CN103101909A - Method for preparing nitrogen-doped graphene material - Google Patents
Method for preparing nitrogen-doped graphene material Download PDFInfo
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Abstract
The invention relates to a preparation method of a nitrogen-doped graphene material. The preparation method comprises the following steps of: 1, synthesizing an iron phosphate (cobalt, nickel)/ organic amine precursor with an inorganic-organic alternated layered structure by adopting a solution chemical route; 2, transforming organic amine contained in the iron phosphate (cobalt, nickel)/ organic amine precursor with the layered structure into a graphene sheet layer in situ under the catalysis of metal species contained in an inorganic layer through high-temperature inert atmosphere treatment so that the integral precursor material is transformed into an iron phosphate (cobalt, nickel) thin layer and graphene sheet layer alternated iron phosphate (cobalt, nickel)/graphene interlining composite material; and (3) removing iron phosphate (cobalt, nickel) to obtain the nitrogen-doped graphene material. The obtained sheet-shaped nitrogen-doped graphene material is a curly sheet, the sheet comprises 1-9 graphene layers, and the nitrogen content (in percentage by weight) of the nitrogen-doped graphene material is 0.5%-20%. The nitrogen-doped graphene material prepared by adopting the method disclosed by the invention is high and adjustable and controllable in nitrogen content. The preparation method disclosed by the invention has simple process, is suitable for industrial large-scale production and is low in cost.
Description
Technical field:
The present invention relates to a kind of nitrogen-doped graphene material preparation method.
Background technology:
Graphene is a kind of two-dimensional material that is comprised of carbon atom, and carbon atom wherein is with sp
2The hexangle type that hybridized orbital forms is the honeycomb bivariate distribution.Graphene be at present the thinnest in the world be the hardest nano material also, its thermal conductivity is higher than carbon nanotube and diamond (up to 5300 W/mK), under normal temperature its electronic mobility is higher than CNT (carbon nano-tube) and crystalline silicon, and resistivity (only has an appointment 10 than copper and Yin Geng are low
-6Ω cm).Therefore Graphene is expected to can be used to develop thinner, conduction speed electronic component of new generation or transistor faster.Simultaneously, due to its highly conc, high-specific surface area, grapheme material is widely used in new energy field such as ultracapacitor, lithium ion and fuel cell aspect, and the aspect such as support of the catalyst.
At present, the concept of grapheme material is also in constantly expansion, all can be called Graphene because having unique character as the structure of the two-dimension graphite sheet of 1-9 layer, and the grapheme material that adulterates of heteroatoms (N, B, P etc.) etc.In numerous grapheme materials, utilize heteroatoms, particularly the performance of nitrogen atom doping modulation grapheme material, attracted people to pay close attention to widely.Research finds, it is lower and be difficult to control, be difficult to the technical problem such as scale operation that the nitrogen-doped graphene material preparation method exists nitrogen content.Wherein, Chinese patent application 201110024899.7 discloses a kind of method that obtains the nitrogen-doped graphene material by calcining trimeric cyanamide and graphene oxide; Chinese patent application 200910175312.5 discloses and has a kind ofly formed nitrogen-doped graphene material preparation method by organic explosive substance containing nitro-group and carbon containing and nitrogen additive are added thermal explosion in airtight container; Chinese patent application 201110033478.0 discloses a kind of method by preparing nitrogen-doped graphene material with hydrothermal process.
The invention provides a kind of method that adopts lamellar precursor situ catalytic graphitizing method to prepare the regulatable nitrogen-doped graphene material of nitrogen content.
Summary of the invention:
The object of the present invention is to provide a kind of method that adopts lamellar precursor situ catalytic graphitizing method to prepare the regulatable nitrogen-doped graphene material of nitrogen content.
Technical scheme of the present invention is as follows:
A kind of method for preparing the nitrogen-doped graphene material, the nitrogen-doped graphene material of its preparation is curling thin slice, and the number of plies of thin slice is the 1-9 layer, and wherein the content of nitrogen (quality percentage composition) is 0.5-20%, and it comprises the following steps:
Step 1. is containing the dihydrogen phosphate ions that concentration is 0.02-2.0 mol/L, 0.02-2.0 in the divalence of the iron of mol/L, cobalt or nickel or the solution of trivalent ion, add organic amine as template, mix and obtain suspension liquid, wherein the amount of organic amine is 0.1-10:1 with the ratio of the amount of substance of dihydrogen phosphate ions;
Step 2. is with the suspension liquid suction filtration in step 1, and filter cake room temperature vacuum-drying 24 hours obtains powder;
Step 3. is ground the powder that step 2 obtains, and puts into tube furnace, under the protection of rare gas element, is warming up to 500-900 ℃ from room temperature, and keeps 4-24 hour, afterwards, naturally cools to room temperature, obtains the powder of black;
The powder that step 4. obtains step 3 grinds puts into the water heating kettle that fills inorganic acid solution, 150-180 ℃ of lower hydro-thermal 24 hours, afterwards, be cooled to room temperature, suction filtration, the filter cake water repeatedly washs, 60 ℃ of vacuum-drying 24 hours, the black powder that obtains is the nitrogen-doped graphene material.
Above-mentioned method for making, the aqueous solution of the described dihydrogen phosphate ions of step 1 are the aqueous solution of phosphoric acid, primary ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.
Above-mentioned method for making, the aqueous solution of the described iron ion of step 1 are the aqueous solution of iron(ic) chloride, ferric sulfate, iron nitrate, Iron diacetate, iron protochloride or ferrous sulfate; The aqueous solution of cobalt ion is the aqueous solution of cobaltrichloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt dichloride or Cobaltous diacetate; The aqueous solution of nickel ion is the aqueous solution of nickelous chloride, single nickel salt, nickelous nitrate, nickel acetate.
Above-mentioned method for making, the described organic amine of step 1 refers to have at least the organic molecule of amino, ammonium or an imino-, wherein the number of institute's carbon containing is 2-30.For example, the C2-C12 diamines, preferably quadrol, butanediamine, pentamethylene diamine, mphenylenediamine etc., or Tetramethylammonium hydroxide, pyrroles, hexahydroaniline, or C6-C24 aromatic amine, as aniline or naphthylamines etc., or aliphatic amide, as the C4-C30 aliphatic amide, preferably hexylamine, octylame, decyl amine, amino dodecane, tetradecy lamine, cetylamine or stearylamine etc., or their mixture.
Above-mentioned method for making, the described rare gas element of step 3 comprises nitrogen, argon gas and helium.
Beneficial effect of the present invention is:
1, utilize phosphorus source cheap and easy to get, source of iron, the cobalt source, nickel source and organic amine are reactant, just can prepare the nitrogen-doped graphene material by chemical liquid phase coprecipitation method and high temperature solid-state autocatalytic method.
2, utilize the content of the nitrogen in the organic amine precursor to control the content of nitrogen-atoms in the nitrogen-doped graphene material.
3, the inventive method technique simple, be applicable to large-scale industrialization production, and cost is low, substantially there is no environmental pollution.
Description of drawings:
Fig. 1 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 1 preparation.
Fig. 2 is the Raman spectrogram of the nitrogen-doped graphene material of the embodiment of the present invention 1 preparation.
Fig. 3 is the N of the nitrogen-doped graphene material of the embodiment of the present invention 1 preparation
2The adsorption desorption curve.
Fig. 4 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 2 preparations.
Fig. 5 is the xps energy spectrum figure of the nitrogen-doped graphene material of the embodiment of the present invention 3 preparations.
Fig. 6 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 4 preparations.
Fig. 7 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 5 preparations.
Fig. 8 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 6 preparations.
Fig. 9 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 7 preparations.
Figure 10 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 7 preparations.
Figure 11 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 7 preparations.
Figure 12 is the TEM transmission electron microscope photo of the nitrogen-doped graphene material of the embodiment of the present invention 7 preparations.
Wherein, powder x-ray diffraction analysis (XRD) instrument is iPhilips X ' Pro X-ray diffractometer (Cu K α, voltage: 40 kV, electric current: 40 mA), transmission electron microscope (TEM) instrument is JEM-2010 (acceleration voltage: 200 kV).Raman (Raman) spectrum instrument is that Renishaw InVia system(testing laser wavelength is 514 nanometers).X-ray photoelectron power spectrum (XPS) analysis is measured on U.S. Thermo ESCALAB 250 x-ray photoelectron spectroscopy instrument, adopts monochromatic AlK (h=1486.6 eV), power 150 W, 500 μ m bundle spots.
Embodiment:
Further illustrate the present invention below in conjunction with embodiment.
Embodiment 1: the nitrogen-doped graphene material preparation
With the primary ammonium phosphate of 0.0016mol and the iron(ic) chloride of 0.0016 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.006 mol quadrol and 0.004mol stearylamine, stirred 120 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 25 ml/min of helium), be warming up to 650 ℃ from room temperature, and kept 14 hours under the protection of helium.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 150 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the nitrogen-doped graphene material powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is that thin slice (tulle) shape (is seen Fig. 1 a), can be found out that from the fold at its edge it has the structure of 4 layers (Graphenes) (seeing Fig. 1 b).Raman spectrum shows that it has the characteristic peak (see figure 2) of Graphene.N
2Adsorption desorption curve (see figure 3) and N
2Adsorption analysis shows that its specific surface area is 680 m
2/ g has confirmed that further (the specific surface area theoretical value of single-layer graphene is 2630 m for the structure of its four layer graphene
2/ g).XPS analysis shows that the content (quality percentage composition) of nitrogen wherein is 5.7%.
Embodiment 2:
With the SODIUM PHOSPHATE, MONOBASIC of 0.016mol and the iron protochloride of 0.016 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.07 mol hexahydroaniline and 0.01mol amino dodecane, stirred 300 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 20 ml/min of argon gas), be warming up to 900 ℃ from room temperature, and kept 4 hours under the protection of argon gas.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 180 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the nitrogen-doped graphene material powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (see figure 4).The analysis of XPS spectrum figure (see figure 5) shows that the content (quality percentage composition) of nitrogen wherein is 5.21%.
Embodiment 3:
With the potassium primary phosphate of 0.0060 mol and the ferrous sulfate of 0.0060 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.042 mol aniline and 0.018mol Tetramethylammonium hydroxide, stirred 120 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 30 ml/min of nitrogen), be warming up to 780 ℃ from room temperature, and kept 10 hours under the protection of nitrogen.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 160 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (see figure 6).The XPS spectrum map analysis shows that the content (quality percentage composition) of nitrogen wherein is 8.6%.
Embodiment 4:
With the primary ammonium phosphate of 0.01 mol and the Iron diacetate of 0.01 mol, be dissolved in 80 ml water, then add 40 ml to contain the butanediamine ethanolic soln of 0.05 mol hexylamine and 0.05 mol, stirred 180 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 25 ml/min of nitrogen), be warming up to 500 ℃ from room temperature, and kept 24 hours under the protection of nitrogen.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 170 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (similar Fig. 4), can see its 6 layers of (see figure 7)s from its edge.The XPS analysis result shows that the content (quality percentage composition) of nitrogen wherein is 20.0%.
Embodiment 5:
The biphosphate of 0.0016 mol is received and the cobalt dichloride of 0.0016 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.006 mol pentamethylene diamine and 0.004 mol tetradecy lamine, stirred 120 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 25 ml/min of helium), be warming up to 650 ℃ from room temperature, and kept 14 hours under the protection of helium.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 150 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (see figure 8).The XPS analysis result shows that the content (quality percentage composition) of nitrogen wherein is 4.3%.
Embodiment 6:
With the potassium primary phosphate of 0.016mol and the rose vitriol of 0.016 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.0016 mol mphenylenediamine, stirred 300 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 20 ml/min of argon gas), be warming up to 900 ℃ from room temperature, and kept 14 hours under the protection of argon gas.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 180 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (similar Fig. 4).Can see its 4 layers of (see figure 9)s from its edge.The XPS spectrum map analysis shows that the content (quality percentage composition) of nitrogen wherein is 1.3%.
Embodiment 7:
With the primary ammonium phosphate of 0.0060 mol and the Cobaltous diacetate of 0.0060 mol, be dissolved in 80 ml water, then add 40 ml to contain 0.02 mol octylame, 0.01mol naphthylamines and 0.01mol pyrroles's ethanolic soln, stirred 120 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 30 ml/min of nitrogen), be warming up to 780 ℃ from room temperature, and kept 10 hours under the protection of nitrogen.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 160 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (see figure 10).The XPS spectrum map analysis shows that the content (quality percentage composition) of nitrogen wherein is 3.5%.
Embodiment 8:
With the primary ammonium phosphate of 0.01 mol and the cobaltrichloride of 0.01 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.05 mol pyridine, stirred 180 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 25 ml/min of nitrogen), be warming up to 500 ℃ from room temperature, and kept 24 hours under the protection of nitrogen.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 170 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (similar Fig. 4).Can see its 5 layers (seeing Figure 11) from its edge.XPS spectrum figure shows that the content (quality percentage composition) of nitrogen wherein is 2.5%.
Embodiment 9:
With the primary ammonium phosphate of 0.0016mol and the nickelous chloride of 0.0016 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.01 mol quadrol and 0.006mol decyl amine, stirred 120 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 25 ml/min of helium), be warming up to 650 ℃ from room temperature, and kept 14 hours under the protection of helium.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 150 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (similar Figure 11).The XPS spectrum map analysis shows that the content (quality percentage composition) of nitrogen wherein is 6.3%.
Embodiment 10:
With the SODIUM PHOSPHATE, MONOBASIC of 0.16mol and the nickel acetate of 0. 16 mol, be dissolved in 80 ml water, then add 100 ml to contain the ethanolic soln of 0. 7 mol hexylamines and 0. 1mol amino dodecane, stirred 300 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 20 ml/min of argon gas), be warming up to 900 ℃ from room temperature, and kept 14 hours under the protection of argon gas.Afterwards, naturally cool to room temperature, obtain the sample powder of black.Get these black powder 4.0 grams and put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 180 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (seeing Figure 12).The XPS spectrum map analysis shows that the content (quality percentage composition) of nitrogen wherein is 14.9%.
Embodiment 11:
With the potassium primary phosphate of 0.0060 mol and the single nickel salt of 0.0060 mol, be dissolved in 80 ml water, then add 40 ml to contain the ethanolic soln of 0.042 mol pyridine and 0.018mol tetramethyl ammonium hydroxide, stirred 120 minutes.With above-mentioned suspension liquid suction filtration, 60 ℃ of lower vacuum-drying 24 hours.The powder that drying is obtained grinds, and puts into tube furnace, and (flow 30 ml/min of nitrogen), be warming up to 780 ℃ from room temperature, and kept 10 hours under the protection of nitrogen.Afterwards, naturally cool to room temperature, obtain the sample powder of black.These black powder 4.0 grams are put into the water heating kettle of 100 milliliters, add the concentrated hydrochloric acid of 80 milliliters, seal rear 160 ℃ of hydro-thermals 24 hours.Afterwards, naturally cool to room temperature, suction filtration, and repeatedly washing, 60 ℃ of lower vacuum-drying 24 hours obtains the sample powder of black.Obtain product through TEM Electronic Speculum testing product pattern, transmission electron microscope photo can be clearly seen that the nitrogen-doped graphene material that makes is thin slice (tulle) shape (similar Fig. 4).The XPS spectrum map analysis shows that the content (quality percentage composition) of nitrogen wherein is 0.5%.
Claims (10)
1. method for preparing the nitrogen-doped graphene material, the nitrogen-doped graphene material of its preparation is curling thin slice, and the number of plies of thin slice is the 1-9 layer, and wherein the content of nitrogen (quality percentage composition) is 0.5-20%, it is characterized in that it comprises the following steps:
Step 1. is containing the dihydrogen phosphate ions that concentration is 0.02-2.0 mol/L, 0.02-2.0 in the divalence of the iron of mol/L, cobalt or nickel or the solution of trivalent ion, add organic amine as template, mix and obtain suspension liquid, wherein the amount of organic amine is 0.1-10:1 with the ratio of the amount of substance of dihydrogen phosphate ions;
Step 2. is with the suspension liquid suction filtration in step 1, and filter cake room temperature vacuum-drying 24 hours obtains powder;
Step 3. is ground the powder that step 2 obtains, and puts into tube furnace, under the protection of rare gas element, is warming up to 500-900 ℃ from room temperature, and keeps 4-24 hour, afterwards, naturally cools to room temperature, obtains the powder of black;
The powder that step 4. obtains step 3 grinds puts into the water heating kettle that fills inorganic acid solution, 150-180 ℃ of lower hydro-thermal 24 hours, afterwards, be cooled to room temperature, suction filtration, the filter cake water repeatedly washs, 60 ℃ of vacuum-drying 24 hours, the black powder that obtains is the nitrogen-doped graphene material.
2. method for making according to claim 2, it is characterized in that: the aqueous solution of the described dihydrogen phosphate ions of step 1 is the aqueous solution of phosphoric acid, primary ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.
3. method for making according to claim 2, it is characterized in that: the aqueous solution of the described iron ion of step 1 is the aqueous solution of iron(ic) chloride, ferric sulfate, iron nitrate, Iron diacetate, iron protochloride or ferrous sulfate; The aqueous solution of cobalt ion is the aqueous solution of cobaltrichloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, cobalt dichloride or Cobaltous diacetate; The aqueous solution of nickel ion is the aqueous solution of nickelous chloride, single nickel salt, nickelous nitrate, nickel acetate.
4. method for making according to claim 2 is characterized in that: the described organic amine of step 1, refer to have at least the organic molecule of amino, ammonium or an imino-, and wherein the number of institute's carbon containing is 2-30.
5. comprise: C2-C12 diamines or Tetramethylammonium hydroxide, pyrroles, hexahydroaniline, C6-C24 aromatic amine or aliphatic amide, or their mixture.
6. method for making according to claim 5, it is characterized in that: described diamines is quadrol, butanediamine, pentamethylene diamine or mphenylenediamine.
7. method for making according to claim 5, it is characterized in that: described aromatic amine is aniline or naphthylamines.
8. method for making according to claim 5, it is characterized in that: described aliphatic amide is the C4-C30 aliphatic amide, or their mixture.
9. method for making according to claim 5, it is characterized in that: described aliphatic amide is hexylamine, octylame, decyl amine, amino dodecane, tetradecy lamine, cetylamine or stearylamine.
10. method for making according to claim 2, it is characterized in that: the described rare gas element of step 3 comprises nitrogen, argon gas or helium.
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| CN103738959A (en) * | 2014-02-19 | 2014-04-23 | 南京大学 | C-14-marked graphene and synthetic method thereof |
| US9327983B2 (en) * | 2014-01-06 | 2016-05-03 | Hanwha Techwin Co., Ltd. | Compositions for preparing graphene and methods for preparing graphene using the same |
| KR101739347B1 (en) * | 2015-04-24 | 2017-05-25 | 재단법인대구경북과학기술원 | Preparation method of N-doped reduced graphene oxide and the N-doped reduced graphene oxide thereby |
| CN112670095A (en) * | 2020-12-04 | 2021-04-16 | 湖南大学 | Derived carbon for reducing graphene oxide-based hydrogel through polymer filling, preparation method thereof and application of derived carbon in super capacitor |
| RU2750709C1 (en) * | 2020-10-19 | 2021-07-01 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) | Graphene modified by nitrogen atoms and its manufacturing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9327983B2 (en) * | 2014-01-06 | 2016-05-03 | Hanwha Techwin Co., Ltd. | Compositions for preparing graphene and methods for preparing graphene using the same |
| CN103738959A (en) * | 2014-02-19 | 2014-04-23 | 南京大学 | C-14-marked graphene and synthetic method thereof |
| KR101739347B1 (en) * | 2015-04-24 | 2017-05-25 | 재단법인대구경북과학기술원 | Preparation method of N-doped reduced graphene oxide and the N-doped reduced graphene oxide thereby |
| US9893199B2 (en) | 2015-04-24 | 2018-02-13 | Daegu Gyeongbuk Institute Of Science And Technology | Preparation method of reduced and N-doped graphene oxide and the reduced and N-doped graphene oxide thereby |
| RU2750709C1 (en) * | 2020-10-19 | 2021-07-01 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) | Graphene modified by nitrogen atoms and its manufacturing method |
| CN112670095A (en) * | 2020-12-04 | 2021-04-16 | 湖南大学 | Derived carbon for reducing graphene oxide-based hydrogel through polymer filling, preparation method thereof and application of derived carbon in super capacitor |
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