CN104944418B - An a kind of step prepares nitrogen content and the method for the adjustable doped graphene of kind in situ - Google Patents
An a kind of step prepares nitrogen content and the method for the adjustable doped graphene of kind in situ Download PDFInfo
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Abstract
An a kind of step prepares nitrogen content and the method for the adjustable doped graphene of kind in situ, and it relates to a kind of method preparing nitrogen content and the regulatable doped graphene of kind.The invention aims to solve current nitrogen-doped graphene complicated process of preparation; preparation cost is higher; it is difficult to the problem that nitrogen element content and kind in the nitrogen-doped graphene of industrialization and preparation are controlled; the inventive method is: put into by carbonitride in the quartz ampoule that one end seals; cylindrical quartz plug is placed at quartz ampoule opening; quartz ampoule is transferred in tube furnace; heat up under inert atmosphere protection; insulation; continue to heat up; and it is incubated nitrogen-doped graphene kind nitrogen element content and kind, i.e. complete.The inventive method is simple, environmental friendliness, and content and the kind of nitrogen-doped graphene kind nitrogen element are controlled, can be used for substituting business Pt/C as oxygen reduction catalyst, and the present invention is applied to battery, photocatalysis, catalysis oxidation, gas sensor and drug delivery field.
Description
Technical field
The present invention relates to an a kind of step and prepare nitrogen content and the method for the adjustable doped graphene of kind in situ.
Background technology
Grapheme material is a kind of monoatomic layer material with bi-dimensional cellular shape structure, and it is to constitute fullerene, CNT
Basic structural unit with graphite.From Univ Manchester UK's peace moral strong K sea nurse (Andre K.Geim) in 2004
Since preparing single-layer graphene (Science 2004,306,666-669), receive the extensive pass of scientific circles and industrial quarters
Note.Graphene has electricity, calorifics and the mechanical property of excellence.(Science.,2009,324,1530-1534；Nature.,
2005,438,201-204.)
Structure and the performance of Graphene can be changed so that it is realize more rich chemical functional and application by element doping.Example
As in Graphene introduce nitrogen-atoms, the lone pair electrons of nitrogen-atoms can with sp2 hydbridized carbon atoms generation delocalization conjugation,
Can be with the reactivity improving Graphene of high degree and electrocatalysis characteristic.The Graphene of doping and common graphite alkene show not
Same structure and character (Angew.Chem., Int.Ed.2009,48,4386 4389；Science 2009,324,
768-771), there is wide application at aspects such as microelectronics, catalysis, composite, lithium battery, ultracapacitor, hydrogen storage
Prospect.So far, synthetic nitrogen doped graphene mainly has two kinds of methods: rear doping method and in situ doping method.Rear doping
Method is first to prepare Graphene or graphene oxide, utilizes and processes it (such as high-temperature heating, hydro-thermal containing nitrogen compound
Deng), obtain the Graphene of N doping.As: chemical vapour deposition technique, arc discharge method, thermal decomposition method etc..Doping in situ
Method is to be doped during preparing Graphene, such as chemical vapour deposition technique, plasma assisted vapor deposition etc..Phase
For rear doping method, the nitrogen-doped graphene prepared by doping method adulterates evenly in situ, nitrogen atom doping state is more controlled,
Nitrogen atom content is the most controlled, is a kind of preferably doping method.As Pan etc. utilizes carbamide and sucrose by the side of heating
Method is prepared for the Graphene (ACS Appl.Mater.Interfaces 2013,5,11108-11114) of N doping.Nitrogen
Changing carbon is the layered semiconductor material that a kind of nitrogen content is the highest, has extensively in fields such as biology, photocatalysis, electro-catalysis and photoelectricity
General application.The nitrogen content of carbonitride Yin Qigao, is doped Graphene as nitrogen source.Recently, Li et al. (Angew.
Chem.Int.Ed.2012,51,9689-9692) carbonitride (g-C is utilized3N4, space group: R3m, band gap is 2.64
EV) it is template, utilizes glucose to be prepared for nitrogen-doped graphene for carbon source, but this method needs by additional carbon
That is: glucose.Owing to containing abundant oxygen-containing functional group in glucose, therefore the membership that adds of sucrose inevitably introduces oxygen,
The prepared nitrogen-doped graphene character at the aspect such as microelectronics, catalysis can be affected further.In nitrogen-doped graphene, nitrogen unit
Content and the kind of element have considerable influence to its application in fields such as microelectronics, catalysis, composites.Different doping methods
In the nitrogen-doped graphene of preparation, content and the kind of nitrogen element have bigger difference.At present, not yet there is effective method that nitrogen is mixed
In miscellaneous Graphene, content and the kind of nitrogen element regulate and control.Therefore, it is badly in need of a kind of simple and feasible method to prepare nitrogen element and contain
Amount and kind are controlled, and High Purity Nitrogen doped graphene is led for high-performance, high stability electronic device, catalysis and the energy etc.
Territory.
Summary of the invention
The invention aims to solve current nitrogen-doped graphene complicated process of preparation, preparation cost is higher, it is difficult to industrialization
And nitrogen element content and the controlled problem of kind in the nitrogen-doped graphene of preparation, it is provided that an a kind of step prepares nitrogen content in situ
The method of doped graphene adjustable with kind.
An a kind of step of the present invention prepares nitrogen content and the method for the adjustable doped graphene of kind in situ, sequentially includes the following steps:
One, 1～500g carbonitride is placed in the quartz ampoule that one end seals, the internal diameter of wherein said quartz ampoule
φ=5～100mm, length=20cm, opening places cylindrical quartz plug, external diameter φ=4 of quartz plug～99mm, length
=5cm, quartz ampoule internal diameter and quartz plug external diameter difference are 1mm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, then vacuum in tube furnace is evacuated to 8 × 10-4～9 × 10-4Pa,
Then being passed through flow in tube furnace is 50～90sccm protective gas；
Three, the tube furnace after step 2 being processed is heated to 740～750 DEG C with the speed of 1～5 DEG C/min, is then incubated
5～120min, obtain nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 800～1000 DEG C with the speed of 5～20 DEG C/min, is then incubated
30～120min, obtain nitrogen content and the adjustable Graphene of kind, i.e. complete.
The present invention includes following beneficial effect:
1, Graphene prepared by the present invention has big specific surface area, and N doping is uniform；Can apply to catalysis, lithium battery,
The fields such as microelectronics.When nitrogen-doped graphene prepared by the present invention is applied to catalytic oxidation-reduction reaction, its catalysis activity and business
Industry platinum carbon is suitable, but has more preferable catalytic stability than business platinum C catalyst.
2, the present invention only uses a kind of nitrogen-containing compound, participates in reaction without other any chemical reagent, is a kind of environmental friendliness
The method preparing high-purity nitrogen doped graphene.
3, the present invention can by adjusting heat time heating time of each step and heating-up temperature regulates and controls the nitrogen content of last products therefrom,
Specific nitrogen content and the nitrogen-doped graphene of nitrogenous kind can be prepared by the present invention.
4, the present invention utilizes carbonitride to directly heat to prepare nitrogen-doped graphene, can pass through feed change consumption, it is achieved gram
The preparation of the above nitrogen-doped graphene of magnitude, is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscopic picture of the nitrogen-doped graphene of embodiment one preparation；
Fig. 2 is the transmission electron microscope picture of the nitrogen-doped graphene of embodiment one preparation；
Fig. 3 is the X-ray diffractogram of the nitrogen-doped graphene of embodiment one preparation；
Fig. 4 is the XPS collection of illustrative plates of the nitrogen-doped graphene of embodiment one preparation；
Fig. 5 is the fine spectrogram of XPS of the N1s of the nitrogen-doped graphene of embodiment one preparation；Wherein a is analogue spectrums, b
For graphite-phase nitrogen, c is pyridine nitrogen, and d is original spectrogram；
Fig. 6 is the polarization curve that nitrogen-doped graphene prepared by test 1 is applied to oxygen reduction reaction catalyst；Wherein 1 is this
The polarization curve of the prepared nitrogen-doped graphene of invention；2 is the polarization curve of business platinum carbon；
Fig. 7 is the nitrogen-doped graphene stability curve as oxygen reduction reaction catalyst of test 1 preparation；Wherein 1 is this
The prepared nitrogen-doped graphene stability curve of invention, 2 is the stability curve of business platinum C catalyst；
Fig. 8 is that embodiment two to nine step 4 is by the nitrogen content prepared by different heating temperature and kind adjustable doping stone
The nitrogen content of ink alkene and Species distributing figure；WhereinFor total nitrogen content ,-■-for graphite-phase nitrogen ,-●-for pyridine
Nitrogen.
Detailed description of the invention
Detailed description of the invention one: an a kind of step of present embodiment prepares nitrogen content and the side of the adjustable doped graphene of kind in situ
Method, sequentially includes the following steps:
One, 1～500g carbonitride is placed in the quartz ampoule that one end seals, the internal diameter of wherein said quartz ampoule
φ=5～100mm, length=20cm, opening places cylindrical quartz plug, external diameter φ=4 of quartz plug～99mm, length
=5cm, quartz ampoule internal diameter and quartz plug external diameter difference are 1mm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, then vacuum in tube furnace is evacuated to 8 × 10-4～9 × 10-4Pa,
Then being passed through flow in tube furnace is 50～90sccm protective gas；
Three, the tube furnace after step 2 being processed is heated to 740～750 DEG C with the speed of 1～5 DEG C/min, is then incubated
5～120min, obtain nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 800～1000 DEG C with the speed of 5～20 DEG C/min, is then incubated
30～120min, obtain nitrogen content and the adjustable doped graphene of kind, i.e. complete.
Present embodiment includes following beneficial effect:
1, Graphene prepared by present embodiment has big specific surface area, and N doping is uniform；Can apply to catalysis, lithium
The field such as battery, microelectronics.When nitrogen-doped graphene prepared by present embodiment is applied to catalytic oxidation-reduction reaction, it is urged
Change activity suitable with business platinum carbon, but have more preferable catalytic stability than business platinum C catalyst.
2, present embodiment only uses a kind of nitrogen-containing compound, participates in reaction without other any chemical reagent, is a kind of environment
The friendly method preparing high-purity nitrogen doped graphene.
3, present embodiment can regulate and control containing of last products therefrom by the heat time heating time and heating-up temperature that adjust each step
Nitrogen quantity, can prepare specific nitrogen content and the nitrogen-doped graphene of nitrogenous kind by present embodiment.
4, present embodiment utilizes carbonitride to directly heat to prepare nitrogen-doped graphene, can pass through feed change consumption, real
The preparation of the existing above nitrogen-doped graphene of gram level, is suitable for large-scale production.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: the protective gas described in step 2 is
High-purity argon gas or high pure nitrogen.Other step is identical with detailed description of the invention one with parameter.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: described in step 3 by step
Tube furnace after two process is heated to 740 DEG C with the speed of 2 DEG C/min.Other step and parameter and detailed description of the invention one or
Two is identical.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: inciting somebody to action described in step 3
Tube furnace after step 2 processes is heated to 750 DEG C with the speed of 2 DEG C/min.Other step and parameter and detailed description of the invention
One of one to three identical.
Detailed description of the invention five: present embodiment is unlike one of detailed description of the invention one to four: inciting somebody to action described in step 4
Tube furnace after step 3 processes is heated to 950 DEG C with the speed of 5 DEG C/min.Other step and parameter and detailed description of the invention
One of one to four identical.
By following example checking beneficial effects of the present invention:
Embodiment one: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 1g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 5mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=4mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 50sccm；
Three, the tube furnace after step 2 being processed is heated to 750 DEG C with the speed of 1 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 900 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
The scanning electron microscopic picture of nitrogen-doped graphene prepared by the present embodiment and transmission electron microscope picture as depicted in figs. 1 and 2, from
Fig. 1 is it can be seen that nitrogen-doped graphene lamella size about 500 nanometer prepared of the present embodiment；Figure it is seen that this
Nitrogen-doped graphene prepared by embodiment is few layer graphene of 4-6 layer.
The X-ray diffractogram of the nitrogen-doped graphene prepared by the present embodiment is as it is shown on figure 3, from figure 3, it can be seen that this reality
Executing the product prepared by example is Graphene.
The XPS spectrum figure of nitrogen-doped graphene prepared by the present embodiment as shown in Figure 4, from fig. 4, it can be seen that the present embodiment system
Standby nitrogen-doped graphene composition is mainly made up of carbon and nitrogen, nitrogen content about 5.4%.
The fine spectrogram of XPS of the N1s of nitrogen-doped graphene prepared by the present embodiment as it is shown in figure 5, from fig. 5, it can be seen that
In nitrogen-doped graphene prepared by the present embodiment, pyridine nitrogen is 1.62%, and graphite-phase nitrogen is 3.78%.
The nitrogen-doped graphene preparing the present embodiment carries out tests below:
Test 1: take 5mg gained nitrogen-doped graphene, adds 0.5ml water and 0.5ml ethanol, 80 μ L 5wt%Nafion
(Alfa) solution supersound process 60min prepare catalyst pulp；With Ag/AgCl as reference electrode, Pt silk is to electricity
Pole, 0.1M KOH be electrolyte to nitrogen-doped carbon carry out hydrogen reduction test.Take above-mentioned catalyst pulp 5 μ L to be added drop-wise to
Circular glassy carbon electrode surface, carries out hydrogen reduction test after natural drying.Carry out business platinum carbon (E-TEK) after the same method
Oxygen reduction catalytic activity test.
The nitrogen-doped graphene of embodiment one preparation and the business platinum carbon polarization curve when 1600 turns are as shown in Figure 6；Wherein
1 prepares the polarization curve of nitrogen-doped graphene for institute's embodiment one；2 is the polarization curve of business platinum carbon.Can from figure
Going out, under the conditions of same test, the Catalytic active phase of the nitrogen-doped graphene prepared by embodiment one and business platinum carbon is worked as.
Nitrogen-doped graphene prepared by this test and business platinum carbon are as the stability test curve such as figure of oxygen reduction catalyst
Shown in 7；The polarization curve that wherein 1 is the prepared nitrogen-doped graphene of this test；2 is the polarization curve of business platinum carbon.From
In figure it can be seen that under identical testing conditions, test through the hydrogen reduction of 35000 hours, the nitrogen prepared by this test
The carrying current conservation rate of doped graphene is 92.8%；The carrying current conservation rate of business platinum carbon is 32%.
Test 1 explanation nitrogen-doped graphene catalysis activity prepared by embodiment one is suitable with business platinum carbon, but for a long time
Catalytic stability is better than business platinum carbon.
Test 2: take 100mg gained nitrogen-doped graphene and 200mg TiO2Granule (P25) is ultrasonic in 40ml ethanol
30min, is sealed in mixed solution in water heating kettle 120 DEG C and reacts 10 hours, be washed with deionized by products therefrom dry,
Obtain nitrogen-doped graphene/TiO2Composite；By gained nitrogen-doped graphene/TiO2Composite and politef and lead
Electricity acetylene black (TIMREXKS-15, TIMCAL, Switzerlan), according to mass ratio 80:10:10 mix homogeneously, is smeared
On the two sides of nickel screen as working electrode, 60 DEG C are dried 6 hours, and tabletting is also dried 24 hours at 120 DEG C；With lithium metal
For to electrode, microporous polypropylene membrane (Celgard 2300) is barrier film, the LiPF of 1mol/L6Ethylene carbonate and carbonic acid
Diethylester (volume ratio 1:1) solution is electrolyte, assembles lithium ion battery；Pure TiO is prepared by same method2Granule electricity
Pond electrode, and assemble lithium ion battery.
Gained battery with 0.1C discharge time specific capacity as 145mAh/g, be pure TiO2Granule is as electrode material of lithium battery capacity
(81mAh/g) 1.8 times.
Test 3: take 100mg gained nitrogen-doped graphene and 200mg SnO2Granule is ultrasonic 30min in 40ml ethanol,
Mixed solution is sealed in water heating kettle 120 DEG C react 10 hours, products therefrom is washed with deionized dry, obtains
Nitrogen-doped graphene/SnO2Composite；By gained nitrogen-doped graphene/SnO2Composite and politef and conduction
Acetylene black (TIMREXKS-15, TIMCAL, Switzerlan), according to mass ratio 85:5:10 mix homogeneously, spreads upon
The two sides of nickel screen is as working electrode, and 60 DEG C are dried 6 hours, and tabletting is also dried 24 hours at 120 DEG C；With lithium metal it is
To electrode, microporous polypropylene membrane (Celgard 2300) is barrier film, the LiPF of 1mol/L6Ethylene carbonate and carbonic acid two
Ethyl ester (volume ratio 1:1) solution is electrolyte, assembles lithium ion battery.
Gained battery with 0.1C discharge time specific capacity as 880mAh/g.
Test 4: take 50mg gained nitrogen-doped graphene and 200mg FeCl3Ultrasonic 30min in 40ml deionized water,
Mixed solution is sealed in water heating kettle 150 DEG C react 10 hours, products therefrom is washed with deionized dry, obtains
Nitrogen-doped graphene/Fe3O4Composite；By gained nitrogen-doped graphene/Fe3O4Composite and politef and conduction
Acetylene black (TIMREXKS-15, TIMCAL, Switzerlan), according to mass ratio 85:5:10 mix homogeneously, spreads upon
The two sides of nickel screen is as working electrode, and 60 DEG C are dried 6 hours, and tabletting is also dried 24 hours at 120 DEG C；With lithium metal it is
To electrode, microporous polypropylene membrane (Celgard 2300) is barrier film, the LiPF of 1mol/L6Ethylene carbonate and carbonic acid two
Ethyl ester (volume ratio 1:1) solution is electrolyte, assembles lithium ion battery.
Gained battery with 0.1C discharge time specific capacity as 630mAh/g.
Test 2～test 4 explanation, the nitrogen-doped graphene prepared by embodiment one can be effectively improved the specific volume of lithium ion battery
Amount.
Test 5: take 10mg nitrogen-doped graphene and 200mg P25 granule ultrasonic 30min in 40ml ethanol, will mixing
Solution is sealed in water heating kettle 160 DEG C and reacts 10 hours, is washed with deionized by products therefrom dry, obtains N doping
Graphene/P25 composite；100mg nitrogen-doped graphene/P25 composite is added in agate mortar, add 80ml
The anhydrous terpineol of appropriate amount of ethanol and ethyl cellulose also grind 1h, are evaporated by ethanol by rotary evaporator and obtain slurry, at ITO
Absorbed layer is prepared with doctor blade method on glass, 450 DEG C of annealing 1h, take out and and platinum after immersing the N719 dyestuff 20h of 0.5mM
Electrode assembling becomes battery.
The photoelectric transformation efficiency (η) of gained solaode is 5.3%.
Test 5 explanation nitrogen-doped graphene prepared by embodiment one is beneficial to the raising of solar energy photoelectric conversion efficiency.
Embodiment two: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 2g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 6mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=5mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 50sccm；
Three, the tube furnace after step 2 being processed is heated to 740 DEG C with the speed of 1 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 800 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 8.2%；Wherein pyridine nitrogen is 4%, and graphite-phase nitrogen is 4.2%.
Embodiment three: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 10g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 10mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=9mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high pure nitrogen that flow is 90sccm；
Three, the tube furnace after step 2 being processed is heated to 740 DEG C with the speed of 2 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 800 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 8.9%；Wherein pyridine nitrogen is 4.6%, and graphite-phase nitrogen is
4.3%.
Embodiment four: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 50g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 20mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=19mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 50sccm；
Three, the tube furnace after step 2 being processed is heated to 750 DEG C with the speed of 2 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 800 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 8.7%；Wherein pyridine nitrogen is 4.3%, and graphite-phase nitrogen is
4.4%.
Embodiment five: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 2g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 5mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=4mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 50sccm；
Three, the tube furnace after step 2 being processed is heated to 750 DEG C with the speed of 2 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 900 DEG C with the speed of 10 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 6.1%；Wherein pyridine nitrogen is 3.6%, and graphite-phase nitrogen is
2.5%.
Embodiment six: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 2g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 5mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=4mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 50sccm；
Three, the tube furnace after step 2 being processed is heated to 750 DEG C with the speed of 4 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 800 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 9.2%；Wherein pyridine nitrogen is 5.4%, and graphite-phase nitrogen is
3.8%.
Embodiment seven: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 2g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 5mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=4mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 50sccm；
Three, the tube furnace after step 2 being processed is heated to 745 DEG C with the speed of 2 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 900 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 6.5%；Wherein pyridine nitrogen is 2.5%, and graphite-phase nitrogen is 4%.
Embodiment eight: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 2g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 5mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=4mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 90sccm；
Three, the tube furnace after step 2 being processed is heated to 750 DEG C with the speed of 2 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 900 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 7.2%；Wherein pyridine nitrogen is 2.0%, and graphite-phase nitrogen is
5.2%.
Embodiment nine: it is by following that a step of the present embodiment prepares the method for nitrogen content and the adjustable doped graphene of kind in situ
Step realizes:
One, 2g carbonitride is placed in the quartz ampoule that one end seals；Internal diameter φ=the 5mm of wherein said quartz ampoule, long
=20cm, opening places cylindrical quartz plug, the external diameter φ of quartz plug=4mm, length=5cm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, with molecular pump, vacuum in tube furnace is evacuated to 8 × 10-4, close
Close molecular pump extraction valve, in tube furnace, be passed through the high-purity argon gas that flow is 50sccm；
Three, the tube furnace after step 2 being processed is heated to 750 DEG C with the speed of 2 DEG C/min, is then incubated 5min, obtains
Nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 1000 DEG C with the speed of 5 DEG C/min, is then incubated 30min,
To the adjustable doped graphene of nitrogen content and kind, i.e. complete.
Nitrogen-doped graphene nitrogen content prepared by the present embodiment is about 0.6%；Wherein pyridine nitrogen is 0.1%, and graphite-phase nitrogen is
0.5%.
The nitrogen content obtaining embodiment two to nine and the adjustable doped graphene of kind carry out XPS test, to the number obtained
According to adding up, obtain the embodiment two to nine nitrogen content by step 4 different heating temperature gained nitrogen-doped graphene sample
With Species distributing figure.As shown in Figure 8, the present invention can be regulated and controled by the heat time heating time and heating-up temperature that adjust each step
The nitrogen content of rear products therefrom and kind, can prepare the N doping graphite of specific nitrogen content and nitrogenous kind by the present invention
Alkene.
Claims (5)
1. a step prepares nitrogen content and the method for the adjustable doped graphene of kind in situ, it is characterised in that the method by with
Lower step is carried out:
One, 1～500g carbonitride is placed in the quartz ampoule that one end seals, internal diameter φ=5 of wherein said quartz ampoule～100mm,
Length=20cm, opening placement cylindrical quartz plug, external diameter φ=4 of quartz plug～99mm, length=5cm, in quartz ampoule
Footpath and quartz plug external diameter difference are 1mm；
Two, the quartz ampoule that will be equipped with carbonitride is placed in tube furnace, then vacuum in tube furnace is evacuated to
8×10-4～9 × 10-4Pa, being then passed through flow in tube furnace is 50～90sccm protective gas；
Three, the tube furnace after step 2 being processed is heated to 740～750 DEG C with the speed of 1～5 DEG C/min, is then incubated
5～120min, obtain nitrogen-doped graphene；
Four, the tube furnace after step 3 being processed is heated to 800～1000 DEG C with the speed of 5～20 DEG C/min, is then incubated
30～120min, obtain nitrogen content and the adjustable doped graphene of kind, i.e. complete.
An a kind of step the most according to claim 1 prepares nitrogen content and the method for the adjustable doped graphene of kind in situ,
It is characterized in that the protective gas described in step 2 is high-purity argon gas or high pure nitrogen.
An a kind of step the most according to claim 1 prepares nitrogen content and the method for the adjustable doped graphene of kind in situ,
It is characterized in that described in step 3 by step 2 process after tube furnace be heated to 740 DEG C with the speed of 2 DEG C/min.
An a kind of step the most according to claim 1 prepares nitrogen content and the method for the adjustable doped graphene of kind in situ,
It is characterized in that described in step 3 by step 2 process after tube furnace be heated to 750 DEG C with the speed of 2 DEG C/min.
An a kind of step the most according to claim 1 prepares nitrogen content and the method for the adjustable doped graphene of kind in situ,
It is characterized in that described in step 4 by step 3 process after tube furnace be heated to 950 DEG C with the speed of 5 DEG C/min.
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