CN106698410B - The preparation method of nitrogen atom doping carbon nanomaterial - Google Patents
The preparation method of nitrogen atom doping carbon nanomaterial Download PDFInfo
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Abstract
The preparation method of nitrogen atom doping carbon nanomaterial disclosed by the invention is first by carbon nanomaterial or derivatives thereof under atmosphere of inert gases, use fluorine gas gaseous mixture as fluorination reagent, direct fluorination treatment is carried out to it and obtains fluorinated carbon nanomaterial, then resulting fluorinated carbon nanomaterial is placed under ammonia/argon gas mixed gas atmosphere and carries out high-temperature post-treatment, obtain nitrogen-doped carbon nano material.Since present invention employs the method for modifying of " first activate-adulterating again ", it is not only that a kind of more efficiently new method for improving nitrogen atom doping amount is explored in this field, and also make nitrogen-doped carbon nano material nitrogen content obtained high, large specific surface area, it is simple for process simultaneously, cost is relatively low, has stronger application prospect.
Description
Technical field
The invention belongs to hydridization carbon material and its preparation technical fields, and in particular to a kind of nitrogen atom doping carbon nanomaterial
Preparation method.
Background technique
Population in the world increases, economic Rapid Expansion development, the demand accelerated growth at an amazing speed to the energy, and
The limited supply of the fossil fuel energy, the low energy source utilization rate of global range, so that energy problem becomes global problem.Cause
This, the Development of Novel energy has become the very important research topic of energy field, and develops advanced energy transfer and storage skill
Art becomes the research hotspot of new energy field again.
Compared with traditional material, carbon nanomaterial have due to its size dependency characteristic unique mechanical, catalysis and
Photoelectric properties etc. can be used for collecting solar energy, the preparation of hydrogen and storage, fuel cell, supercapacitor and lithium battery etc.
Field.Existing theoretical calculation and experiment show the doping of the hetero atom (N, B, P, S, F etc.) in carbon material skeleton for its own
Capacitance, redox reaction catalytic effect, absorption and storage hydrogen ability etc. suffer from significant facilitation, in addition miscellaneous original
Son also has the function of to be used as effective catalyst coordination activity point etc..Therefore researcher has carried out a large amount of correlative study to this
Work, and remarkable effect is achieved developing corresponding carbon nanomaterial efficient energy conversion and storing equipment aspect.Wherein, nitrogen is used
The preparation of atom doped carbon nanomaterial and performance study are even more most potential one of research direction.Though nitrogen-atoms and carbon atom
The two atomic radius is close, but because of electronic structure difference, the incorporation of N can realize what carbon material lattice mismatched degree minimized
Meanwhile so that electronic structure is changed.The property of nitrogen-doped carbon material by nitrogen content and specific surface area mainly by being influenced.
It is reported that the mode of N doping can be divided into two kinds: being mixed by carbon source and nitrogen source, in the mistake of carbon nanomaterial preparation
It is adulterated in journey；First prepare carbon nanomaterial or corresponding derivative (such as oxide/carbon nanometer tube, graphene oxide), then by its
Pass through post-processing doping with containing heteroatomic presoma.In general, hetero atom can be equably doped into carbon skeleton by the former
In, and Heteroatom doping amount is relatively easy to control；The latter is more likely to form heterocycle structure at edge and fault location, though it is easy to have operation
It realizes, is at low cost, the advantage that can be mass-produced, but facing that Heteroatom doping amount in carbon skeleton is relatively low and regulation hetero atom structure
The problems such as type configurations difficult.For example, carbon skeleton can be achieved through (>=800 DEG C) of high-temperature heat treatment under ammonia atmosphere in single-layer graphene
Post-processing N hydridization, however N content is only 1.1at.%；Using the graphene oxide of thermal reduction as raw material at 800 DEG C and
It is heat-treated under 900 DEG C of ammonia atmosphere, though N content is promoted, still not satisfactory, only 2.8at.%.Analyze N content compared with
Low concrete reason substantially has following three: first, has between carbon nanomaterial and nitrogen-atoms compared with high graphitization degree
It is active inadequate, the C-N key of sufficient amount can not be formed；Second, defect and fringe region are less in above-mentioned carbon nanomaterial；Third,
Excessively high heat treatment temperature may cause established C-N key fracture.
It is found in follow-up study, in graphene oxide, a large amount of oxygen-containing group may make graphene oxide and nitrogen former
The reactivity of son significantly improves, while more defects and fringe region can provide reaction position to form heterocycle structure in lamella
Point, therefore graphene oxide post-processes nitrogen content in obtained hydridization graphene in 500 DEG C in ammonia atmosphere and can be improved
5.0%.In other words, it is believed that oxidation processes play the role of a kind of " activation " to the N doping of graphene sheet layer, are conducive to nitrogen
Atom enters the carbon skeleton of graphene.However, when further increasing post-processing temperature (>=550 DEG C), nitrogen content but roll back
3.0% or so.In this regard, Li et al. people (X.Li, H.Wang, J.T.Robinson, G.Diankov, H.Dai, Journal of the
American Chemical Society, 2009,131:15939-15944) think that this is mainly due to the heat of graphene oxide
Stability is poor (because major cleavage peak is at 200 DEG C, temperature to lose most oxygen-containing groups after 500 DEG C), in higher temperatures
If being post-processed under degree, the reactivity that will be greatly reduced between graphene oxide and nitrogen-atoms of leaving away of oxygen-containing group,
Nitrogen-atoms is introduced into carbon skeleton to be difficult to obtain enough C-N keys one step to form the loop of going forward side by side；If reducing post-processing temperature, then
It is unable to get some nitrogen bonding patterns (such as graphite mould nitrogen and pyrroles's type nitrogen) haveing excellent performance.Therefore, the rear place of graphene oxide
Reason N doping, which needs to solve oxygen-containing group cracking under high temperature, leads to that particular configuration nitrogen can not be obtained under the decline of N doping amount and low temperature
Contradictory problems.
In the recent period, people are still more using change nitrogen source when seeking raising nitrogen atom doping amount method and path
Close object method, as Li Jing et al. (Li Jing, Wang Xianbao, Yang Jia, Yang Xuyu, Wan Li, Chemical Journal of Chinese Universities, 2013,34:
High temperature N doping 800-805) is carried out to graphene oxide using urea as nitrogen source；Sheng etc. (Z.H.Sheng, L.Shao,
J.J.Chen, W.J.Bao, F.G.Wang, X.H.Xia, ACS Nano 2011,5:4350-4358) utilize melamine and oxygen
Graphite alkene, which is blended, carries out high-temperature heat treatment etc..Although these methods all effectively increase the N doping of product, gained is produced
The specific surface area of object decreased significantly, this is detrimental to Performance optimization.That is, people still predominantly stay in so far
Using changing in thinking of the method for nitrogen source compound to improve nitrogen atom doping amount, not from raising graphene or graphene
The basic thinking of derivative itself hydridization chemical reactivity (especially under higher temperature) is set out, and inherently goes to seek new way
Diameter is low to solve the problems, such as nitrogen atom doping amount.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of preparation sides of nitrogen atom doping carbon nanomaterial
Method.
The preparation method of nitrogen atom doping carbon nanomaterial provided by the invention, the processing step and condition of this method are such as
Under:
It (1) is 3~80KPa's with fluorine gas initial partial pressure by carbon nanomaterial or derivatives thereof under atmosphere of inert gases
Fluorine gas gaseous mixture is warming up to 30~250 DEG C as fluorination reagent, with the heating rate of 1~20 DEG C/min, and keeps the temperature 10~600 points
Clock carries out direct fluorination treatment to it, then cools to room temperature, and obtains fluorinated carbon nanomaterial；
(2) resulting fluorinated carbon nanomaterial is placed under ammonia/inert gas mixed gas atmosphere, with 1~20 DEG C/
The heating rate of min is warming up to 400~1200 DEG C, and keeps the temperature 0.5~24 hour progress high-temperature post-treatment, obtains nitrogen-doped carbon and receives
Rice material.
Carbon nanomaterial or derivatives thereof is graphene, graphene oxide, porous graphite in method and step (1) made above
Any in alkene, fullerene, multi-walled carbon nanotube, oxide/carbon nanometer tube, single-walled carbon nanotube, carbon nanometer micro ball or mesoporous carbon
Kind.
Fluorine gas gaseous mixture described in method and step (1) made above is fluorine gas and nitrogen, argon gas, helium and carbon dioxide gas
At least one of body gas is formed, preferably the gaseous mixture of fluorine gas and nitrogen formation, and the initial partial pressure of fluorine gas preferably 10~
60KPa。
Heating rate preferably 3~20 DEG C/min of fluorination treatment, the temperature of fluorination treatment in method and step (1) made above
It is preferred that 150~250 DEG C, soaking time preferably 60~600 minutes.
Atmosphere of inert gases described in method and step (1) made above is in nitrogen, argon gas, helium and carbon dioxide gas
It is at least one formed, preferred nitrogen atmosphere.
The concentration of ammonia is 2~30% in ammonia/inert gas mixed gas described in method and step (2) made above,
Flow is 1~20Torr.
In ammonia/inert gas mixed gas described in method and step (2) made above inert gas be nitrogen, argon gas,
The formation of any one of helium and carbon dioxide gas, preferably argon gas.
Heating rate preferably 3~20 DEG C/min of method and step (2) high temperature post-processing made above, high-temperature post-treatment
Preferably 550~900 DEG C of temperature, soaking time preferably 1~15 hour.
Compared with prior art, the invention has the following advantages:
(1) since the present invention is to provide the method for modifying of a kind of " first activate-adulterating again ", thus compared with prior art
It is applicable not only to the aza modification to all kinds of carbon nanomaterials or derivatives thereof, and is also explored for this field and provides one kind more
For the new method for effectively improving nitrogen atom doping amount.
(2) since the method for the present invention is to be lived using the higher fluorine gas of reactivity to carbon nanomaterial or derivatives thereof
Change, thus reacts the active functional group group C-F key generated and not only have the reactivity with nitrogen-atoms, but also be also equipped in high temperature
Under thermal stability, to guarantee that it is living with reacting for nitrogen-atoms that the carbon nanomaterial or derivatives thereof after activation remains at high temperature
Property, it haves laid a good foundation for the final nitrogen atom doping amount for improving material.
(3) since the method for the present invention is to be carried out at activation using direct fluorination technology to carbon nanomaterial or derivatives thereof
Reason, thus can fluorine content, defect concentration, thermal stability to resulting fluorinated carbon nanomaterial or derivatives thereof etc. carry out gradient
(as shown in Figure 1) is reconciled in gradual change, different to meet to obtain a series of product of nitrogen-doped carbon nano material of structure gradual changes
Demand.
(4) since the present invention is the method for modifying for using " first activate-adulterating again ", thus make nitrogen-doped carbon obtained
Not only nitrogen content is high for nano material, and large specific surface area.
(5) method and process provided by the invention is simple and easy, and cost is relatively low, has stronger application prospect.
Detailed description of the invention
Attached drawing is the XPS C1s spectrogram of the fluorinated graphene of direct fluorination treatment preparation under different temperatures.It is corresponding in figure
Be fluorinated temperature be 50,100,150,200 DEG C respectively, it can be seen from the figure that the quantity of C-F key be with fluorination temperature increase and
It is gradually increasing, and then reflects that direct fluorination prepares the Modulatory character of the fluorine content of fluorinated graphene.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique in the field
Some nonessential modifications and adaptations that member makes according to the content of aforementioned present invention, still fall within protection scope of the present invention
It is worth noting that: 1) the contain nitrogen content of following embodiment and comparative example products therefrom be by X-ray light
Electron spectrum test gained；2) following embodiment and the specific surface area of comparative example products therefrom are to pass through Brunner-Emmet-
Teller (BET) test gained.By embodiment 1 and comparative example 1 as can be seen that the method in the present invention is conducive to obtain nitrogen and contain
Measure higher, the bigger nitrogen-doped carbon nano material of specific surface area.
Embodiment 1
Graphene is placed in closed vacuum reactor, is vacuumized afterwards three times with the air in argon gas metathesis reactor,
Be re-filled with the gaseous mixture of fluorine gas and argon gas, and control fluorine gas in the reactor initial partial pressure be 30KPa, then with 10 DEG C/min's
Heating rate is warming up to 80 DEG C and keeps the temperature 300 minutes, to reactor cooled to room temperature, takes out fluorinated graphene.It will fluorination
Graphene is passed through ammonia/argon gas mixed gas after being put into tube furnace, wherein the concentration of ammonia be 30%, flow 1Torr, simultaneously
700 DEG C are warming up to the heating rate of 10 DEG C/min, and keeps the temperature 0.5 hour.It is cooled to room temperature to tube furnace, the nitrogen taken out
Doped graphene.
The nitrogen content of the nitrogen-doped graphene is 5.4%, specific surface area 443m2/g。
Embodiment 2
Multi-walled carbon nanotube is placed in closed vacuum reactor, is taken out afterwards three times with the air in nitrogen metathesis reactor
Vacuum, is re-filled with the gaseous mixture of fluorine gas and nitrogen, and control fluorine gas in the reactor initial partial pressure be 80KPa, then with 20 DEG C/
The heating rate of min is warming up to 250 DEG C and keeps the temperature 10 minutes, to reactor cooled to room temperature, takes out fluorination multi wall carbon and receives
Mitron.Fluorination multi-walled carbon nanotube is put into after tube furnace and is passed through ammonia/nitrogen mixed gas, wherein the concentration of ammonia is 2%,
Flow is 20Torr, while being warming up to 400 DEG C with the heating rate of 20 DEG C/min, and keep the temperature 24 hours.It is cooled to tube furnace
Room temperature, the N doping multi-walled carbon nanotube taken out.
The nitrogen content of the N doping multi-walled carbon nanotube is 2.4%, specific surface area 240m2/g。
Embodiment 3
Graphene oxide is placed in closed vacuum reactor, is taken out afterwards three times with the air in nitrogen metathesis reactor true
Sky, is re-filled with the gaseous mixture of fluorine gas and argon gas, and control fluorine gas in the reactor initial partial pressure be 3KPa, then with 1 DEG C/min
Heating rate be warming up to 150 DEG C and keep the temperature 60 minutes, to reactor cooled to room temperature, take out Fluorinated graphene oxide.
Fluorinated graphene oxide is put into after tube furnace and is passed through ammonia/argon gas mixed gas, wherein the concentration of ammonia is 15%, and flow is
10Torr, while 550 DEG C are warming up to the heating rate of 3 DEG C/min, and keep the temperature 6 hours.It is cooled to room temperature, takes out to tube furnace
Obtain nitrogen-doped graphene.
The nitrogen content of the nitrogen-doped graphene is 6.4%, specific surface area 643m2/g。
Embodiment 4
Graphene oxide is placed in closed vacuum reactor, is taken out afterwards three times with the air in nitrogen metathesis reactor true
Sky, is re-filled with the gaseous mixture of fluorine gas and argon gas, and control fluorine gas in the reactor initial partial pressure be 40KPa, then with 1 DEG C/min
Heating rate be warming up to 30 DEG C and keep the temperature 200 minutes, to reactor cooled to room temperature, take out Fluorinated graphene oxide.
Fluorinated graphene oxide is put into after tube furnace and is passed through ammonia/argon gas mixed gas, wherein the concentration of ammonia is 15%, and flow is
10Torr, while 600 DEG C are warming up to the heating rate of 3 DEG C/min, and keep the temperature 12 hours.It is cooled to room temperature, takes to tube furnace
Nitrogen-doped graphene is obtained out.
The nitrogen content of the nitrogen-doped graphene is 7.0%, specific surface area 622m2/g。
Embodiment 5
Porous graphene is placed in closed vacuum reactor, is taken out afterwards three times with the air in argon gas metathesis reactor true
Sky, is re-filled with the gaseous mixture of fluorine gas, nitrogen and argon gas, and control fluorine gas in the reactor initial partial pressure be 10KPa, then with 3
DEG C/heating rate of min is warming up to 200 DEG C and keeps the temperature 600 minutes, to reactor cooled to room temperature, it is porous to take out fluorination
Graphene.Fluorination porous graphene is put into after tube furnace and is passed through ammonia/helium mix gas, wherein the concentration of ammonia is
10%, flow 5Torr, while 900 DEG C are warming up to the heating rate of 1 DEG C/min, and keep the temperature 1 hour.It is cooling to tube furnace
To room temperature, taking-up obtains N doping porous graphene.
The nitrogen content of the N doping porous graphene is 6.7%, specific surface area 1505m2/g。
Embodiment 6
Single-walled carbon nanotube is placed in closed vacuum reactor, is taken out afterwards three times with the air in argon gas metathesis reactor
Vacuum, is re-filled with the gaseous mixture of fluorine gas and argon gas, and control fluorine gas in the reactor initial partial pressure be 70KPa, then with 20 DEG C/
The heating rate of min is warming up to 180 DEG C and keeps the temperature 300 minutes, to reactor cooled to room temperature, takes out fluorination single wall carbon and receives
Mitron.Fluorination single-walled carbon nanotube is put into after tube furnace and is passed through ammonia, argon gas and helium mix gas, wherein the concentration of ammonia
It is 20%, flow 20Torr, while 1200 DEG C are warming up to the heating rate of 15 DEG C/min, and keep the temperature 0.5 hour.To tubular type
Furnace is cooled to room temperature, and taking-up obtains nitrogen-doped single-walled carbon nanotubes.
The nitrogen content of the nitrogen-doped single-walled carbon nanotubes graphene is 4.4%, specific surface area 863m2/g。
Embodiment 7
Single-walled carbon nanotube is placed in closed vacuum reactor, is taken out afterwards three times with the air in argon gas metathesis reactor
Vacuum, is re-filled with the gaseous mixture of fluorine gas and argon gas, and control fluorine gas in the reactor initial partial pressure be 60KPa, then with 15 DEG C/
The heating rate of min is warming up to 220 DEG C and keeps the temperature 400 minutes, to reactor cooled to room temperature, takes out fluorination single wall carbon and receives
Mitron.Fluorination single-walled carbon nanotube is put into after tube furnace and is passed through ammonia, argon gas and helium mix gas, wherein the concentration of ammonia
It is 5%, flow 15Torr, while 800 DEG C are warming up to the heating rate of 10 DEG C/min, and keep the temperature 2 hours.It is cold to tube furnace
But to room temperature, taking-up obtains nitrogen-doped single-walled carbon nanotubes.
The nitrogen content of the nitrogen-doped single-walled carbon nanotubes graphene is 4.7%, specific surface area 860m2/g。
Embodiment 8
Mesoporous carbon is placed in closed vacuum reactor, with the air in argon gas and nitrogen mixed gas metathesis reactor
Vacuumize afterwards three times, be re-filled with the gaseous mixture of fluorine gas and nitrogen, and control fluorine gas in the reactor initial partial pressure be 20KPa, so
100 DEG C are warming up to the heating rate of 15 DEG C/min afterwards and keeps the temperature 100 minutes, to reactor cooled to room temperature, take out fluorine
Change mesoporous carbon.Fluorination mesoporous carbon is put into after tube furnace and is passed through ammonia/argon gas mixed gas, wherein the concentration of ammonia is 30%,
Flow is 10Torr, while being warming up to 550 DEG C with the heating rate of 1 DEG C/min, and keep the temperature 15 hours.Room is cooled to tube furnace
Temperature, taking-up obtain N doping mesoporous carbon.
The nitrogen content of the N doping mesoporous carbon is 6.3%, specific surface area 1440m2/g。
Comparative example 1
Graphene is put into after tube furnace and is passed through ammonia/argon gas mixed gas, wherein the concentration of ammonia is 30%, and flow is
1Torr, while 700 DEG C are warming up to the heating rate of 10 DEG C/min, and keep the temperature 0.5 hour.It is cooled to room temperature, takes to tube furnace
Nitrogen-doped graphene is obtained out.
The nitrogen content of the nitrogen-doped graphene is 1.4%, specific surface area 243m2/g。
Comparative example 2
Multi-walled carbon nanotube is put into after tube furnace and is passed through ammonia/nitrogen mixed gas, wherein the concentration of ammonia is 30%,
Flow is 20Torr, while being warming up to 400 DEG C with the heating rate of 20 DEG C/min, and keep the temperature 24 hours.It is cooled to tube furnace
Room temperature, taking-up obtain N doping multi-walled carbon nanotube.
The nitrogen content of the N doping multi-walled carbon nanotube is 0.9%, specific surface area 233m2/g。
Claims (8)
1. a kind of preparation method of nitrogen atom doping carbon nanomaterial, the processing step and condition of this method are as follows:
(1) by carbon nanomaterial or derivatives thereof under atmosphere of inert gases, the fluorine gas for being 3~80KPa with fluorine gas initial partial pressure
Gaseous mixture is warming up to 30~250 DEG C as fluorination reagent, with the heating rate of 1~20 DEG C/min, and heat preservation 10~600 minutes right
It carries out direct fluorination treatment, then cools to room temperature, obtains fluorinated carbon nanomaterial or fluorinated carbon nanomaterial derivative；
(2) resulting fluorinated carbon nanomaterial or fluorinated carbon nanomaterial derivative are placed in ammonia/argon gas mixed gas atmosphere
Under, 400~1200 DEG C are warming up to the heating rate of 1~20 DEG C/min, and keep the temperature 0.5~24 hour progress high-temperature post-treatment,
Nitrogen-doped carbon nano material is obtained,
Wherein in ammonia described in step (2)/argon gas mixed gas ammonia concentration be 2~30%, flow be 1~
20Torr。
2. the preparation method of nitrogen atom doping carbon nanomaterial according to claim 1, described in this method step (1)
Carbon nanomaterial or derivatives thereof is graphene, fullerene, multi-walled carbon nanotube, oxide/carbon nanometer tube, single-walled carbon nanotube, carbon
Any one of nanosphere or mesoporous carbon.
3. the preparation method of nitrogen atom doping carbon nanomaterial according to claim 1 or 2, institute in this method step (1)
The fluorine gas gaseous mixture stated is that at least one of fluorine gas and nitrogen, argon gas, helium and carbon dioxide gas gas are formed, fluorine gas
Initial partial pressure is 10~60KPa.
4. the preparation method of nitrogen atom doping carbon nanomaterial according to claim 1 or 2, institute in this method step (1)
The heating rate for the fluorination treatment stated is 3~20 DEG C/min, and the temperature of fluorination treatment is 150~250 DEG C, soaking time is 60~
600 minutes.
5. the preparation method of nitrogen atom doping carbon nanomaterial according to claim 3, described in this method step (1)
The heating rate of fluorination treatment is 3~20 DEG C/min, and the temperature of fluorination treatment is 150~250 DEG C, and soaking time is 60~600
Minute.
6. the preparation method of nitrogen atom doping carbon nanomaterial according to claim 1 or 2, institute in this method step (2)
The heating rate for the high-temperature post-treatment stated is 3~20 DEG C/min, and the temperature of high-temperature post-treatment is 550~900 DEG C, and soaking time is
1~15 hour.
7. the preparation method of nitrogen atom doping carbon nanomaterial according to claim 3, described in this method step (2)
The heating rate of high-temperature post-treatment is 3~20 DEG C/min, and the temperature of high-temperature post-treatment is 550~900 DEG C, soaking time is 1~
15 hours.
8. the preparation method of nitrogen atom doping carbon nanomaterial according to claim 5, described in this method step (2)
The heating rate of high-temperature post-treatment is 3~20 DEG C/min, and the temperature of high-temperature post-treatment is 550~900 DEG C, soaking time is 1~
15 hours.
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