CN104261388A - Method for preparing nitrogen-doped graphene by treating carbonate by shock waves - Google Patents
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Abstract
The invention discloses a method for preparing nitrogen-doped graphene by treating carbonate by shock waves and belongs to the technical field of processes. The method comprises the following steps: uniformly mixing a carbon source, a reducing agent and a nitrogen source and compacting to obtain an initial blank; colliding a sample box by using a flyer to induce chemical reaction to obtain powder; putting the powder into a reactor, adding concentrated nitric acid for purification, reacting and filtering and washing to obtain a solid a; and drying to obtain the nitrogen-doped graphene. The number of molecular layers of the nitrogen-doped graphene is 1-6, and the nitrogen doping content is high, so that the nitrogen-doped graphene has good oxygen reduction catalytic activity. The method is low in cost, short in production period, simple in process and low in requirements on production conditions, hardly causes dangers in the production process and can be put into industrial production conveniently.
Description
Technical field
The present invention relates to a kind of method of shock wave treatment manufacture of carbonates nitrogen-doped graphene, belong to Technology field.
Background technology
Within 2004, utilize the method for tape stripping high orientation graphite to obtain by the Novoselov etc. of Univ Manchester UK, and find the relativistic particles characteristic of Graphene current carrier.Truly self-existent two-dimensional material has been declared in the discovery of Graphene, the zero dimension soccerballene (Fullerene) found with 1985 and the one dimension carbon nanotube (carbon nanotubes) found for 1991, also have the three dimensional diamond of sp3 hydridization known by people and the three-dimensional graphite of sp2 hydridization, jointly constitute carbon system extended familys, expand the category of the allotropic substance of carbon, also make the diversity of people to carbon have more deep understanding.Graphene is the new carbon of carbon atom tightly packed one-tenth bi-dimensional cellular shape crystalline network, it similarly is a net be made up of regular hexagon aperture be made into by carbon atom, the thickness of net only has 0.335nm, be only hair 200,000/, the elementary cell building other dimension carbonaceous materials (zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite), symmetrical configuration and perfect.
Graphene, less than the infinite glamour fully presented in the time of 10 years in theoretical investigation and practical application, becomes rapidly the study frontier that field of scientific study enlivens the most.This special two-dirnentional structure causes Graphene to show various special performance.Graphene obtains in fields such as matrix material, fuel cell and hydrogen storage materials and pays close attention to widely.
More than ten years in past, a variety of method successfully synthesizes Graphene and nitrogen-doped graphene, but is the method that Graphene prepared by raw material with carbonate, only there is one: mix with carbonate powder with metal magnesium powder, make it at high temperature redox reaction occur.2012, Shanxi Datong University successfully utilized magnesium powder in sealed reaction vessel, by being mixed with calcium carbonate powders by magnesium; under argon gas atmosphere protection; with soak 0.5 ~ 5h continuous heating of 850 DEG C, make mixed powder generation redox reaction, successfully prepare Graphene.The method has raw material to be easy to the advantage obtained, but also there is severe reaction conditions, and duration of the reaction is long, the shortcoming that production cost is high.In the method production process, raw material powder needs the high temperature being heated to 850 DEG C, and is incubated 0.5 ~ 5h, makes the method carry out in suitability for industrialized production, is easy to occur production hidden danger, once have an accident, lose larger.In addition, owing to there being high temperature resistant and resistance to air loss requirement to reaction vessel, make reaction vessel cost high, reaction process needs rare gas argon gas to do shielding gas, thus causes the method production cost high.
By contrast, the great advantage of ballistic method is that output is large, speed is fast, efficiency is high, saves the energy and good economy performance.Thus, to be easy to acquisition, cheap raw material, with the required product of ballistic method synthesis, by the time more a large amount of than other method saving and cost, there is better economy.
Summary of the invention
For existing manufacture of carbonates Graphene method, raw material is needed to be in the environment of airtight high temperature for a long time, high to the requirement of conversion unit, duration of the reaction is long, thus there is the problem that production cost is high, complex process, production process easily go out hazardous condition, the object of the present invention is to provide a kind of method of shock wave treatment manufacture of carbonates nitrogen-doped graphene, described method cost be low, with short production cycle, technique be simply convenient to can suitability for industrialized production, not easily there is danger in, production process low to working condition requirement.
Object of the present invention is realized by following technical scheme:
A method for shock wave treatment manufacture of carbonates nitrogen-doped graphene, described method concrete steps are as follows:
(1) carbon source, reductive agent and nitrogenous source are mixed, obtain powder 1; Powder 1 is loaded sample box, compacting, obtain the first base that density is 80 ~ 95%;
(2) clash into sample box induced chemical reaction with film flying, obtain powder 2;
(3) powder 2 is put into reactor, add concentrated nitric acid and purify, at 65 ~ 80 DEG C, react 12 ~ 15h, filtration washing, obtains solid a, and dry, obtain powder 3, powder 3 is nitrogen-doped graphene of the present invention;
Wherein, step (1) described carbon source is carbonate, the one in the preferred calcium carbonate of carbonate and magnesiumcarbonate; One in reductive agent preferably magnesium powder, sodium powder or potassium powder; One in the preferred ammonium nitrate of nitrogenous source and urea;
Mass ratio preferably 2 ~ 4:1:0.2 ~ 0.8 of step (1) described carbon source, reductive agent and nitrogenous source;
The described compacting of step (1) adopts hydropress, the preferred 7.5MPa of pressure, and the dwell time is 1 ~ 2min preferably;
The stainless steel sample box of the preferred cupric liner of step (1) described sample box; The thickness preferably 1 ~ 3mm of copper liner; Stainless steel sample box wall thickness preferably 2 ~ 3mm; Meeting under copper liner and the non-destructive prerequisite of stainless steel sample box, selecting minimum thickness, powder raw material can be made like this to obtain larger pressure.
Step (2) described film flying is the film flying driven with explosive detonation, the one in the preferred Nitromethane 99Min. liquid of explosive, 8701 explosives and B explosive; Flyer velocity is 2.83 ~ 3.37km/s preferably;
The preferred vacuum freezedrying of step (3) described drying.
Beneficial effect
(1) the method for the invention requires low to working condition, can carry out under normal temperature, and without the need to protective atmosphere, to reaction unit without resistance to air loss requirement; Because the mode that shockwave loads can make the temperature of raw material rise 1000 ~ 3000 DEG C at 1 ~ 10 μ s, and produces high pressure (500 ~ 2000MPa); And at 1 ~ 10 μ s subsequently, temperature and pressure declines rapidly, and reactant residual temperature is at about 100 DEG C, and pressure gets back to normal pressure; Whole chemical reaction completes at this 1 ~ 10 μ s, and cooling rate is exceedingly fast, and because temperature and pressure is too low after reaction, reactant can not react with other materials such as oxygen.Therefore, adopt shock wave treatment raw material, without the need to additionally for raw material provides high temperature and high pressure environment, also without the need to providing protective atmosphere.
(2) the method for the invention is with short production cycle, has reclaimed from preparatory stage to product, only needs 10 ~ 30 minutes;
(3) the method for the invention production cost is low, and without the need to adopting special steel material or other non-ferrous metal alloy materials, be convenient to processing, raw material is easy to get and cheap;
(4) the nitrogen-doped graphene number of molecule layers that the method for the invention is produced is 1 ~ 6 layer, and N doping amount is high, has good redox catalysis active.
Accompanying drawing explanation
Fig. 1 is the device schematic diagram of shock wave synthesis Graphene;
Fig. 2 is x-ray photoelectron power spectrum (XPS) figure of embodiment 1 products therefrom;
Fig. 3 is X-ray diffraction (XRD) figure of embodiment 1 products therefrom;
Fig. 4 is the transmission electron microscope picture of embodiment 1 products therefrom;
Fig. 5 is the transmission electron microscope picture Regional High Resolution figure of embodiment 1 products therefrom;
Fig. 6 is the transmission electron microscope picture Regional High Resolution figure of embodiment 1 products therefrom;
Fig. 7 is the cyclic voltammetry curve of embodiment 1 products therefrom;
Fig. 8 is linear sweep voltammetry (LSV) curve of the lower different rotating speeds of embodiment 1 products therefrom;
Fig. 9 is x-ray photoelectron power spectrum (XPS) figure of embodiment 2 products therefrom;
Figure 10 is X-ray diffraction (XRD) figure of embodiment 2 products therefrom;
Figure 11 is the transmission electron microscope picture of embodiment 2 products therefrom;
Figure 12 is the transmission electron microscope picture Regional High Resolution figure of embodiment 2 products therefrom;
Figure 13 is the transmission electron microscope picture Regional High Resolution figure of embodiment 2 products therefrom;
Figure 14 is the cyclic voltammetry curve of embodiment 2 products therefrom.
Figure 15 is linear sweep voltammetry (LSV) curve of the lower different rotating speeds of embodiment 2 products therefrom.
Figure 16 is x-ray photoelectron power spectrum (XPS) figure of embodiment 3 products therefrom;
Figure 17 is X-ray diffraction (XRD) figure of embodiment 3 products therefrom;
Figure 18 is the transmission electron microscope picture of embodiment 3 products therefrom;
Figure 19 is the transmission electron microscope picture Regional High Resolution figure of embodiment 3 products therefrom;
Figure 20 is the transmission electron microscope picture Regional High Resolution figure of embodiment 3 products therefrom;
Figure 21 is the cyclic voltammetry curve of embodiment 3 products therefrom;
Figure 22 is linear sweep voltammetry (LSV) curve of the lower different rotating speeds of embodiment 3 products therefrom.
In note: Fig. 4 and 6, " L " represents the number of plies of Graphene.
Wherein, top cover, 5-stainless steel film flying, 6-plastics retaining ring, 7-stainless steel sample box, 8-copper backing, 9-copper liner, 10-stainless steel stem stem, 11-cavity, 12-stainless steel base under 1-aluminium matter detonator cover, 2-plastics upper top cover, 3-PVC pipe, 4-plastics.
Embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited thereto.
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
The main agents information mentioned in following examples is in table 1; Key instrument and facility information are in table 2.
Table 1
Table 2
In following examples, as shown in Figure 1, described device comprises the device of shock wave synthesis Graphene used: top cover 4, stainless steel film flying 5, plastics retaining ring 6, stainless steel sample box 7, copper backing 8, copper liner 9, stainless steel stem stem 10, cavity 11, stainless steel base 12 under aluminium matter detonator cover 1, plastics upper top cover 2, pvc pipe 3, plastics.
Wherein, copper liner 9 is provided with bottom stainless steel sample box 7, powder raw material is put bottom copper liner 9, copper backing 8 is provided with above powder raw material, stainless steel stem stem 10 screws in stainless steel sample box 7 from top and withstands copper backing 8, copper backing 8 and powder raw material close contact, cavity 11 is left in stainless steel stem stem 10 and stainless steel sample box 7 side, is inverted by stainless steel sample box 7 in the circular groove loaded in stainless steel base 12.
Plastics retaining ring 6 is fixed on above stainless steel base 12, under plastics, top cover 4 is positioned at the top of plastics retaining ring 6, and pvc pipe 3 is fixed on the top of top cover 4 under plastics, and plastics upper top cover 2 is installed on the top of pvc pipe 3, plastics upper top cover 2 center is provided with circular hole, puts into aluminium matter detonator cover 1.Fill booster explosive bottom aluminium matter detonator cover 1, detonator is put in top.Detonator is positioned at plastics upper top cover 2 upper center.
Under pvc pipe 3 and plastics, top cover 4 is bonded together by glass cement, and stainless steel film flying 5 502 glue are bonded in top cover 4 circular groove under plastics, and explosive, just to sample box 7, loads in pvc pipe 3 by film flying 5, and detonator inserts booster explosive top center.Primer detonator carries out explosion shock wave treatment, recovery sample.
Flyer velocity is calculated by following known formula:
In formula (1),
u
maxfor flyer velocity, η is relative compressibility, and m is quality of explosive, and M is film flying quality, ρ
0for explosive density, l is shot elevation, ρ
mfor film flying density, d is film flying thickness, and D is detonation rate, and S is film flying area.It can thus be appreciated that flyer velocity is final relevant with explosive density, shot elevation, film flying thickness, film flying density and detonation rate.Suitable flyer velocity can be obtained by adjustment correlation parameter.
In following examples, film flying thickness is 1.5mm or 2mm, and film flying density is 7.93g/cm
3, explosive adopts liquid Nitromethane 99Min., and explosive density is 1.13g/cm
3, detonation rate is 6300m/s.
Density calculation formula: the density of the compacted density/powder of density=powder raw material itself.
Embodiment 1
(1) magnesiumcarbonate (8g), sodium (4g) and ammonium nitrate (3.2g) are mixed, obtain powder 1; Powder 1 is loaded the stainless steel box of cupric liner, adopt hydropress compacting, obtain the first base that density is 95%;
Wherein, the thickness of copper liner is 1mm; Stainless steel box wall thickness is 2mm; Hydropress pressure is 7.5MPa, dwell time 2min;
(2) clash into sample box induced chemical reaction with the film flying that speed is 2.83km/s, obtain powder 2; Wherein, film flying is the film flying by Nitromethane 99Min. liquid detonation driven;
(3) powder 2 is put into reactor, add concentrated nitric acid to purify, at 70 DEG C, react 13h, filtering and washing, obtain solid a, vacuum freezedrying, obtain black powder, as shown in Figure 2, in the element binding energy collection of illustrative plates of black powder, occur element binding energy peak at 284eV, 400eV, 532eV place, corresponding C element peak, N element peak, O element peak respectively, N element content molecular percentage ratio reaches 3.84% as calculated.As seen from Figure 3, the XRD figure spectrum of black powder observes (002) crystallographic plane diffraction peak in typical graphite-structure in 2 θ=26 °, and interfloor distance d is about 0.34nm, illustrates that in black powder, main component is the Graphitic carbon structure containing sp2.According to black powder transmission electron microscope picture spectrogram 4, Fig. 5, Fig. 6, black powder microscopic appearance is the film like structures of distortion, and its number of molecule layers is 1 ~ 6 layer, is typical few layer graphene.To sum up, described black powder is nitrogen-doped graphene, and its number of molecule layers is 1 ~ 6 layer, and N doping amount is 3.84%;
Fig. 7 is that nitrogen-doped graphene is at N
2saturated lower and O
2cyclic voltammetry curve under saturated, under oxygen saturation, the initial peak of redox is positioned at-0.14V, and has oxidation reduction peak at-0.26V place, and at N
2redox peak is not had to occur under saturated.Fig. 8 is the LSV curve of nitrogen-doped graphene different rotating speeds under oxygen saturation, and along with rotating speed increases, current density increases.The electronic number being obtained each oxygen molecule reduction transfer by Koutechy-Levich Equation for Calculating is about 3.4, illustrate that the redox reaction of carrying out on nitrogen-doped graphene mainly generates water according to the transfer of 2-4 electronic channel, result shows that the redox catalysis that the nitrogen-doped graphene of impact synthesis is good is active.
Embodiment 2
(1) calcium carbonate (12g), sodium (3g) and ammonium nitrate (0.6g) are mixed, obtain powder 1; Powder 1 is loaded the stainless steel box of cupric liner, adopt hydropress compacting, obtain the first base that density is 80%; Wherein, the thickness of copper liner is 2mm; Stainless steel box wall thickness is 3mm; Hydropress pressure is 7.5MPa, dwell time 1min;
(2) clash into sample box induced chemical reaction with the film flying that speed is 2.95km/s, obtain powder 2; Wherein, film flying is the film flying by Nitromethane 99Min. liquid detonation driven;
(3) powder 2 is put into reactor, add concentrated nitric acid to purify, at 65 DEG C, react 15h, filtering and washing, obtain solid a, vacuum freezedrying, obtain black powder, as shown in Figure 9, in the element binding energy collection of illustrative plates of black powder, occur element binding energy peak at 284eV, 400eV, 532eV place, corresponding C element peak, N element peak, O element peak respectively, N element content molecular percentage ratio reaches 1.81% as calculated.As seen from Figure 10, the XRD figure spectrum of black powder observes (002) crystallographic plane diffraction peak in typical graphite-structure in 2 θ=26 °, and interfloor distance d is about 0.34nm, illustrates that in black powder, main component is the Graphitic carbon structure containing sp2.According to transmission electron microscope picture spectrogram 11, Figure 12, Figure 13 of black powder, the microscopic appearance of black powder is the film like structures of distortion, and its number of molecule layers is 1 ~ 4 layer, is typical few layer graphene.To sum up, described black powder is nitrogen-doped graphene, and its number of molecule layers is 1 ~ 4 layer, and N doping amount is 1.81%;
Figure 14 is that nitrogen-doped graphene is at N
2saturated and O
2cyclic voltammetry curve under saturated, under oxygen saturation, the initial peak of redox is positioned at-0.17V, and has oxidation reduction peak at-0.27V place; And at N
2redox peak is not had to occur under saturated.Figure 15 is the LSV curve of nitrogen-doped graphene different rotating speeds under oxygen saturation, and along with rotating speed increases, current density increases.The electronic number being obtained each oxygen molecule reduction transfer by Koutechy-Levich Equation for Calculating is about 3.2, illustrate that the redox reaction of carrying out on nitrogen-doped graphene mainly generates water according to the transfer of 2-4 electronic channel, result shows that the redox catalysis that the nitrogen-doped graphene of impact synthesis is good is active.
Embodiment 3
(1) calcium carbonate (9g), magnesium (3g) and urea (1.8g) are mixed, obtain powder 1; Powder 1 is loaded the stainless steel box of cupric liner, adopt hydropress compacting, obtain the first base that density is 88%; Wherein, the thickness of copper liner is 3mm; Stainless steel box wall thickness is 3mm; Hydropress pressure is 7.5MPa, dwell time 2min;
(2) clash into sample box induced chemical reaction with the film flying that speed is 3.37km/s, obtain powder 2; Wherein, film flying is the film flying by Nitromethane 99Min. liquid detonation driven;
(3) powder 2 is put into reactor, add concentrated nitric acid to purify, at 80 DEG C, react 12h, filtering and washing, obtain solid a, vacuum freezedrying, obtain black powder, as shown in Figure 16, in the element binding energy collection of illustrative plates of black powder, occur element binding energy peak at 284eV, 400eV, 532eV place, corresponding C element peak, N element peak, O element peak respectively, N element content molecular percentage ratio reaches 4.33% as calculated.As seen from Figure 17, the XRD figure spectrum of black powder observes (002) crystallographic plane diffraction peak in typical graphite-structure in 2 θ=26 °, and interfloor distance d is about 0.34nm, illustrates that in black powder, main component is the Graphitic carbon structure containing sp2.According to transmission electron microscope picture spectrogram 18, Figure 19, Figure 20 of black powder, the microscopic appearance of black powder is the film like structures of distortion, and its number of molecule layers is 1 ~ 4 layer, is typical few layer graphene.To sum up, described black powder is nitrogen-doped graphene, and its number of molecule layers is 1 ~ 4 layer, and N doping amount is 4.33%;
Figure 21 is that nitrogen-doped graphene is at N
2saturated and O
2cyclic voltammetry curve under saturated, under oxygen saturation, the initial peak of redox is positioned at-0.16V, and has oxidation reduction peak at-0.27V place; And at N
2redox peak is not had to occur under saturated.Figure 22 is the LSV curve of nitrogen-doped graphene different rotating speeds under oxygen saturation, and along with rotating speed increases, current density increases.The electronic number being obtained each oxygen molecule reduction transfer by Koutechy-Levich Equation for Calculating is about 3.3, illustrate that the redox reaction of carrying out on nitrogen-doped graphene mainly generates water according to the transfer of 2-4 electronic channel, result shows that the redox catalysis that the nitrogen-doped graphene of impact synthesis is good is active.
The present invention includes but be not limited to above embodiment, every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.
Claims (7)
1. a method for shock wave treatment manufacture of carbonates nitrogen-doped graphene, is characterized in that: described method concrete steps are as follows:
(1) carbon source, reductive agent and nitrogenous source are mixed, obtain powder 1; Powder 1 is loaded sample box, compacting, obtain the first base that density is 80 ~ 95%;
(2) clash into sample box induced chemical reaction with film flying, obtain powder 2;
(3) powder 2 is put into reactor, add concentrated nitric acid, at 65 ~ 80 DEG C, react 12 ~ 15h, filtration washing, obtains solid a, and dry, obtain powder 3, powder 3 is described nitrogen-doped graphene.
2. the method for a kind of shock wave treatment manufacture of carbonates nitrogen-doped graphene according to claim 1, is characterized in that: step (1) described carbon source is the one in calcium carbonate and magnesiumcarbonate; Reductive agent is the one in magnesium powder, sodium powder or potassium powder; Nitrogenous source is the one in ammonium nitrate and urea.
3. the method for a kind of shock wave treatment manufacture of carbonates nitrogen-doped graphene according to claim 1, is characterized in that: the mass ratio of step (1) described carbon source, reductive agent and nitrogenous source is 2 ~ 4:1:0.2 ~ 0.8.
4. the method for a kind of shock wave treatment manufacture of carbonates nitrogen-doped graphene according to claim 1, is characterized in that: the described compacting of step (1) adopts hydropress, and pressure is 7.5MPa, and the dwell time is 1 ~ 2min.
5. the method for a kind of shock wave treatment manufacture of carbonates nitrogen-doped graphene according to claim 1, is characterized in that: step (1) described sample box is the stainless steel sample box of cupric liner; The thickness of copper liner is 1 ~ 3mm; The outer wall thickness of stainless steel sample box is 2 ~ 3mm.
6. the method for a kind of shock wave treatment manufacture of carbonates nitrogen-doped graphene according to claim 1, it is characterized in that: step (2) described film flying is the film flying driven with explosive detonation, and explosive is the one in Nitromethane 99Min. liquid, 8701 explosives and B explosive; Flyer velocity is 2.83 ~ 3.37km/s.
7. the method for a kind of shock wave treatment manufacture of carbonates nitrogen-doped graphene according to claim 1, is characterized in that: step (3) described drying is vacuum freezedrying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860308A (en) * | 2015-05-20 | 2015-08-26 | 哈尔滨工业大学 | Method for preparing nitrogen-doped graphene with combustion synthesis method |
| CN112850694A (en) * | 2021-02-23 | 2021-05-28 | 中国工程物理研究院总体工程研究所 | Impact reaction preparation device and preparation method of graphene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757029A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Nitrogen doped graphene material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102757029A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Nitrogen doped graphene material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860308A (en) * | 2015-05-20 | 2015-08-26 | 哈尔滨工业大学 | Method for preparing nitrogen-doped graphene with combustion synthesis method |
| CN112850694A (en) * | 2021-02-23 | 2021-05-28 | 中国工程物理研究院总体工程研究所 | Impact reaction preparation device and preparation method of graphene |
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