CN102874796A - Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof - Google Patents
Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof Download PDFInfo
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- CN102874796A CN102874796A CN201210341778XA CN201210341778A CN102874796A CN 102874796 A CN102874796 A CN 102874796A CN 201210341778X A CN201210341778X A CN 201210341778XA CN 201210341778 A CN201210341778 A CN 201210341778A CN 102874796 A CN102874796 A CN 102874796A
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Abstract
The invention provides nitrogen mixed grapheme hydrogel of which the water content is 90 to 99.5 percent, the electric conductivity is 10-3-100 S/m, and the molar ratio of N and C is 1 to 25 percent. The invention further provides nitrogen mixed aerogel of which the molar ratio of N and C is 2 to 20 percent, the molar ratio of C and O is 15 to 5, nitrogen atoms existing in the form of amidogen nitrogen accounts for 40 to 70 percent, pyridine type nitrogen accounts for 10 to 40 percent, graphite type nitrogen accounts for 10 to 30 percent, the specific area is 300 to 1500 m<2>/g, the apertures which are micropore account for 10 to 20 percent, the apertures which are mesoporous 20 to 50 percent, the apertures which are macropore 30 to 70 percent, the apparent density is 0.01 to 0.2 g/cm<3>, the pore volume is 5 to 20 cm<3>/g, and the electric conductivity is 1 to 1000 S/m. The nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof provided by the invention has the characteristics that the operation is simple, the equipment requirement is low, the production efficiency is high, the scale-up of the technology is easy, the nitrogen mixed content is controllable and the compounding with other functional substances is simple.
Description
Technical field
The invention belongs to the gentle gel technique of a kind of hydrogel, relate more specifically to a kind of nitrogen-doped graphene hydrogel or aerogel and preparation method.
Background technology
Graphene is a kind of novel carbon material after soccerballene, carbon nanotube, from Geim in 2004 etc. with the preparation of mechanically peel method success single-layer graphene, it has just started the upsurge of Graphene research in every field with the performance of uniqueness.Graphene is SP
2The carbon atom of hydridization is arranged the sheet individual layer that forms in hexagonal lattice, be a kind of perfect two-dirnentional structure material; It has specific surface (2600 m of superelevation
2g
-1), high thermal conductivity (5000 Wm
-1K
-1), great carrier mobility speed (2 * 10
5Cm
2V
-1s
-1) and strong Young's modulus (1 TPa), so the research of Graphene at aspects such as energy storage, catalysis, sensor, electron device, matrix materials receives much concern.In order further to widen the Application Areas of grapheme material, need to carry out modulation to the performance of Graphene, have dual mode available: the one, by changing Graphene pattern (size, edge type etc.), reach the purpose of modulation performance, such as graphene nanobelt, graphene quantum dot; The 2nd, by the method for chemical doping, change the chemical constitution of Graphene by the introducing of impurity atoms (N, B etc.), thereby reach the purpose of modulation.Wherein, the nitrogen significantly performance of modulation Graphene of mixing has been given the higher electroconductibility of Graphene, N-shaped doping behavior, to the catalytic performance of oxygen reduction reaction etc.The preparation of nitrogen-doped graphene is a more branch of present Graphene research, and main method has chemical Vapor deposition process, segregation growth method, arc process, high-temperature heat treatment method, plasma method.
On the other hand, in nanotechnology, in order to obtain the upper novel structure and function of macroscopic view, need to assemble the nano material unit that has special property on the microcosmic.Graphene is no exception, assembles by the oxidation of precursor Graphene to Graphene, has prepared at present transparent graphene conductive film, Graphene paper, hydrogel, aerogel etc.The Graphene hydrogel be a class take water as dispersion medium, have the gel of highly cross-linked network skeleton, have the high and good characteristics such as electroconductibility, mechanical property and chemical property of water content.The microcosmos network structure has abundant hole, and large specific surface area is provided, and is a kind of desirable electrode materials.Be the gel of air and graphene aerogel is dispersion medium, have high porosity (75-99.9%), extremely low density (0.001-0.1g/cm
3) and large specific surface area (200-1500 m
2/ g), at aspects such as lagging material, sound-proof material, sorbent material, energy storage, support of the catalyst, biocompatible materials a large amount of research is arranged.Graphene hydrogel and aerogel belong to the carbon back gel, possess carbon back characteristic that gel has, such as biocompatibility, electroconductibility, adsorptivity etc.
But up to the present, the assembling of nitrogen-doped graphene research does not also almost launch the especially preparation of nitrogen-doped graphene hydrogel and aerogel.Major cause is the self assembling process of at present preparation nitrogen-doped graphene institute employing method restriction Graphene unit.
Therefore, a kind of with low cost, simple to operate, be easy to produce amplification, the method for preparing nitrogen-doped graphene hydrogel and aerogel has to be developed.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of nitrogen-doped graphene hydrogel or aerogel, that the method has is simple to operate, mild condition, with low cost, advantage that technique is easy to amplify.
Nitrogen-doped graphene hydrogel water content of the present invention is 90-99.5%, electric conductivity 10
-3-100 S/m, N/C molar ratio are 1-25%.
Nitrogen-doped graphene aerogel N/C molar ratio of the present invention is 2-20%, and the C/O molar ratio is 15-5; The existence form of nitrogen-atoms is that amido nitrogen is 40-70%), pyridine type nitrogen is 10-40%, graphite mould nitrogen is 10-30%; Specific surface area 300-1500m
2/ g, the aperture is micropore 10-20%, mesoporous 20-50%, macropore 30-70%; Apparent density 0.01-0.2g/cm
3, pore volume 5-20cm
3/ g, specific conductivity 1-1000 S/m.
Preparation method of the present invention specifically may further comprise the steps:
(1) preparation of graphene oxide dispersion liquid: graphite oxide is ground to form the fine powder of 1-100 micron, subsequently with solvent, be stirred to and be uniformly dispersed; Afterwards above-mentioned system is carried out the 0.1-2h supersound process, power is 10-1000W, makes the dispersion liquid that concentration is 0.1-9mg/mL; Remove a small amount of insolubles through centrifugal treating subsequently, gained liquid is the graphene oxide dispersion liquid;
(2) nitrogen-doped graphene preparation of gels: the graphene oxide dispersion liquid that step (1) is obtained mixes with nitrogenous source, and stirring or ultra-sonic dispersion are even, and at 30-220 ℃ of lower reaction 0.5-36h, self-assembly makes the nitrogen-doped graphene hydrogel;
(3) preparation of nitrogen-doped graphene aerogel: the nitrogen-doped graphene hydrogel prepared to step (2) carries out drying, makes the nitrogen-doped graphene aerogel.
Described graphite oxide is take natural graphite, crystalline flake graphite, compact crystal shape graphite or synthetic graphite as raw material, adopts Hummers method, Staudenmaier method or Brodie legal system standby;
Described solvent is water, ethanol, methyl alcohol or its mixed solution;
Described nitrogenous source comprises: hydrazine hydrate, ammoniacal liquor, urea, cyanamide, trimeric cyanamide, vinyl cyanide etc.; The mass ratio of graphene oxide is 0.1-100:1 in nitrogenous source and the dispersion liquid.
Described drying mode comprises lyophilize and supercritical drying; In the lyophilize, freezing temp is-15--196 ℃, and drying temperature is-10-30 ℃, be 1-72h time of drying; In the supercritical drying, drying medium is carbonic acid gas, ethanol, methyl alcohol, acetone or water etc.
Related raw material, solvent, nitrogenous source, medium, plant and instrument etc. are not subjected to the restriction of concrete model, processing condition, operation steps etc. among the present invention, can be the products of any commerce or non-commercial.
Wherein, prepared nitrogen-doped graphene hydrogel regular shape is adjustable, and circle, trilateral, cylindrical etc. are arranged; Although its hydrogel water content is greater than 99%, its intensity is considerably beyond the intensity of common Self-Assembled, even can support the weight of 2000 times of himself weight (dry weight); No matter be at polar solvent or in strong acid, highly basic, all embodied satisfactory stability, between the freezing point of water and boiling point, sol-gel transition does not occur.
When the nitrogen-doped graphene hydrogel that the present invention is prepared is used as the sorbent material of wastewater treatment, no matter be that the nitrogen-doped graphene hydrogel is directly joined in the container that fills waste water, or the nitrogen-doped graphene hydrogel is encapsulated in the water treatment pipeline, under pressure-driven, allow waste water pass through hydrogel, good treatment effect is all arranged.The nitrogen-doped graphene hydrogel not only has very strong adsorptive power (50-5000mg/g) to the derivative of contained micro-benzene in the water, to the heavy metal ion mercury (Hg in the waste water
2+), plumbous (Pb
2+), chromium (Cr
6+), cadmium (Cd
2+), arsenic (As
3+, As
5+), cobalt (Co
2+) have strong complex ability (10-750mg/g), can be used as the sorbent material of wastewater treatment; Next can be used as the pharmaceutical carrier of control drug releasing rate.
The prepared nitrogen-doped graphene aerogel of the present invention has not only kept the face shaping of corresponding hydrogel also to have abundant pore structure, and can effectively regulate and control the type (micropore, mesoporous and macroscopical macropore) in hole, nitrogen-doped graphene sheet in the aerogel is very thin, is transparence under the electron beam of Electronic Speculum.The nitrogen-doped graphene aerogel had good prospect as double layer capacitor, storage hydrogen carrier, sensor, lagging material.
Compare with existing Graphene package technique, that the method that the present invention prepares nitrogen-doped graphene hydrogel and aerogel has is simple to operate, low for equipment requirements, production efficiency is high, technique is amplified easily, the nitrogen doping content is controlled, with the compound simple characteristics of other functional mass.Nitrogen-doped graphene hydrogel water content is high, and physical strength is large, and good stability is strong to derivative and the heavy metal ion adsorbed ability of benzene, can be used for wastewater treatment and pharmaceutical carrier.Prepared nitrogen-doped graphene aerogel has the advantages that pore structure is abundant, the aperture is adjustable, electroconductibility is good, specific surface area is large, can be used as ultracapacitor, lithium ion battery, catalytic carrier, hydrogen storage material etc.
Description of drawings
Fig. 1 is the optics picture of the prepared nitrogen-doped graphene hydrogel of the embodiment of the invention 1
Fig. 2 is the optics picture of the prepared nitrogen-doped graphene hydrogel of the embodiment of the invention 2;
Fig. 3 is the contrast before and after the prepared nitrogen-doped graphene hydrogel load-bearing of the embodiment of the invention 3, shows that prepared hydrogel has high physical strength, can support the weight of 2000 times of its dry weight weight;
Fig. 4 is the stress under compression strain curve of the prepared nitrogen-doped graphene hydrogel of the embodiment of the invention 3;
Fig. 5 is the optics picture of the prepared nitrogen-doped graphene aerogel of the embodiment of the invention 1;
Fig. 6 and Fig. 7 are the scanning electron microscope picture of the embodiment of the invention 1 prepared nitrogen-doped graphene aerogel;
Fig. 8 is the nitrogen adsorption/desorption curve synoptic diagram of the embodiment of the invention 1 prepared nitrogen-doped graphene aerogel;
Fig. 9 and Figure 10 are that the embodiment of the invention 4 prepared nitrogen-doped graphene aerogel XPS spectrum figure and N1s compose.
Specific implementation method
For the present invention is further explained, be elaborated below in conjunction with specific embodiments and the drawings, described embodiment is that unrestriced mode proposes in the mode of example.
Embodiment 1:
(1) preparation of graphene oxide dispersion liquid:
Take natural graphite as raw material, adopt the standby graphite oxide of Hummers legal system, concrete steps are as follows: 5 g Graphite Powder 99s are joined 1.5 L fill 115 mL 98%H
-2SO
4There-necked flask in, stir 24 h under the normal temperature; The NaNO that adds 2.5 g in the there-necked flask
3, continue to stir 30 min, and there-necked flask is placed ice bath (＜5 ℃), keep 30 min; In the situation of vigorous stirring, slowly add 15 g KMnO to the flask that places ice bath
4, hierarchy of control temperature＜20 ℃; Flask transferred in 35 ± 3 ℃ the water-bath, and keep 30 min; The deionized water of 230 mL is slowly joined in the system system temperature〉90 ℃, continue afterwards to stir 15 min.Add 700 mL deionized waters and dilute, add again 50 mL, 30% H
20
2Reduce unreacted KMnO
4And MnO
2, termination reaction; While hot mixed system is carried out vacuum filtration, and with 700 mL deionized water rinsing filter cakes, resulting solid is dry, for subsequent use in 40 ℃ vacuum drying oven.The gained graphite oxide is ground to form the fine powder of 1-100 micron, and take water as solvent, magnetic agitation made the graphite oxide dispersion liquid of 2mg/ml to being uniformly dispersed in 24 hours; Carry out afterwards the supersound process of 0.5h under 40KHz/100W, and carry out the centrifugal treating of 0.5h under the 3000rpm centrifugation rate, the gained supernatant liquor is the graphene oxide dispersion liquid.
(2) nitrogen-doped graphene preparation of gels:
Be 100:1 according to 28% ammoniacal liquor and graphene oxide mass ratio, in above-mentioned dispersion liquid, add 28% strong aqua, mix under the magnetic agitation, be transferred in the hydrothermal reaction kettle; Then place 180 ℃ homogeneous reactor, reaction 5h reacts complete rear normal temperature cooling, makes the nitrogen-doped graphene hydrogel.Prepared nitrogen-doped graphene hydrogel water content is the 99.4%(massfraction), N/C=15%, electric conductivity is 55S/m.
(3) preparation of nitrogen-doped graphene aerogel:
Above-mentioned gained nitrogen-doped graphene hydrogel is successively carried out 4 days water exchange and 1 day ethanol exchange, make the alcogel of nitrogen-doped graphene, afterwards with CO
2For drying medium carries out the supercritical drying of 12h, can obtain the nitrogen-doped graphene aerogel.Prepared nitrogen-doped graphene aerogel N/C=15%, O/C=9%, amido nitrogen are 41%, and pyridine type nitrogen is 39%, and graphite mould nitrogen is 20%; Specific surface area is 1100m
2/ g, micropore 20%, mesoporous 50%, macropore 30%; Apparent density 0.1g/cm
3, pore volume 9.8cm
3/ g, specific conductivity 900S/m.
Embodiment 2:
(1) preparation of graphene oxide dispersion liquid:
Take crystalline flake graphite as raw material, adopt the standby graphite oxide of Hummers legal system; The gained graphite oxide is ground to form the fine powder of 1-100 micron, and take water/ethanol (volume ratio 1:1) as solvent, magnetic agitation made the graphite oxide dispersion liquid of 4mg/ml to being uniformly dispersed in 24 hours; Carry out afterwards the supersound process of 1h under 40KHz/100W, and carry out the centrifugal treating of 0.5h under the 4500rpm centrifugation rate, the gained supernatant liquor is the graphene oxide dispersion liquid.
(2) nitrogen-doped graphene preparation of gels:
Be 10:1 according to 80% hydrazine hydrate and graphene oxide mass ratio, in above-mentioned dispersion liquid, add 80% hydrazine hydrate, mix under the magnetic agitation, be transferred in the encloses container; Then in 35 ℃ of lower reaction 36h, react complete rear normal temperature cooling, make the nitrogen-doped graphene hydrogel.Prepared nitrogen-doped graphene hydrogel water content is the 95%(massfraction), N/C=10%, electric conductivity is 4S/m.
(3) preparation of nitrogen-doped graphene aerogel:
Above-mentioned gained nitrogen-doped graphene hydrogel is successively carried out 3 days water exchange, under liquid nitrogen temperature, carry out afterwards freezingly, between freezing point to 30 ℃, carry out the 48h drying, can obtain the nitrogen-doped graphene aerogel.Prepared nitrogen-doped graphene aerogel N/C=10%, O/C=18%, amido nitrogen are 45%, and pyridine type nitrogen is 43%, and graphite mould nitrogen is 12%; Specific surface area is 700m
2/ g, micropore 15%, mesoporous 58%, macropore 27%; Apparent density 0.15g/cm
3, pore volume 6.5cm
3/ g, specific conductivity 57S/m.
Embodiment 3:
(1) preparation of graphene oxide dispersion liquid:
Take synthetic graphite as raw material, adopt the standby graphite oxide of Staudenmaier legal system; The gained graphite oxide is ground to form the fine powder of 1-100 micron, and take water/methyl alcohol (volume ratio 3:1) as solvent, magnetic agitation made the graphite oxide dispersion liquid of 1.5mg/ml to being uniformly dispersed in 24 hours; Carry out afterwards the supersound process of 20min under 40KHz/200W, and carry out the centrifugal treating of 15min under the 5000rpm centrifugation rate, the gained supernatant liquor is the graphene oxide dispersion liquid.
(2) nitrogen-doped graphene preparation of gels:
Be 20:1 according to urea and graphene oxide mass ratio, add urea in above-mentioned dispersion liquid, ultra-sonic dispersion is even, is transferred in the hydrothermal reaction kettle; Then place 200 ℃ homogeneous reactor, reaction 4h reacts complete rear normal temperature cooling, makes the nitrogen-doped graphene hydrogel.Prepared nitrogen-doped graphene hydrogel water content is the 99%(massfraction), N/C=11%, electric conductivity is 34S/m.
(3) preparation of nitrogen-doped graphene aerogel:
Above-mentioned gained nitrogen-doped graphene hydrogel is successively carried out 4 days water exchange and 1 day methyl alcohol exchange, make the alcogel of nitrogen-doped graphene, carry out afterwards the supercritical drying of 24h take methyl alcohol as drying medium, can obtain the nitrogen-doped graphene aerogel.Prepared nitrogen-doped graphene aerogel N/C=11%, O/C=7.5%, amido nitrogen are 51%, and pyridine type nitrogen is 39%, and graphite mould nitrogen is 10%; Specific surface area is 950m
2/ g, micropore 27%, mesoporous 47%, macropore 26%; Apparent density 0.02g/cm
3, pore volume 20cm
3/ g, specific conductivity 540S/m.
Embodiment 4
(1) preparation of graphene oxide dispersion liquid:
Take fine and close crystalloid graphite as raw material, adopt the standby graphite oxide of Brodie legal system; The gained graphite oxide is ground to form fine powder about 20 microns, and take water as solvent, mechanical stirring made the graphite oxide dispersion liquid of 0.8mg/ml to being uniformly dispersed in 12 hours; Carry out afterwards the supersound process of 1h under 40KHz/100W, and carry out the centrifugal treating of 10min under the 8000rpm centrifugation rate, the gained supernatant liquor is the graphene oxide dispersion liquid.
(2) nitrogen-doped graphene preparation of gels:
Be 5:1 according to cyanamide and graphene oxide mass ratio, in above-mentioned dispersion liquid, add cyanamide, be uniformly dispersed under the magnetic agitation, be transferred in the hydrothermal reaction kettle; Then place 160 ℃ homogeneous reactor, reaction 10h reacts complete rear normal temperature cooling, makes the nitrogen-doped graphene hydrogel.Prepared nitrogen-doped graphene hydrogel water content is the 99.3%(massfraction), N/C=6%, electric conductivity is 20S/m.
(3) preparation of nitrogen-doped graphene aerogel:
Above-mentioned gained nitrogen-doped graphene hydrogel is carried out 10 times water exchange, make the hydrogel of pure nitrogen-doped graphene, under liquid nitrogen temperature, carry out afterwards freezingly, between freezing point to 10 ℃, carry out the 48h drying, can obtain the nitrogen-doped graphene aerogel.Prepared nitrogen-doped graphene aerogel N/C=6%, O/C=9%, amido nitrogen are 48%, and pyridine type nitrogen is 47%, and graphite mould nitrogen is 5%; Specific surface area is 690m
2/ g, micropore 24%, mesoporous 47%, macropore 29%; Apparent density 0.036g/cm
3, pore volume 50cm
3/ g, specific conductivity 690S/m.
Embodiment 5:
(1) preparation of graphene oxide dispersion liquid: identical with embodiment 1 step (1).
(2) nitrogen-doped graphene preparation of gels:
Be 0.5:1 according to trimeric cyanamide and graphene oxide mass ratio, add trimeric cyanamide in above-mentioned dispersion liquid, magnetic agitation also heats 2h to mixing, and is transferred in the hydrothermal reaction kettle; Then place 220 ℃ homogeneous reactor, reaction 6h reacts complete rear normal temperature cooling, makes the nitrogen-doped graphene hydrogel.Prepared nitrogen-doped graphene hydrogel water content is the 99.2%(massfraction), N/C=4%, electric conductivity is 70S/m.
(3) preparation of nitrogen-doped graphene aerogel:
Above-mentioned gained nitrogen-doped graphene hydrogel is carried out 4 days water exchange under 80 ℃, carry out again afterwards the ethanol exchange, under liquid nitrogen temperature, carry out afterwards freezingly, between freezing point to 10 ℃, carry out the 10h drying, can obtain the nitrogen-doped graphene aerogel.Prepared nitrogen-doped graphene aerogel N/C=4%, O/C=7.7%, amido nitrogen are 53%, and pyridine type nitrogen is 36, and graphite mould nitrogen is 11%; Specific surface area is 690m
2/ g, micropore 19%, mesoporous 67%, macropore 14%; Apparent density 0.024g/cm
3, pore volume 41cm
3/ g, specific conductivity 360S/m.
Embodiment 6:
(1) preparation of graphene oxide dispersion liquid: identical with embodiment 1 step (1).
(2) nitrogen-doped graphene preparation of gels:
Be 100:1 according to 28% ammoniacal liquor and graphene oxide mass ratio, in above-mentioned dispersion liquid, add 28% strong aqua, mix under the magnetic agitation, be transferred in the flask with reflux; Then place 100 ℃ oil bath, reaction 24h reacts complete rear normal temperature cooling, makes the nitrogen-doped graphene hydrogel.Prepared nitrogen-doped graphene hydrogel water content is the 99.5%(massfraction), N/C=12%, electric conductivity is 4S/m.
(3) preparation of nitrogen-doped graphene aerogel: identical with embodiment 1 step (3).
Prepared nitrogen-doped graphene aerogel N/C=12%, O/C=12.5%, amido nitrogen are 66%, and pyridine type nitrogen is 28, and graphite mould nitrogen is 6%; Specific surface area is 510m
2/ g, micropore 27%, mesoporous 56%, macropore 17%; Apparent density 0.04g/cm
3, pore volume 25cm
3/ g, specific conductivity 130/m.
Claims (8)
1. a nitrogen-doped graphene hydrogel is characterized in that nitrogen-doped graphene hydrogel water content is 90-99.5%, electric conductivity 10
-3-100 S/m, N/C molar ratio are 1-25%.
2. nitrogen-doped graphene aerogel, the N/C molar ratio that it is characterized in that the nitrogen-doped graphene aerogel is 2-20%, the C/O molar ratio is 15-5; The existence form of nitrogen-atoms is that amido nitrogen is 40-70%, and pyridine type nitrogen is 10-40%, and graphite mould nitrogen is 10-30%; Specific surface area 300-1500m
2/ g, the aperture is micropore 10-20%, mesoporous 20-50%, macropore 30-70%; Apparent density 0.01-0.2g/cm
3, pore volume 5-20cm
3/ g, specific conductivity 1-1000 S/m.
3. a kind of nitrogen-doped graphene preparation of gels method as claimed in claim 1 is characterized in that may further comprise the steps:
(1) preparation of graphene oxide dispersion liquid: graphite oxide is ground to form the fine powder of 1-100 micron, subsequently with solvent, be stirred to and be uniformly dispersed; Afterwards above-mentioned system is carried out the 0.1-2h supersound process, power is 10-1000W, makes the dispersion liquid that concentration is 0.1-9mg/mL; Remove a small amount of insolubles through centrifugal treating subsequently, gained liquid is the graphene oxide dispersion liquid;
(2) nitrogen-doped graphene preparation of gels: the graphene oxide dispersion liquid that step (1) is obtained mixes with nitrogenous source, and stirring or ultra-sonic dispersion are even, and at 30-220 ℃ of lower reaction 0.5-36h, self-assembly makes the nitrogen-doped graphene hydrogel.
4. a kind of nitrogen-doped graphene preparation of gels method as claimed in claim 3, it is characterized in that described graphite oxide is take natural graphite, crystalline flake graphite, compact crystal shape graphite or synthetic graphite as raw material, adopt Hummers method, Staudenmaier method or Brodie legal system standby.
5. a kind of nitrogen-doped graphene preparation of gels method as claimed in claim 3 is characterized in that described solvent is water, ethanol, methyl alcohol or its mixed solution.
6. a kind of nitrogen-doped graphene preparation of gels method as claimed in claim 3 is characterized in that described nitrogenous source is hydrazine hydrate, ammoniacal liquor, urea, cyanamide, trimeric cyanamide or vinyl cyanide; The mass ratio of graphene oxide is 0.1-100:1 in nitrogenous source and the dispersion liquid.
7. the preparation method of a kind of nitrogen-doped graphene aerogel as claimed in claim 2 is characterized in that may further comprise the steps:
(1) preparation of graphene oxide dispersion liquid: graphite oxide is ground to form the fine powder of 1-100 micron, subsequently with solvent, be stirred to and be uniformly dispersed; Afterwards above-mentioned system is carried out the 0.1-2h supersound process, power is 10-1000W, makes the dispersion liquid that concentration is 0.1-9mg/mL; Remove a small amount of insolubles through centrifugal treating subsequently, gained liquid is the graphene oxide dispersion liquid;
(2) nitrogen-doped graphene preparation of gels: the graphene oxide dispersion liquid that step (1) is obtained mixes with nitrogenous source, and stirring or ultra-sonic dispersion are even, and at 30-220 ℃ of lower reaction 0.5-36h, self-assembly makes the nitrogen-doped graphene hydrogel;
(3) preparation of nitrogen-doped graphene aerogel: the nitrogen-doped graphene hydrogel prepared to step (2) carries out drying, makes the nitrogen-doped graphene aerogel.
8. the preparation method of a kind of nitrogen-doped graphene aerogel as claimed in claim 7 is characterized in that described drying is lyophilize and supercritical drying; In the lyophilize, freezing temp is-15--196 ℃, and drying temperature is-10-30 ℃, be 1-72h time of drying; In the supercritical drying, drying medium is carbonic acid gas, ethanol, methyl alcohol, acetone or water.
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