CN103274393B - Method for preparing nitrogen-doped graphene and nitrogen-doped graphene - Google Patents
Method for preparing nitrogen-doped graphene and nitrogen-doped graphene Download PDFInfo
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Abstract
The invention discloses a method for preparing nitrogen-doped graphene which comprises the following steps of: drying a mixture of a carbon-containing precursor and a carbon-nitrogen-containing precursor; raising the temperature of the dried mixture to be 450-600 DEG C, and keeping the temperature to generate gray solid; and continuously raising the temperature of the gray solid to be 700-1000 DEG C, introducing protective gas, keeping the temperature to generate black solid, and obtaining the nitrogen-doped graphene. According to the method for preparing nitrogen-doped graphene in the embodiment, the nitrogen-doped graphene is obtained under normal pressure and high temperature through a solid-phase reaction, the whole preparation method is simple in process, the nitrogen-doped graphene can be obtained without complex equipment, and industrial production is easily performed. In addition, the invention also provides nitrogen-doped graphene.
Description
[technical field]
The present invention relates to a kind of grapheme material field, particularly relate to a kind of preparation method and nitrogen-doped graphene of nitrogen-doped graphene.
[background technology]
Fuel cell (Fuel Cell) is generally acknowledged efficient, convenient and be of value to the green novel power generation device of environment, uses recyclable fuel as hydrogen, can reduce the dependence for Imported oil of our country.Fuel cell may be used for numerous terminal uses, as distributed standby power supply, thermo-electric union system, automobile, auxiliary powerplant and portable type electronic product.Fuel cell is expected to greatly affect clean energy economy in 21 century.
Fuel cell is a kind of electrochemical cell chemical energy be stored in fuel and oxygenant being directly transformed into electric energy of isothermal.Objective, although fuel cell has many good qualities, its commercialization is still needed satisfied three key conditions: performance, cost and stability.Just at present, the development of fuel cell still faces an important technical barrier: electrochemical reaction speed is low, and catalytic material life-span and poor stability, particularly Cathodic oxygen reduction, catalyzer is expensive.In direct alcohol fuel battery, it is inertia that catalyzer also needs alcohol.Therefore, developing high, cheap, that environmental friendliness, the earth are rich in, stability the is high eelctro-catalyst of oxygen reduction activity is one of key issue.
The Graphene of N doping, is different from pure Graphene, and it has good long-time running stability as the catalyzer without metal, has resistivity to fuel infiltration.The most important thing is, the electro catalytic activity of its electrocatalytic oxidation reduction reaction (ORR) is close to the Pt/C of business.The oxygen reduction activity of Graphene is very poor, and after N doping, the active reason obviously promoted is: the spin density of carbon atom and charge distribution around nitrogen-atoms can affect in synthesize, thus activated carbon.
The Graphene (N-graphene) of N doping has two kinds of different main synthetic methods at present: 1. directly synthesize, such as chemical Vapor deposition process, segregation growth method, solvent-thermal method; 2. post treatment method, such as thermal treatment in ammonia, Cement Composite Treated by Plasma and hydrazine hydrate facture.But these methods mostly technology and equipment relative complex, production cost are higher, and be difficult to realize suitability for industrialized production, and can not realize high nitrogen-containing and the mutually homogeneous doping of body, the amount of doping is generally all less than 20%.
[summary of the invention]
The technical problem to be solved in the present invention is to overcome technical sophistication in the Graphene of N doping in prior art, cost is high, is difficult to the defect of suitability for industrialized production, provides a kind of preparation method of with low cost, the simple nitrogen-doped graphene of technique.
For solving the problems of the technologies described above, the present invention adopts following technical proposals:
A preparation method for nitrogen-doped graphene, comprises the steps:
Step S10: will dry containing carbon matrix precursor and carbon containing nitrogen precursor mixture;
Step S20: the mixture after drying is warming up to 450 DEG C ~ 600 DEG C, and insulation is to generating gray solid; And
Step S30: above-mentioned gray solid continued to be warming up to 700 DEG C ~ 1000 DEG C, pass into shielding gas simultaneously, insulation, to producing black solid, obtains nitrogen-doped graphene.
In the present embodiment, in step S10, described is 3g ~ 1000g containing carbon matrix precursor and carbon containing nitrogen precursor mixture quality.
In the present embodiment, described is the carbohydrate molecule of carbon containing containing carbon matrix precursor, and described carbon containing nitrogen presoma is the organic molecule of carbon containing nitrogen.
In the present embodiment, the carbohydrate molecule of described carbon containing is at least one in glucose or sucrose, and the organic molecule of described carbon containing nitrogen is at least one in trimeric cyanamide, cyanamide, dicyanamide, urea, biuret, Trimustine.
In the present embodiment, the organic molecule quality of described carbon containing nitrogen is 20 times of the carbohydrate molecule quality of described carbon containing.
In the present embodiment, in step S20, the speed range of described intensification is 2 DEG C/min ~ 8 DEG C/min.
In the present embodiment, in step S30, the speed range of described intensification is 5 DEG C/min ~ 15 DEG C/min.
In the present embodiment, in step S30, described shielding gas is argon gas, and the flow of described argon gas is 100sccm ~ 300sccm.
In addition, present invention also offers a kind of nitrogen-doped graphene, described nitrogen-doped graphene is by carbon and the elementary composition aromatic heterocycle two dimensional structure of nitrogen, and in two-dimensional layer class formation.
In the present embodiment, in described nitrogen-doped graphene, nitrogen element content is 33% ~ 3%, and the atomic ratio of carbon/nitrogen two kinds of elements is 1.9 ~ 29.
Adopt technique scheme, beneficial effect of the present invention is:
The preparation method of the nitrogen-doped graphene that the above embodiment of the present invention provides, obtains nitrogen-doped graphene by solid state reaction under constant-pressure and high-temperature, and whole preparation method's technique is simple, and the equipment without the need to complexity can obtain nitrogen-doped graphene, is easy to suitability for industrialized production.
Simultaneously, the preparation method of the nitrogen-doped graphene that the above embodiment of the present invention provides is containing carbon matrix precursor with the carbohydrate molecule of carbon containing, with the organic molecule of carbon containing nitrogen for carbon containing nitrogen presoma, after the two being carried out according to a certain percentage mixing oven dry, then obtain nitrogen-doped graphene through solid state reaction.Due to the carbohydrate molecule of carbon containing and the organic molecule of carbon containing nitrogen cheap, be easy to obtain, and without the need to through special processing, under constant-pressure and high-temperature, can nitrogen-doped graphene be obtained by solid state reaction, effectively reduce the manufacturing cost of nitrogen-doped graphene, be suitable for scale operation.
In addition, the nitrogen-doped graphene that the above embodiment of the present invention provides, dispersible in liquid or solid solvent etc., because its physico-chemical property Modulatory character is strong, can be used for fuel cell, lithium ion battery, sensor, field-effect transistor, ultracapacitor homenergic conversion industry.
[accompanying drawing explanation]
The flow chart of steps of the preparation method of the nitrogen-doped graphene that Fig. 1 provides for the embodiment of the present invention.
The transmission electron microscope photo of the nitrogen-doped graphene powder that Fig. 2 provides for the embodiment of the present invention 1.
The X-ray diffractogram of the nitrogen-doped graphene powder that Fig. 3 provides for the embodiment of the present invention 1.
The current-voltage curve of the nitrogen-doped graphene powder that Fig. 4 provides for the embodiment of the present invention 1.
The nitrogen-doped graphene powder that Fig. 5 a ~ Fig. 5 d provides for the embodiment of the present invention 1 is coated on electrode, and at the performance curve of electrode surface generation oxygen reduction reaction.
Fig. 6 a ~ Fig. 6 b is coated in the stability and anti-toxic curve that electrode are used as eelctro-catalyst for the nitrogen-doped graphene powder that the embodiment of the present invention 1 provides.
[embodiment]
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and the specific embodiments, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Refer to Fig. 1, steps flow chart Figure 100 of the preparation method of the nitrogen-doped graphene that Fig. 1 provides for the embodiment of the present invention, as can be seen from Fig. 1, the preparation method of nitrogen-doped graphene comprises the steps:
Step S10: will dry containing carbon matrix precursor and carbon containing nitrogen precursor mixture.
In the present embodiment, be 3g ~ 1000g containing carbon matrix precursor and carbon containing nitrogen precursor mixture quality.
In the present embodiment, be the carbohydrate molecule of carbon containing containing carbon matrix precursor, carbon containing nitrogen presoma is the organic molecule of carbon containing nitrogen.Preferably, the carbohydrate molecule of carbon containing is at least one in glucose or sucrose, and the organic molecule of carbon containing nitrogen is trimeric cyanamide, cyanamide, dicyanamide, urea, contracting two are urinated, at least one in Trimustine; Preferably, the organic molecule quality of carbon containing nitrogen is 20 times of the carbohydrate molecule quality of carbon containing.
Particularly, appropriate is put into crucible containing carbon matrix precursor and carbon containing nitrogen precursor mixture, and dries.Wherein, the material of crucible comprises pottery, aluminum oxide, magnesium oxide, zirconium white, silicon carbide, mullite, stainless steel, titanium or titanium alloy etc.
Be appreciated that, choose suitable containing carbon matrix precursor and carbon containing nitrogen presoma particularly important, technical scheme provided by the invention is containing carbon matrix precursor with the carbohydrate molecule of carbon containing, with the organic molecule of carbon containing nitrogen for carbon containing nitrogen presoma, after the two being carried out according to a certain percentage mixing oven dry, then obtain nitrogen-doped graphene through solid state reaction.Due to the carbohydrate molecule of carbon containing and the organic molecule of carbon containing nitrogen cheap, be easy to obtain, and without the need to through special processing, under constant-pressure and high-temperature, can nitrogen-doped graphene be obtained by solid state reaction, effectively reduce the manufacturing cost of nitrogen-doped graphene, be suitable for scale operation.
Step S20: the mixture after drying is warming up to 450 DEG C ~ 600 DEG C, and insulation is to generating gray solid.
Particularly, the mixture after drying and processing in step S10 is placed in process furnace, with after the temperature rise rate to 450 of 2 DEG C/min ~ 8 DEG C/min DEG C ~ 600 DEG C, and more than insulation reaction 3h at such a temperature, until production gray solid.
Step S30: above-mentioned gray solid continued to be warming up to 700 DEG C ~ 1000 DEG C, pass into shielding gas simultaneously, insulation, to producing black solid, obtains nitrogen-doped graphene.
Particularly, the gray solid obtained through step S20 is transferred in porcelain boat, be warming up to 700 DEG C ~ 1000 DEG C with the temperature rise rate of 5 DEG C/min ~ 15 DEG C/min under a shielding gas, until generate black solid, obtain nitrogen-doped graphene.Wherein, shielding gas is preferably argon gas.The flow of argon gas is 100sccm ~ 300sccm.Preferably, the material of porcelain boat can be selected from but be not limited to corundum boat.
The nitrogen-doped graphene that the present invention also adopts aforesaid method to prepare, it is by carbon and the elementary composition aromatic heterocycle two dimensional structure of nitrogen, and in two-dimensional layer class formation.In nitrogen-doped graphene, nitrogen element content is 33% ~ 3%, and the atomic ratio of carbon/nitrogen two kinds of elements is 1.9 ~ 29.
The nitrogen-doped graphene that the present invention adopts aforesaid method to prepare is black powder shape, has oxygen reduction catalytic activity, insensitive to Aalcohols fuel, anti-carbon monoxide gassing, has ion insertion characteristic, capacitance characteristic and gas responsiveness.
The nitrogen-doped graphene that the above embodiment of the present invention provides, dispersible in liquid or solid solvent etc., because its physico-chemical property Modulatory character is strong, can be used for fuel cell, lithium ion battery, sensor, field-effect transistor, ultracapacitor homenergic conversion industry.
Set forth the present invention further by the following examples, these embodiments are only presented for purposes of illustration, do not limit the scope of the invention.Except the actual conditions indicated, the test method in embodiment all conveniently condition is carried out.
embodiment 1
The step that the preparation method of the nitrogen-doped graphene that the embodiment of the present invention 1 provides comprises is followed successively by:
Put into crucible after 10g trimeric cyanamide and 0.5g glucose are mixed, and dry at a suitable temperature; Mixture after drying is put into process furnace, with the temperature rise rate to 550 DEG C of 5 DEG C/min, reacts more than 3h at such a temperature, until generate gray solid; Afterwards above-mentioned gray solid is transferred in tube furnace; be simultaneously that 200sccm passes into shielding gas Ar with speed; and more than 30min is incubated at 100 DEG C; 800 DEG C are warming up to again with the temperature rise rate of 10 DEG C/min; and react at such a temperature after 1h until generate black solid; and cool in air ambient, obtain nitrogen-doped graphene.The atomic ratio of its carbon/nitrogen of the Graphene obtained according to above-mentioned preparation method two kinds of elements is 2.9.
Refer to Fig. 2, Fig. 3 and Fig. 4, wherein, the transmission electron microscope photo of the nitrogen-doped graphene powder that Fig. 2 provides for the embodiment of the present invention 1, the X-ray diffractogram of the nitrogen-doped graphene powder that Fig. 3 provides for the embodiment of the present invention 1, the current-voltage curve of the nitrogen-doped graphene powder that Fig. 4 provides for the embodiment of the present invention 1.Show in Fig. 3, the peak in 2 θ=14 °, respective layer spacing d=0.63nm, shows that this nitrogen-doped graphene has typical stratiform two-dirnentional structure; Show in Fig. 4, this nitrogen-doped graphene resistance value is 10
2Ω, electroconductibility is restored.
embodiment 2
The step that the preparation method of the nitrogen-doped graphene that the embodiment of the present invention 2 provides comprises is followed successively by:
Put into crucible after 10g urea and 0.5g glucose are mixed, and dry at a suitable temperature; Mixture after drying is put into process furnace, with the temperature rise rate to 550 DEG C of 5 DEG C/min, reacts more than 3h at such a temperature, until generate gray solid; Afterwards above-mentioned gray solid is transferred in tube furnace; be simultaneously that 200sccm passes into shielding gas Ar with speed; and more than 30min is incubated at 100 DEG C; 800 DEG C are warming up to again with the temperature rise rate of 10 DEG C/min; and react at such a temperature after 1h until generate black solid; and cool in air ambient, obtain nitrogen-doped graphene.The atomic ratio of its carbon/nitrogen of the Graphene obtained according to above-mentioned preparation method two kinds of elements is 3.
embodiment 3
The step that the preparation method of the nitrogen-doped graphene that the embodiment of the present invention 3 provides comprises is followed successively by:
Put into crucible after 100g cyanamide and 5g sucrose are mixed, and dry at a suitable temperature; Mixture after drying is put into process furnace, with the temperature rise rate to 500 DEG C of 2 DEG C/min, reacts more than 3h at such a temperature, until generate gray solid; Afterwards above-mentioned gray solid is transferred in tube furnace; be simultaneously that 100sccm passes into shielding gas Ar with speed; and more than 30min is incubated at 100 DEG C; 700 DEG C are warming up to again with the temperature rise rate of 5 DEG C/min; and react at such a temperature after 1h until generate black solid; and cool in air ambient, obtain nitrogen-doped graphene.The atomic ratio of its carbon/nitrogen of the Graphene obtained according to above-mentioned preparation method two kinds of elements is 1.9.
embodiment 4
The step that the preparation method of the nitrogen-doped graphene that the embodiment of the present invention 4 provides comprises is followed successively by:
Put into crucible after 20g dicyanamide and 1g sucrose are mixed, and dry at a suitable temperature; Mixture after drying is put into process furnace, with the temperature rise rate to 600 DEG C of 2 DEG C/min, reacts more than 3h at such a temperature, until generate gray solid; Afterwards above-mentioned gray solid is transferred in tube furnace; be simultaneously that 300sccm passes into shielding gas Ar with speed; and more than 30min is incubated at 100 DEG C; 1000 DEG C are warming up to again with the temperature rise rate of 5 DEG C/min; and react at such a temperature after 1h until generate black solid; and cool in air ambient, obtain nitrogen-doped graphene.The atomic ratio of its carbon/nitrogen of the Graphene obtained according to above-mentioned preparation method two kinds of elements is 29.
embodiment 5
The step that the preparation method of the nitrogen-doped graphene that the embodiment of the present invention 5 provides comprises is followed successively by:
Put into crucible after 200g biuret and 10g sucrose are mixed, and dry at a suitable temperature; Mixture after drying is put into process furnace, with the temperature rise rate to 500 DEG C of 8 DEG C/min, reacts more than 3h at such a temperature, until generate gray solid; Afterwards above-mentioned gray solid is transferred in tube furnace; be simultaneously that 250sccm passes into shielding gas Ar with speed; and more than 30min is incubated at 100 DEG C; 900 DEG C are warming up to again with the temperature rise rate of 15 DEG C/min; and react at such a temperature after 1h until generate black solid; and cool in air ambient, obtain nitrogen-doped graphene.The atomic ratio of its carbon/nitrogen of the Graphene obtained according to above-mentioned preparation method two kinds of elements is 10.5.
embodiment 6
The step that the preparation method of the nitrogen-doped graphene that the embodiment of the present invention 6 provides comprises is followed successively by:
Put into crucible after 1000g trimeric cyanamide and 50g sucrose are mixed, and dry at a suitable temperature; Mixture after drying is put into process furnace, with the temperature rise rate to 450 DEG C of 6 DEG C/min, reacts more than 3h at such a temperature, until generate gray solid; Afterwards above-mentioned gray solid is transferred in tube furnace; be simultaneously that 300sccm passes into shielding gas Ar with speed; and more than 30min is incubated at 100 DEG C; 1000 DEG C are warming up to again with the temperature rise rate of 15 DEG C/min; and react at such a temperature after 1h until generate black solid; and cool in air ambient, obtain nitrogen-doped graphene.The atomic ratio of its carbon/nitrogen of the Graphene obtained according to above-mentioned preparation method two kinds of elements is 25.
In order to verify that the above embodiment of the present invention provides the electric property of Graphene further, below choosing above-described embodiment gained nitrogen-doped graphene powder and supporting in electrode surface, and testing electrochemical oxygen reduction reactive behavior.Its step is followed successively by:
Preparation work electrode: first 2mg nitrogen-doped graphene powder is dispersed in the mixing solutions of 1.8ml deionized water (18.2M Ω) and 0.2ml5wt%Nafion; Ultrasonic for above-mentioned mixing solutions 15 minutes are obtained the dark solution uniformly containing nitrogen-doped graphene; By the 1mg mL of 15.00 μ L
-1nitrogen-doped graphene dispersant liquid drop is with Al
2o
3on polished glass-carbon electrode, and at 60 DEG C air drying.
Experiment condition is arranged: on electrochemical workstation, use traditional three-electrode system, and carry out electro-chemical test with under aeration condition.Adopt Ag/AgCl and Pt line as reference electrode with to electrode.Standard rating cycle volt-ampere test (CV) and rotating ring disk electrode (r.r.d.e) test (RRDE) is carried out in the KOH electrolyte solution of 0.1M.Before testing, the minimum logical 30min N of electrolyte solution
2/ O
2.Standard rating cycle volt-ampere is tested under 0.2V to-1.0V with 50mV s
-1speed carry out.For rotating ring disk electrode (r.r.d.e) (RRDE) test, electrode preparation method ditto described in.The test of ORR polarization curve at 0.2V ~-1.2V (vs Ag/AgCl), with 10mV s under 600 ~ 2500rpm rotating speed
-1speed of sweeping carry out.
Refer to Fig. 5 a ~ Fig. 5 d, wherein, the nitrogen-doped graphene powder that Fig. 5 a ~ Fig. 5 d provides for the embodiment of the present invention 1 is coated on electrode, and at the performance curve of electrode surface generation oxygen reduction reaction.
Wherein, Fig. 5 a is oxygen O
2with nitrogen N
2cyclic voltammetry curve (CV) in saturated 0.1M KOH solution, as can be seen from Fig. 5 a, when being full of nitrogen in solution, between 0.2 to-1.0V, CV curve does not have characteristic peak to occur.Be full of in oxygen atmosphere, CV curve can see a negative electrode peak clearly at-0.36V place, this peak is the peak of oxygen reduction.This shows that it has catalytic activity to oxygen;
Wherein, Fig. 5 b is the linear sweep voltammetry curve (LSV) of rotating ring disk electrode (r.r.d.e) under 1600rpm rotating speed.LSV shows current density and increases along with the increase of rotating speed.This is because diffusion length shortens at high speed;
Wherein, Fig. 5 c is the Koutecky-Levich curve under different electromotive force.Can to obtain in Fig. 5 d electron transfer number under-0.5V ~-1.0V by Koutecky-Levich equation, under-0.9V, in oxygen reaction process, electron transfer number reaches 3.7, reacts close to 4e-.
Refer to Fig. 6 a ~ Fig. 6 b, Fig. 6 a ~ Fig. 6 b is coated in the stability and anti-toxic curve that electrode are used as eelctro-catalyst for the nitrogen-doped graphene powder that the embodiment of the present invention 1 provides.
Wherein, Fig. 6 a carries out polarogram current-time curvel test (chronoamperometric tests) to nitrogen-doped graphene and Pt/C (20wt%Pt) electrode in the 0.1M KOH solution that oxygen is saturated under-0.5V.Fig. 6 a shows, adds 3M methyl alcohol when 250s, and the current density of Pt/C electrode obviously declines.And the electric current of nitrogen-doped graphene electrode does not have considerable change, illustrate that it is insensitive to alcohol ate;
Wherein, Fig. 6 b is the opposing cathode electric current running 3000s.Fig. 6 b shows, after the continuance test of a rapid lapse of time, the current density on nitrogen-doped graphene electrode is not significantly lost.By contrast, the decline that the current density on Pt/C continues.
By providing the electric property checking of Graphene to find to the above embodiment of the present invention, this nitrogen-doped graphene powder has catalytic activity to oxygen, and close to four electron reactions.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be do not depart from technical solution of the present invention content, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (5)
1. a preparation method for nitrogen-doped graphene, is characterized in that, comprises the steps:
Step S10: will dry containing carbon matrix precursor and carbon containing nitrogen precursor mixture, described is the carbohydrate molecule of carbon containing containing carbon matrix precursor, described carbon containing nitrogen presoma is the organic molecule of carbon containing nitrogen, described is 3g ~ 1000g containing carbon matrix precursor and carbon containing nitrogen precursor mixture quality, and the organic molecule quality of described carbon containing nitrogen is 20 times of the carbohydrate molecule quality of described carbon containing;
Step S20: by the mixture after drying and processing, with after the temperature rise rate to 450 of 2 DEG C/min ~ 8 DEG C/min DEG C ~ 600 DEG C, and more than insulation reaction 3h at such a temperature, until production gray solid; And
Step S30: by above-mentioned gray solid, is warming up to 700 DEG C ~ 1000 DEG C with the temperature rise rate of 5 DEG C/min ~ 15 DEG C/min under a shielding gas, until generate black solid, obtains N doping graphite.
2. the preparation method of nitrogen-doped graphene according to claim 1, it is characterized in that, the carbohydrate molecule of described carbon containing is at least one in glucose or sucrose, and the organic molecule of described carbon containing nitrogen is at least one in trimeric cyanamide, cyanamide, dicyanamide, urea, biuret, Trimustine.
3. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that, in step S30, described shielding gas is argon gas, and the flow of described argon gas is 100sccm ~ 300sccm.
4. a nitrogen-doped graphene, is characterized in that, described nitrogen-doped graphene is by carbon and the elementary composition aromatic heterocycle two dimensional structure of nitrogen, and in two-dimensional layer class formation, wherein, the preparation method of described nitrogen-doped graphene is as follows:
Step S10: will dry containing carbon matrix precursor and carbon containing nitrogen precursor mixture, described is the carbohydrate molecule of carbon containing containing carbon matrix precursor, described is 3g ~ 1000g containing carbon matrix precursor and carbon containing nitrogen precursor mixture quality, and the organic molecule quality of described carbon containing nitrogen is 20 times of the carbohydrate molecule quality of described carbon containing;
Step S20: by the mixture after drying and processing, with after the temperature rise rate to 450 of 2 DEG C/min ~ 8 DEG C/min DEG C ~ 600 DEG C, and more than insulation reaction 3h at such a temperature, until production gray solid; And
Step S30: by above-mentioned gray solid, is warming up to 700 DEG C ~ 1000 DEG C with the temperature rise rate of 5 DEG C/min ~ 15 DEG C/min under a shielding gas, until generate black solid, obtains nitrogen-doped graphene.
5. nitrogen-doped graphene according to claim 4, is characterized in that, in described nitrogen-doped graphene, nitrogen element content is 33% ~ 3%, and the atomic ratio of carbon/nitrogen two kinds of elements is 1.9 ~ 29.
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| CN108246329B (en) * | 2018-01-09 | 2020-06-26 | 杭州诚洁环保有限公司 | N-doped graphene-cerium oxide composite catalyst and application thereof in acidic degradation-resistant wastewater treatment |
| TWI659558B (en) * | 2018-03-20 | 2019-05-11 | 中原大學 | Method of fabricating anode material for secondary battery |
| CN108793131A (en) * | 2018-07-18 | 2018-11-13 | 南方医科大学 | The method for preparing graphene as raw material with glucose mixture using cellobiose or cellobiose |
| CN108821265B (en) * | 2018-07-24 | 2020-10-27 | 武汉轻工大学 | In g-C3N4Method for preparing graphene for template |
| CN110655067B (en) * | 2019-10-09 | 2021-05-07 | 南昌大学 | Environment-friendly preparation method of nitrogen-doped graphene |
| CN115285979B (en) * | 2022-07-29 | 2023-07-11 | 中国人民解放军军事科学院防化研究院 | Preparation method of pyrrole nitrogen doped graphene |
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| CN102120572A (en) * | 2011-01-24 | 2011-07-13 | 南京大学 | Method for preparing nitrogen-doped graphene |
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| Growth of graphene from solid carbon sources;Zhengzong Sun et.al.;《Nature》;20101125;第468卷;549-552 * |
| Pyridinic N-doped graphene: synthesis, electronic structure, and electrocatalytic property;Zhiqiang Luo et.al.;《J. Mater. Chem.》;20110421;第21卷;8038-8044 * |
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