CN108862250A - 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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- CN108862250A CN108862250A CN201811002484.8A CN201811002484A CN108862250A CN 108862250 A CN108862250 A CN 108862250A CN 201811002484 A CN201811002484 A CN 201811002484A CN 108862250 A CN108862250 A CN 108862250A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
A kind of preparation method of nitrogen-doped graphene, by after metering ammonium thiocyanate and carbon source be separately added into mortar grinding and uniformly obtain solid powder mixture, solid powder mixture is placed in 50~80 DEG C of baking oven and dries 2~4h and obtain presoma；Presoma is transferred in porcelain boat and is placed in tube furnace together and is pyrolyzed; lead to nitrogen protection in tube furnace; tube furnace is first warming up to furnace chamber temperature with the rate of 3~7 DEG C/min as 540~580 DEG C; keep the temperature 1~3h; furnace chamber temperature is warming up to as 750~950 DEG C with the rate of 6~10 DEG C/min again; 0.5~1.5h is kept the temperature, then when furnace chamber temperature naturally cools to room temperature, taking-up product obtains nitrogen-doped graphene.This method can be improved production efficiency, without using metallic catalyst in preparation process, can simplify technique and reduce the pollution to environment；The present invention reduces production cost using cheap ammonium thiocyanate as raw material.
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 form that is primarily present of carbon material has three classes：Graphite, diamond and amorphous carbon.With the development of technology, many
New carbon continuously emerges, such as carbon nanotube, graphene, mesoporous carbon.Wherein graphene has biggish specific surface area, excellent
Good conduction and heat transfer property, high tensile, it is corrosion-resistant the advantages that, have in fields such as the energy, environment, catalysis and widely answer
With, but the hydrophily of graphene is bad, its application is caused to be subject to certain restrictions.At present mainly by adulterating nitrogen into graphene
Member usually improves the hydrophily of graphene, to 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.Wei D S, LiuYQ etc. are to adhere to copper on a silicon substrate for catalysis
Agent is reacted using methane and ammonia as carbon source and nitrogen source at 800 DEG C, obtain nitrogen-doped graphene (Wei D S,
LiuYQ,WangY,Zhang H L,Huang LP,Yu G.Nano Lett.,2009,9(5):1752~1758.), this method
Need to use metallic catalyst, meeting polluted product, and technique is more complex；(2) graphene oxide nitriding, the method are to aoxidize stone
Black alkene is raw material, using nitrogen substance as nitrogen source, the nitrating under high temperature or hydrothermal condition.TangP, GaoYJ etc. are with graphene oxide
Carry out nitrating at high temperature using acetonitrile or ammonium hydroxide as nitrogen source for raw material, obtain N doping graphene oxide (TangP, GaoY J,
Yang JH,Li W J,Zhao HZ,MaD.Chin.J.Catal.,2014,35(6):922~928.), this method is to aoxidize stone
Black alkene is raw material, and higher cost, which is restricted；(3) hydro-thermal (solvent heat) method, the patent of Publication No. CN102167310A
The method of preparing nitrogen-doped graphene material with hydrothermal process is disclosed, this method is carried out using graphite oxide and nitrogenous compound as raw material
Hydro-thermal reaction, hydrothermal temperature are 100~190 DEG C, and the hydro-thermal reaction time is 4~48h, in 60~110 DEG C of conditions after washing
Lower drying is dried in vacuo 6~8h under the conditions of 60~80 DEG C and obtains nitrogen-doped graphene material；Publication No.
The patent of 105384163A discloses the method that solvent-thermal method prepares nitrogen-doped graphene, which is by nitrogenous precursor, tetrachloro
Change carbon and metallic potassium is added in water heating kettle under inert gas protection, in 160~240 DEG C, heat treatment 10min~12h is obtained
Nitrogen-doped graphene material, too long using hydro-thermal method preparation time, production efficiency is lower.Since the above method is asked there are many
Therefore topic seeks a kind of simple process, the high efficiency preparation method that cost is relatively low, environmental-friendly has a very important significance.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of nitrogen-doped graphene, production efficiency is can be improved in this method,
Without using metallic catalyst in preparation process, so as to simplify technique and reduce the pollution to environment；In addition, the present invention is with honest and clean
The ammonium thiocyanate of valence is 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) by after metering ammonium thiocyanate and carbon source be separately added into mortar grinding and uniformly obtain solid powder mixture,
Solid powder mixture is placed in in 50~80 DEG C of baking oven dry 2~4h and obtains presoma；The ammonium thiocyanate and carbon source
Between mass ratio be (5~15)：1；
(2) presoma is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, nitrogen protection is led in tube furnace,
Tube furnace is first warming up to furnace chamber temperature with the rate of 3~7 DEG C/min as 540~580 DEG C, 1~3h is kept the temperature, then with 6~10
DEG C/to be warming up to furnace chamber temperature be 750~950 DEG C for the rate of min, 0.5~1.5h is kept the temperature, then when furnace chamber temperature is naturally cold
But room temperature is arrived, product is taken out and obtains nitrogen-doped graphene.
Preferably, the carbon source is one of glucose, sucrose, fructose, ribose, maltose, lactose, oligosaccharide or several
Kind.
Preferably, tube furnace is first warming up to furnace chamber temperature with the rate of 4 DEG C/min as 550 DEG C in step (2), keeps the temperature
2h。
Preferably, tube furnace is warming up to furnace chamber temperature with the rate of 8 DEG C/min again as 850 DEG C in step (2), keeps the temperature
1h。
Preferably, solid powder mixture is placed in in 60 DEG C of baking oven dry 3h in step (1) and obtains presoma.
Preferably, the mass ratio described in step (1) between ammonium thiocyanate and carbon source is 10：1.
The present invention is using using cheap inorganic nitrogen-sourced ammonium thiocyanate and carbon source as raw material, after carrying out mill-drying respectively, in nitrogen
Carry out high temperature pyrolysis under gas shielded, in pyrolytic process, ammonium thiocyanate is first transformed into thiocarbamide, and as the temperature rises, thiocarbamide is into one
Step condensation generates graphite phase carbon nitride.Carbon source is template in its surface carbonation using graphite phase carbon nitride.With pyrolytic reaction
Lasting to carry out, graphite phase carbon nitride is further broken into small molecule nitrogenous compound, these compounds are as nitrogen dopant to carbon
Change product and carry out nitrating, finally obtains nitrogen-doped graphene.
Compared with prior art, system of the present invention directly obtains nitrogen-doped graphene by pyrolysis under high-temperature pressure, and makes
Without using metal and metallic compound during standby, the later period without carrying out sour processing, simplifies production technology, improves production
Efficiency, and it is environmental-friendly, it is easy to industrialized production without using the instrument and equipment of complex and expensive；Raw material is inexpensively easy in the present invention
And be not necessarily to any specially treated, ammonium thiocyanate is used as template, and as nitrogen dopant, during the preparation process without making
With metal and metallic compound, production cost is effectively reduced；Preparation method obtains nitrogen-doped graphene and will through the invention
Its catalyst as potassium borohydride reduction p-nitrophenol, catalytic activity with higher and reproducible, in sewage treatment
Aspect has potential utility value.
Detailed description of the invention
Fig. 1 is the x-ray diffraction pattern of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 2 is the x-ray photoelectron spectroscopy figure of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 3 is the transmission electron microscope picture of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 4 is isothermal adsorption-desorption curve of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 5 is the pore size distribution curve of nitrogen-doped graphene prepared by the embodiment of the present invention two；
Fig. 6 is the purple of the catalysis potassium 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 potassium 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) by after metering ammonium thiocyanate and carbon source be separately added into mortar grinding and uniformly obtain solid powder mixture,
Solid powder mixture is placed in in 50 DEG C of baking oven dry 4h and obtains presoma；Matter between the ammonium thiocyanate and carbon source
Amount is than being 5：1；The carbon source is one or more of glucose, sucrose, fructose, ribose, maltose, lactose, oligosaccharide；
(2) presoma is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, nitrogen protection is led in tube furnace,
Tube furnace is first warming up to furnace chamber temperature with the rate of 3 DEG C/min as 540 DEG C, keeps the temperature 3h, is then heated up with the rate of 6 DEG C/min
It is 750 DEG C to furnace chamber temperature, keeps the temperature 1.5h, then when furnace chamber temperature naturally cools to room temperature, taking-up product obtains nitrogen and mixes
Miscellaneous graphene.
Pass through x-ray diffraction pattern, x-ray photoelectron spectroscopy figure, transmission electron microscope picture, isothermal adsorption-desorption curve and hole
The test analysis such as diameter distribution curve, the sample being prepared are nitrogen-doped graphene, and mesoporous pore size distribution is relatively concentrated, most of hole
Diameter is 3~5nm, specific surface area 156.2m2/ g, nitrogen content (atomic percent) are 9.12%
Embodiment two
A kind of preparation method of nitrogen-doped graphene, includes the following steps：
(1) by after metering ammonium thiocyanate and carbon source be separately added into mortar grinding and uniformly obtain solid powder mixture,
Solid powder mixture is placed in in 60 DEG C of baking oven dry 3h and obtains presoma；Matter between the ammonium thiocyanate and carbon source
Amount is than being 10：1；The carbon source is one or more of glucose, sucrose, fructose, ribose, maltose, lactose, oligosaccharide；
(2) presoma is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, nitrogen protection is led in tube furnace,
Tube furnace is first warming up to furnace chamber temperature with the rate of 4 DEG C/min as 550 DEG C, keeps the temperature 2h, is then heated up with the rate of 8 DEG C/min
It is 850 DEG C to furnace chamber temperature, keeps the temperature 1h, then when furnace chamber temperature naturally cools to room temperature, taking-up product obtains N doping
Graphene.
The x-ray diffraction pattern of the preparation-obtained nitrogen-doped graphene of above-mentioned steps, x-ray photoelectron spectroscopy figure, thoroughly
Electron microscope, isothermal adsorption-desorption curve and pore size distribution curve is penetrated to distinguish as shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4 and Fig. 5.
From figure 1 it appears that the diffraction maximum in figure at 26 ° is more sharp, show the sample that the present embodiment is prepared
Degree of graphitization is higher.
From figure 2 it can be seen that being N 1s diffraction maximum at the peak that combination can be appearance at 400eV, show that nitrogen successfully adulterates
In the sample that the present embodiment is prepared, it is according to the content (atomic percent) that peak area in figure can calculate nitrogen
9.32%.
From figure 3, it can be seen that showing that the sample that the present embodiment is prepared is transparent and with crisp laminar material
Material shows that product is graphene.
The BET specific surface area that the sample that the present embodiment is prepared can be calculated from Fig. 4 is 135.7m2/g。
From fig. 5, it can be seen that the sample that the present embodiment is prepared has a more micropore and mesoporous, mesoporous pore size distribution compared with
It concentrates, most of aperture is 3~5nm.
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 for the reaction of potassium borohydride reduction p-nitrophenol, tests its catalytic activity.Specific verification process is as follows：
Take the p-nitrophenyl phenol solution of 100mL 2mmol/L to be put into beaker, then plus 0.01g the present embodiment prepared by nitrogen
Doped graphene places the beaker in water-bath, control bath temperature be 20~30 DEG C, magnetic stirring speed be 800~
1000r/min.After temperature reaches set temperature, 0.43g potassium borohydride is added into beaker, immediately sampling and timing, then
It is sampled every 1~4min, scans sample with ultraviolet-visible spectrophotometer, monitor absorbance of the sample at 400nm, monitoring
Reaction process, until sample absorbance, less than 0.1, reaction solution is in colourless, stopping reaction at this time.Reacted material carries out centrifugation point
From after the nitrogen-doped graphene of recycling is washed with distilled water 3 times, reuse, this process is repeated 10 times.
Fig. 6 be the present embodiment prepared by nitrogen-doped graphene be catalyzed potassium borohydride reduction p-nitrophenol it is ultraviolet-can
Light-exposed spectrogram, it can be seen from the figure that the absorbance at 400nm is gradually reduced with the progress of reaction, i.e. p-nitrophenol
Concentration is gradually reduced, and 6min fundamental reaction is complete, and catalytic effect is significant.
Fig. 7 is repetition of the nitrogen-doped graphene prepared by the present embodiment as catalysis potassium borohydride reduction p-nitrophenol
Property histogram decreased significantly for 9th time from figure it is found that preceding 8 activity changes are little, show that the catalytic activity of the material is more steady
It is fixed；After first 8 times each uses, catalytic activity has reduction, mainly due to caused by the material loss in separation process.
Embodiment three
A kind of preparation method of nitrogen-doped graphene, includes the following steps：
(1) by after metering ammonium thiocyanate and carbon source be separately added into mortar grinding and uniformly obtain solid powder mixture,
Solid powder mixture is placed in in 80 DEG C of baking oven dry 2h and obtains presoma；Matter between the ammonium thiocyanate and carbon source
Amount is than being 15：1；The carbon source is one or more of glucose, sucrose, fructose, ribose, maltose, lactose, oligosaccharide；
(2) presoma is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, nitrogen protection is led in tube furnace,
Tube furnace is first warming up to furnace chamber temperature with the rate of 7 DEG C/min as 580 DEG C, 1h is kept the temperature, then with the rate liter of 10 DEG C/min
Temperature to furnace chamber temperature is 950 DEG C, keeps the temperature 0.5h, and then when furnace chamber temperature naturally cools to room temperature, taking-up product obtains nitrogen
Doped graphene.
Pass through x-ray diffraction pattern, x-ray photoelectron spectroscopy figure, transmission electron microscope picture, isothermal adsorption-desorption curve and hole
The test analysis such as diameter distribution curve, the sample being prepared are nitrogen-doped graphene, and mesoporous pore size distribution is relatively concentrated, most of hole
Diameter is 3~5nm, specific surface area 187.6m2/ g, nitrogen content (atomic percent) are 8.96%.
Claims (6)
1. a kind of preparation method of nitrogen-doped graphene, which is characterized in that include the following steps：
(1) by after metering ammonium thiocyanate and carbon source be separately added into mortar grinding and uniformly obtain solid powder mixture, will consolidate
Body mixture of powders is placed in 50~80 DEG C of baking oven dry 2~4h and obtains presoma；Between the ammonium thiocyanate and carbon source
Mass ratio be (5~15)：1；
(2) presoma is transferred in porcelain boat and is placed in tube furnace together and be pyrolyzed, nitrogen protection, tubular type are led in tube furnace
Furnace is first warming up to furnace chamber temperature with the rate of 3~7 DEG C/min as 540~580 DEG C, keeps the temperature 1~3h, then with 6~10 DEG C/
It is 750~950 DEG C that the rate of min, which is warming up to furnace chamber temperature, keeps the temperature 0.5~1.5h, then works as furnace chamber temperature natural cooling
To room temperature, takes out product and obtain nitrogen-doped graphene.
2. a kind of preparation method of nitrogen-doped graphene according to claim 1, which is characterized in that the carbon source is grape
One or more of sugar, sucrose, fructose, ribose, maltose, lactose, oligosaccharide.
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 4 DEG C/min as 550 DEG C, keeps the temperature 2h.
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 8 DEG C/min again as 850 DEG C, keeps the temperature 1h.
5. a kind of preparation method of nitrogen-doped graphene according to claim 1 or 2, which is characterized in that will in step (1)
Solid powder mixture is placed in 60 DEG C of baking oven dry 3h and obtains presoma.
6. 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 the mass ratio between ammonium thiocyanate and carbon source is 10：1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110064388A (en) * | 2019-05-29 | 2019-07-30 | 黑龙江省科学院石油化学研究院 | A kind of graphene oxide-loaded superfine nano palladium catalyst of N doping and its in-situ preparation method |
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| CN110064388A (en) * | 2019-05-29 | 2019-07-30 | 黑龙江省科学院石油化学研究院 | A kind of graphene oxide-loaded superfine nano palladium catalyst of N doping and its in-situ preparation method |
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Application publication date: 20181123 |