CN108821266A - A kind of preparation method of nitrogen-doped graphene - Google Patents
A kind of preparation method of nitrogen-doped graphene Download PDFInfo
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Abstract
A kind of preparation method of nitrogen-doped graphene, lime nitrogen, carbon source and deionized water after metering is separately added into beaker, controlling bath temperature is 60~80 DEG C, stirring, adjusting reaction mass pH is 9~12, reaction mass is uniformly spread out in enamel tray after 3~5h of reaction, material is ground after dry and uniformly obtains solid powder；Solid powder is transferred in porcelain boat; it places it in tube furnace and is pyrolyzed; lead to nitrogen protection in furnace, tube furnace is warming up to 540~580 DEG C with 1~3 DEG C/min, keeps the temperature 2~3h; 750~950 DEG C are warming up to again with 3~8 DEG C/min; 1~2h is kept the temperature, room temperature is then naturally cooled to, impregnates product with dilute hydrochloric acid; it is repeatedly washed with water to neutrality, obtains nitrogen-doped graphene after dry.This method can reduce production cost and simplify production technology using cheap lime nitrogen as raw material, and without using metallic catalyst in preparation process.
Description
Technical field
The invention belongs to the preparation of carbon material and applied technical fields, and in particular to a kind of preparation side of nitrogen-doped graphene
Method.
Background technique
The two-dimension periodic honeycomb lattice structure that graphene is made of carbon hexatomic ring has high conductivity, highly thermally conductive property
And the advantages that high mechanical strength, composite material also show excellent performance.However, since graphene does not have band gap,
Electric conductivity cannot be controlled completely as traditional semiconductor, and graphene surface is smooth, inert, with other media
Interaction it is weaker, in addition, there is stronger active force between graphene film, be easy aggregation, cause graphene be not easy and other
Material it is compound, to hinder its application.At present mainly by into graphene nitrogen doped change the electricity of graphene
Minor structure and the metallic active sites for increasing graphene surface absorption increase to improve the electric conductivity and stability of graphene
The interaction of strong graphene and metallic, and then expand its application range.
The currently used method for preparing nitrogen-doped graphene mainly has：(1) chemical vapour deposition technique (CVD), the method are
It reacts gaseous precursor on matrix, forms film.Cui P, Choi J-H etc. is using penta chloropyridine as presoma, on copper surface
Prepare nitrogen-doped graphene (Cui P, Choi J-H, Zeng C, Li Z, Wang J, Zhang Z.J.Am.Chem.Soc.,
2017,139:7196-7202.), this method needs to use metallic catalyst, separating metallic catalyst and nitrogen-doped graphene ratio
More difficult, technique is more complex；(2) graphene oxide nitriding, the method are using graphene oxide as raw material, using nitrogen substance as nitrogen
Source, the nitrating under high temperature or hydrothermal condition.Tang P, GaoY J etc. is using graphene oxide as raw material, using acetonitrile or ammonium hydroxide as nitrogen
Source carries out nitrating at high temperature, obtains N doping graphene oxide (Tang P, Gao Y J, Yang J H, Li W J, Zhao
H Z,Ma D.Chin.J.Catal.,2014,35(6):922~928.)；The patent of Publication No. CN104465113 discloses
The method that hydro-thermal method prepares nitrogen-doped graphene, the method be using graphene oxide as raw material, after being mixed with urea and sulfuric acid,
180 DEG C of hydro-thermal reaction 2h, obtain nitrogen-doped graphene.Since graphene oxide is not easy to obtain, higher cost, the method is limited
System；(3) nitrogenous precursor transformation approach, the method are by nitrogen substance and transition metal compound catalyst (such as molysite, cobalt salt, nickel
Salt) mixing after, react at high temperature, remove metallic compound after obtain nitrogen-doped graphene.Wang C, Kang J etc. is by grape
Sugar, iron chloride and urea are dissolved in water, and after 80 DEG C of dryings for 24 hours, are pyrolyzed at 700 DEG C, are removed de-iron with hydrochloric acid and are obtained nitrogen and mix
Miscellaneous graphene (Wang C, Kang J, Sun H, Ang H M, Tade M O, Wang S.Carbon, 2016,102:279~
287.), metallic catalyst used in the method can generate metal carbides, it is difficult to thoroughly remove, influence later period use.Due to upper
Stating method, there are problems, therefore, seek that a kind of simple process, raw material is easy to get, cost is relatively low, without using metallic catalyst
Preparation method have a very important significance.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of nitrogen-doped graphene, and this method is without using metal catalytic
Agent to save step of this difficulty of separating metallic catalyst and nitrogen-doped graphene, and can avoid in the fabrication process
Metal carbides are generated, technique is simplified；In addition, the present invention using cheap lime nitrogen as raw material, can reduce production cost.
To achieve the above object, a kind of preparation method of nitrogen-doped graphene, includes the following steps：
(1) lime nitrogen, carbon source and the deionized water after metering are separately added into beaker, heating water bath obtains while stirring
Reaction mass, control bath temperature are 60~80 DEG C, and the pH for being passed through into beaker carbon dioxide gas to reaction mass be 9~
12, reaction mass is uniformly spread out in enamel tray after reacting 3~5h, then does the air blast that enamel tray is placed in 45~55 DEG C
Material in enamel tray after drying, is finally transferred in mortar and grinds uniformly, obtain solid powder by dry 3.5~4.5h in dry case
End；The lime nitrogen, carbon source, the mass ratio between deionized water are (1~4)：1：(2~20)；
(2) solid powder that step (1) obtains is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, tubular type
Lead to nitrogen protection in furnace, it is 540~580 DEG C that the first rate with 1~3 DEG C/min of tube furnace, which is warming up to furnace chamber temperature, heat preservation 2~
Then 3h is warming up to furnace chamber temperature with the rate of 3~8 DEG C/min as 750~950 DEG C, 1~2h is kept the temperature, then when in furnace chamber
Temperature takes out product after naturally cooling to room temperature, and product is immersed in dilute hydrochloric acid, uses distilled water again after washing and filtering
Washing obtains nitrogen-doped graphene after dry 3.5~4.5h under the conditions of product is finally placed in 75~85 DEG C to neutrality.
Preferably, bath temperature is 70 DEG C in step (1), and the pH for controlling reaction mass is 10, reacts 4h.
Preferably, tube furnace is first warming up to furnace chamber temperature with the rate of 2 DEG C/min as 550 DEG C in step (2), keeps the temperature
2.5h。
Preferably, tube furnace is warming up to furnace chamber temperature with the rate of 5 DEG C/min again as 850 DEG C in step (2), keeps the temperature
1.5h。
Preferably, lime nitrogen described in step (1) and the mass ratio of carbon source, deionized water are 2.5：1：10.
Preferably, the carbon source is one or more of citric acid, tartaric acid, malic acid, glucose, sucrose, fructose.
Preferably, enamel tray is placed in in 50 DEG C of air dry oven dry 4h in step (1)；It is last in step (2)
Nitrogen-doped graphene is obtained after dry 4h under the conditions of product is placed in 80 DEG C.
The present invention using cheap lime nitrogen as nitrogen source, hydrolyzed, polymerize after obtain the mixture of dicyandiamide and calcium carbonate, it is double
Cyanamide, calcium carbonate and carbon source carry out high temperature pyrolysis, and dicyandiamide polymerization generates graphite phase carbon nitride in pyrolytic process, at the same carbon source with
Graphite phase carbon nitride and calcium carbonate are template in its surface carbonation.Continue to increase with temperature, pyrolytic reaction continue into
Row, graphite phase carbon nitride are further broken into small molecule nitrogenous compound, these compounds are as nitrogen dopant to carbonized product
Nitrating is carried out, nitrogen-doped graphene is finally obtained.
Compared with prior art, the present invention is to obtain nitrogen-doped graphene, technique letter by pyrolysismethod under high-temperature pressure
It is single, it is easy to industrialized production without using the instrument and equipment of complex and expensive；Raw material in the present invention is cheap and easy to get and without any
Specially treated, the hydrolysate of lime nitrogen are not only used as template, but also as nitrogen dopant, add during the preparation process without other
Enter metal and metallic compound, be effectively simplified production technology and reduce production cost；Preparation method obtains through the invention
Nitrogen-doped graphene and as the catalyst of sodium borohydride reduction p-nitrophenol, catalytic activity with higher, in dirt
There is potential utility value in terms of water process.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 2 is the x-ray diffraction pattern of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 3 is the x-ray photoelectron spectroscopy figure of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 4 is the pore size distribution curve of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 5 is isothermal adsorption-desorption curve of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 6 is the purple of the catalysis sodium borohydride reduction p-nitrophenol of nitrogen-doped graphene prepared by the embodiment of the present invention two
Outside-visible light spectrogram；
Fig. 7 is the weight of the catalysis sodium borohydride reduction p-nitrophenol of nitrogen-doped graphene prepared by the embodiment of the present invention two
Renaturation histogram.
Specific embodiment
Below in conjunction with drawings and examples, invention is further described in detail.
Embodiment one
A kind of preparation method of nitrogen-doped graphene, includes the following steps：
(1) lime nitrogen, carbon source and the deionized water after metering are added in beaker, heating water bath obtains instead while stirring
Material is answered, control bath temperature is 60 DEG C, and the pH for being passed through carbon dioxide gas to reaction mass into beaker is 9, reacts 5h
Reaction mass is uniformly spread out in enamel tray afterwards, then enamel tray is placed in in 45 DEG C of air dry oven dry 4.5h,
Material after finally will be dry in enamel tray, which is transferred to, grinds middle grinding uniformly, obtains solid powder；The lime nitrogen and carbon source,
The mass ratio of deionized water is 1：1：2；The carbon source is citric acid, tartaric acid, malic acid, glucose, sucrose, one in fructose
Kind is several；
(2) solid powder that step (1) obtains is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, tubular type
Lead to nitrogen protection in furnace, tube furnace is first warming up to furnace chamber temperature with the rate of 1 DEG C/min as 540 DEG C, 3h is kept the temperature, then with 3
DEG C/to be warming up to furnace chamber temperature be 750 DEG C for the rate of min, 2h is kept the temperature, is then taken after furnace chamber temperature naturally cools to room temperature
Product is immersed in dilute hydrochloric acid by product out, is washed with distilled water to neutrality again after washing and filtering, is finally put product
Nitrogen-doped graphene is obtained after dry 4.5h under the conditions of being placed in 75 DEG C.
By carrying out transmission electron microscope, X-ray diffraction, x-ray photoelectron spectroscopy, pore-size distribution to the sample of preparation and waiting
The characterization such as warm adsorption-desorption curve, the results showed that the sample being prepared is nitrogen-doped graphene, and aperture is mainly micropore, than
Surface area is 181.5m2/ g, nitrogen content (atomic percent) are 10.89%.
Embodiment two
A kind of preparation method of nitrogen-doped graphene, includes the following steps：
(1) lime nitrogen, carbon source and the deionized water after metering are separately added into beaker, heating water bath obtains while stirring
To reaction mass, controlling bath temperature is 70 DEG C, and the pH for being passed through carbon dioxide gas to reaction mass into beaker is 10, instead
Reaction mass is uniformly spread out in enamel tray after answering 4h, is then placed in enamel tray in 50 DEG C of air dry oven dry
Material in enamel tray after drying is finally transferred in mortar and grinds uniformly, obtains solid powder by 4h；The lime nitrogen, carbon
Mass ratio between source, deionized water is 2.5：1：10；The carbon source be citric acid, tartaric acid, malic acid, glucose, sucrose,
One or more of fructose；
(2) solid powder that step (1) obtains is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, tubular type
Lead to nitrogen protection in furnace, tube furnace is first warming up to furnace chamber temperature with the rate of 2 DEG C/min as 550 DEG C, keeps the temperature 2.5h, then with
It is 850 DEG C that the rate of 5 DEG C/min, which is warming up to furnace chamber temperature, keeps the temperature 1.5h, then when furnace chamber temperature naturally cools to room temperature
After take out product, product is immersed in dilute hydrochloric acid, is washed with distilled water to neutrality again after washing and filtering, finally will produce
Object obtains nitrogen-doped graphene after dry 4h under the conditions of being placed in 80 DEG C.
Transmission electron microscope picture, x-ray diffraction pattern, the X-ray photoelectricity of the preparation-obtained nitrogen-doped graphene of above-mentioned steps
Sub- energy spectrum diagram, pore size distribution curve and isothermal adsorption-desorption curve are distinguished as shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4 and Fig. 5.
From figure 1 it appears that showing that the sample that the present embodiment is prepared is by transparent and with crisp flake
Material is random to be accumulated, and shows that product is graphene.
From figure 2 it can be seen that at 26 ° and 43 ° or so there are two diffraction maximum in figure, respectively correspond graphite (002) and
(100) crystal face shows that the sample that the present embodiment is prepared is graphited carbon material, and the diffraction maximum at 26 ° is more sharp, shows
The sample degree of graphitization that the present embodiment is prepared is higher.
From figure 3, it can be seen that can be three peaks of appearance, the respectively 1s of C, N and O at 285,400 and 530eV in combination
Peak shows that nitrogen is successfully entrained in the sample that the present embodiment is prepared, and the content that can calculate nitrogen according to peak area in figure is (former
Sub- percentage) it is 8.25%.
From fig. 4, it can be seen that the sample that the present embodiment is prepared, based on micropore, most of aperture is less than 3nm.
The BET specific surface area that the sample that the present embodiment is prepared can be calculated from Fig. 5 is 166.0m2/g。
For the catalytic performance for further verifying nitrogen-doped graphene manufactured in the present embodiment, the present embodiment is prepared
Nitrogen-doped graphene is used to be catalyzed the reaction of sodium borohydride reduction p-nitrophenol, tests its catalytic activity and repeatability.Specifically
Verification process is as follows：
It takes the p-nitrophenyl phenol solution of 5mL 40mmol/L to be put into beaker, is diluted with water to 100mL, then add into beaker
Enter 0.32g sodium borohydride, starting magnetic agitation dissolves sodium borohydride, and control bath temperature is 30 DEG C, then adds into beaker
Enter nitrogen-doped graphene prepared by 0.01g the present embodiment, immediately sampling and timing, then every 1min sample, with it is ultraviolet-can
See that spectrophotometer scans sample.Since absorbance of the p-nitrophenol product at 400nm in alkaline solution and its concentration are in
Direct ratio, therefore reaction process is monitored by the variation of monitoring sample absorbance at 400nm.After the reaction was completed, it is centrifugated
Catalyst is reused, test repeatability after being washed with deionized 3 times.
Fig. 6 is the UV-visible spectrum of the catalysis reduction p-nitrophenol of nitrogen-doped graphene prepared by the present embodiment,
It can be seen from the figure that the absorbance at 400nm is gradually reduced with the progress of reaction, i.e., the concentration of p-nitrophenol is gradually
Reduce, 5min fundamental reaction is complete, and catalytic effect is significant.
Fig. 7 is weight of the nitrogen-doped graphene as catalyst sodium borohydride reduction p-nitrophenol prepared by the present embodiment
Renaturation histogram decreased significantly for 9th time from figure it is found that preceding 10 activity changes are little, show the catalytic activity of the material compared with
Stablize；After first 10 times each uses, catalytic activity has to be declined by a small margin, mainly due in separation process the material damage on a small quantity
It becomes homeless cause.
Embodiment three
A kind of preparation method of nitrogen-doped graphene, includes the following steps：
(1) lime nitrogen, carbon source and the deionized water after metering are separately added into beaker, heating water bath obtains while stirring
To reaction mass, controlling bath temperature is 80 DEG C, and the pH for being passed through carbon dioxide gas to reaction mass into beaker is 12, instead
Reaction mass is uniformly spread out in enamel tray after answering 3h, is then placed in enamel tray in 55 DEG C of air dry oven dry
Material in enamel tray after drying is finally transferred in mortar and grinds uniformly, obtains solid powder by 3.5h；The lime nitrogen,
Mass ratio between carbon source, deionized water is (1~4)：1：(2~20)；The carbon source is citric acid, tartaric acid, malic acid, Portugal
One or more of grape sugar, sucrose, fructose；
(2) solid powder that step (1) obtains is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, tubular type
Lead to nitrogen protection in furnace, tube furnace is first warming up to furnace chamber temperature with the rate of 3 DEG C/min as 580 DEG C, 2h is kept the temperature, then with 8
DEG C/to be warming up to furnace chamber temperature be 950 DEG C for the rate of min, 1h is kept the temperature, is then taken after furnace chamber temperature naturally cools to room temperature
Product is immersed in dilute hydrochloric acid by product out, is washed with distilled water to neutrality again after washing and filtering, is finally put product
Nitrogen-doped graphene is obtained after dry 3.5h under the conditions of being placed in 85 DEG C.
By carrying out transmission electron microscope, X-ray diffraction, x-ray photoelectron spectroscopy, pore-size distribution to the sample of preparation and waiting
The characterization such as warm adsorption-desorption curve, the results showed that the sample being prepared is nitrogen-doped graphene, and aperture is mainly micropore, than
Surface area is 134.5m2/ g, nitrogen content (atomic percent) are 7.82%.
Claims (7)
1. a kind of preparation method of nitrogen-doped graphene, which is characterized in that include the following steps：
(1) lime nitrogen, carbon source and the deionized water after metering are separately added into beaker, heating water bath is reacted while stirring
Material, control bath temperature are 60~80 DEG C, and the pH for being passed through carbon dioxide gas to reaction mass into beaker is 9~12,
Reaction mass is uniformly spread out in enamel tray after 3~5h of reaction, then enamel tray is placed in 45~55 DEG C of forced air drying
Material in enamel tray after drying, is finally transferred in mortar and grinds uniformly, obtain solid powder by dry 3.5~4.5h in case
End；The lime nitrogen, carbon source, the mass ratio between deionized water are (1~4)：1：(2~20)；
(2) solid powder that step (1) obtains is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, in tube furnace
Logical nitrogen protection, tube furnace are first warming up to furnace chamber temperature with the rate of 1~3 DEG C/min as 540~580 DEG C, keep the temperature 2~3h,
Then furnace chamber temperature is warming up to as 750~950 DEG C with the rate of 3~8 DEG C/min, keeps the temperature 1~2h, then works as furnace chamber temperature
Product is taken out after naturally cooling to room temperature, product is immersed in dilute hydrochloric acid, is washed with distilled water again after washing and filtering
To neutrality, nitrogen-doped graphene is obtained after dry 3.5~4.5h under the conditions of product is finally placed in 75~85 DEG C.
2. a kind of preparation method of nitrogen-doped graphene according to claim 1, which is characterized in that water-bath in step (1)
Temperature is 70 DEG C, and the pH for controlling reaction mass is 10, reacts 4h.
3. a kind of preparation method of nitrogen-doped graphene according to claim 1 or 2, which is characterized in that pipe in step (2)
Formula furnace is first warming up to furnace chamber temperature with the rate of 2 DEG C/min as 550 DEG C, keeps the temperature 2.5h.
4. a kind of preparation method of nitrogen-doped graphene according to claim 1 or 2, which is characterized in that pipe in step (2)
Formula furnace is warming up to furnace chamber temperature with the rate of 5 DEG C/min again as 850 DEG C, keeps the temperature 1.5h.
5. a kind of preparation method of nitrogen-doped graphene according to claim 1 or 2, which is characterized in that institute in step (1)
Stating lime nitrogen, carbon source, the mass ratio between deionized water is 2.5：1：10.
6. a kind of preparation method of nitrogen-doped graphene according to claim 1 or 2, which is characterized in that the carbon source is
One or more of citric acid, tartaric acid, malic acid, glucose, sucrose, fructose.
7. a kind of preparation method of nitrogen-doped graphene according to claim 1 or 2, which is characterized in that will in step (1)
Enamel tray is placed in 50 DEG C of air dry oven dry 4h；It is dry under the conditions of product is finally placed in 80 DEG C in step (2)
Nitrogen-doped graphene is obtained after 4h.
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| CN110560122A (en) * | 2019-08-16 | 2019-12-13 | 徐州工程学院 | Porous carbon nitride material, and preparation method and application thereof |
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| CN109626364A (en) * | 2019-01-29 | 2019-04-16 | 东北大学 | A kind of preparation method of nitrogen sulphur codope three-dimensional grapheme |
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| CN114522686A (en) * | 2021-09-07 | 2022-05-24 | 盐城工学院 | Cu/Cu prepared by loading metal-organic framework on corncob2O/C composite material and application thereof |
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