Example two
A preparation method of nitrogen-doped graphene comprises the following steps:
(1) respectively adding the metered lime nitrogen, the carbon source and the deionized water into a beaker, heating in a water bath while stirring to obtain a reaction material, controlling the temperature of the water bath to be 70 ℃, introducing carbon dioxide gas into the beaker until the pH of the reaction material is 10, uniformly spreading the reaction material into an enamel plate after reacting for 4 hours, then placing the enamel plate in a blast drying oven at 50 ℃ for drying for 4 hours, and finally transferring the dried material in the enamel plate into a mortar for uniformly grinding to obtain solid powder; the mass ratio of the lime nitrogen to the carbon source to the deionized water is 2.5: 1: 10; the carbon source is one or more of citric acid, tartaric acid, malic acid, glucose, sucrose and fructose;
(2) transferring the solid powder obtained in the step (1) into a porcelain boat, putting the porcelain boat and the solid powder into a tubular furnace together for pyrolysis, introducing nitrogen into the tubular furnace for protection, heating the tubular furnace to 550 ℃ at the speed of 2 ℃/min, preserving the heat for 2.5h, heating to 850 ℃ at the speed of 5 ℃/min, preserving the heat for 1.5h, naturally cooling the temperature in the furnace to room temperature, taking out the product, soaking the product in dilute hydrochloric acid, washing and filtering the product, washing the product with distilled water to be neutral, and finally drying the product at 80 ℃ for 4h to obtain the nitrogen-doped graphene.
The transmission electron microscope image, the X-ray diffraction pattern, the X-ray photoelectron spectrum, the pore size distribution curve and the isothermal adsorption-desorption curve of the nitrogen-doped graphene prepared in the above steps are respectively shown in fig. 1, fig. 2, fig. 3, fig. 4 and fig. 5.
As can be seen from fig. 1, the sample prepared in this example is randomly stacked from transparent and wrinkled thin sheet-like materials, indicating that the product is graphene.
As can be seen from fig. 2, there are two diffraction peaks at about 26 ° and 43 ° in the graph, which correspond to the (002) and (100) crystal planes of graphite, respectively, indicating that the sample prepared in this example is a graphitized carbon material, and the diffraction peak at 26 ° is relatively sharp, indicating that the sample prepared in this example has a relatively high graphitization degree.
As can be seen from fig. 3, three peaks, C, N and O1 s, appear at the binding energies of 285, 400 and 530eV, indicating that the nitrogen is successfully doped in the sample prepared in this example, and the nitrogen content (atomic%) is 8.25% as calculated from the peak area in the graph.
As can be seen from FIG. 4, the sample prepared in this example is mainly microporous, and the majority of the pores have a diameter less than 3 nm.
From FIG. 5, it can be calculated that the BET specific surface area of the sample prepared in this example is 166.0m2/g。
In order to further verify the catalytic performance of the nitrogen-doped graphene prepared in the embodiment, the nitrogen-doped graphene prepared in the embodiment is used for catalyzing the reaction of reducing p-nitrophenol by sodium borohydride, and the catalytic activity and the repeatability of the nitrogen-doped graphene are tested. The specific verification process is as follows:
putting 5mL of 40mmol/L p-nitrophenol solution into a beaker, adding water to dilute the solution to 100mL, adding 0.32g of sodium borohydride into the beaker, starting magnetic stirring to dissolve the sodium borohydride, controlling the water bath temperature to be 30 ℃, then adding 0.01g of the nitrogen-doped graphene prepared in the embodiment into the beaker, immediately sampling and timing, then sampling every 1min, and scanning the sample by using an ultraviolet-visible spectrophotometer. Since the absorbance of p-nitrophenol in alkaline solution at 400nm is proportional to its concentration, the progress of the reaction is monitored by monitoring the change in absorbance of the sample at 400 nm. After the reaction, the catalyst was centrifuged, washed with deionized water for 3 times and reused to test the repeatability.
Fig. 6 is an ultraviolet-visible spectrum of the nitrogen-doped graphene catalytic reduction p-nitrophenol prepared in the embodiment, and it can be seen from the ultraviolet-visible spectrum that the absorbance at 400nm gradually decreases with the progress of the reaction, that is, the concentration of p-nitrophenol gradually decreases, the reaction is basically complete in 5min, and the catalytic effect is significant.
Fig. 7 is a repetitive histogram of the reduction of p-nitrophenol by using nitrogen-doped graphene prepared in this example as a catalyst, sodium borohydride, from which it can be seen that the activity change is not large for the first 10 times and is significantly reduced for the 9 th time, indicating that the catalytic activity of the material is relatively stable; after each of the first 10 uses, there was a small decrease in catalytic activity, mainly due to a small loss of the material during the separation process.
EXAMPLE III
A preparation method of nitrogen-doped graphene comprises the following steps:
(1) respectively adding the metered lime nitrogen, the carbon source and the deionized water into a beaker, heating in a water bath while stirring to obtain a reaction material, controlling the temperature of the water bath to be 80 ℃, introducing carbon dioxide gas into the beaker until the pH of the reaction material is 12, uniformly spreading the reaction material into an enamel plate after reacting for 3 hours, then placing the enamel plate in a blast drying oven at 55 ℃ for drying for 3.5 hours, and finally transferring the dried material in the enamel plate into a mortar for uniformly grinding to obtain solid powder; the mass ratio of the lime nitrogen to the carbon source to the deionized water is (1-4): 1: (2-20); the carbon source is one or more of citric acid, tartaric acid, malic acid, glucose, sucrose and fructose;
(2) transferring the solid powder obtained in the step (1) into a porcelain boat, putting the porcelain boat and the solid powder into a tubular furnace together for pyrolysis, introducing nitrogen into the tubular furnace for protection, heating the tubular furnace to 580 ℃ at the speed of 3 ℃/min, preserving the heat for 2h, heating to 950 ℃ at the speed of 8 ℃/min, preserving the heat for 1h, naturally cooling the temperature in the furnace to room temperature, taking out the product, soaking the product in dilute hydrochloric acid, washing and filtering the product, washing the product with distilled water to be neutral, and finally drying the product at 85 ℃ for 3.5h to obtain the nitrogen-doped graphene.
By subjecting the prepared sample to transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, pore size distribution, isothermal adsorption-desorption curve and the likeThe characterization result shows that the prepared sample is nitrogen-doped graphene, the aperture is mainly micropores, and the specific surface area is 134.5m2The nitrogen content (atomic%) was 7.82%.
Claims (6)
1. A preparation method of nitrogen-doped graphene is characterized by comprising the following steps:
(1) respectively adding the measured lime nitrogen, carbon source and deionized water into a beaker, heating in a water bath while stirring to obtain a reaction material, controlling the temperature of the water bath to be 60-80 ℃, introducing carbon dioxide gas into the beaker until the pH of the reaction material is 9-12, uniformly spreading the reaction material into an enamel plate after reacting for 3-5 h, then placing the enamel plate in a blast drying oven at 45-55 ℃ for drying for 3.5-4.5 h, and finally transferring the dried material in the enamel plate into a mortar for uniformly grinding to obtain solid powder; the mass ratio of the lime nitrogen to the carbon source to the deionized water is (1-4): 1: (2-20); the carbon source is one or more of citric acid, tartaric acid, malic acid, glucose, sucrose and fructose;
(2) transferring the solid powder obtained in the step (1) into a porcelain boat, putting the porcelain boat and the solid powder into a tubular furnace for pyrolysis, introducing nitrogen into the tubular furnace for protection, heating the tubular furnace to 540-580 ℃ in a furnace cavity at the speed of 1-3 ℃/min, preserving heat for 2-3 h, heating to 750-950 ℃ in the furnace cavity at the speed of 3-8 ℃/min, preserving heat for 1-2 h, taking out a product after the temperature in the furnace cavity is naturally cooled to room temperature, soaking the product in dilute hydrochloric acid, washing and filtering, washing with distilled water to be neutral, and drying the product at 75-85 ℃ for 3.5-4.5 h to obtain the nitrogen-doped graphene.
2. The preparation method of nitrogen-doped graphene according to claim 1, wherein the temperature of the water bath in the step (1) is 70 ℃, the pH of the reaction material is controlled to be 10, and the reaction is carried out for 4 hours.
3. The method for preparing nitrogen-doped graphene according to claim 1 or 2, wherein in the step (2), the temperature of the tubular furnace is increased to 550 ℃ at a speed of 2 ℃/min, and the temperature is kept for 2.5 hours.
4. The method for preparing nitrogen-doped graphene according to claim 1 or 2, wherein in the step (2), the temperature of the tubular furnace is increased to 850 ℃ at a speed of 5 ℃/min, and the temperature is maintained for 1.5 h.
5. The method for preparing nitrogen-doped graphene according to claim 1 or 2, wherein the mass ratio of the lime nitrogen, the carbon source and the deionized water in the step (1) is 2.5: 1: 10.
6. the preparation method of nitrogen-doped graphene according to claim 1 or 2, wherein in the step (1), the enamel tray is placed in a forced air drying oven at 50 ℃ for drying for 4 hours; and (3) finally, drying the product at 80 ℃ for 4h to obtain the nitrogen-doped graphene.
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| CN105032469A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军国防科学技术大学 | Biomass base nitrogen-doped graphene/carbon fiber electrocatalyst and preparation method thereof |
| CN105417532A (en) * | 2015-12-22 | 2016-03-23 | 北京理工大学 | One-step preparation method for high nitrogen doped graphene |
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| CN105032469A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军国防科学技术大学 | Biomass base nitrogen-doped graphene/carbon fiber electrocatalyst and preparation method thereof |
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