CN106784872A - A kind of method that the nitrogen-doped carbon material containing pure pyridine nitrogen is prepared based on chemical vapor deposition - Google Patents
A kind of method that the nitrogen-doped carbon material containing pure pyridine nitrogen is prepared based on chemical vapor deposition Download PDFInfo
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Abstract
The invention discloses a kind of method that the nitrogen-doped carbon material containing pure pyridine nitrogen is prepared based on chemical vapor deposition, the method is to first pass through chemical gaseous phase depositing process to generate carbon nano-fiber in substrate surface, the carbon nano-fiber uses hydrofluoric acid corrosion treatment, N doping is carried out to the carbon nano-fiber after corrosion treatment, nitrogen-doped carbon material is obtained final product;The preparation method is simple to operate, low cost, is suitable to large-scale production;The nitrogen-doped carbon material of preparation has the characteristics of N doping amount is high, doping is controllable, and N structure containing pure pyridine, meets fuel cells applications requirement.
Description
Technical field
It is more particularly to a kind of to be prepared based on chemical vapor deposition the present invention relates to a kind of preparation method of nitrogen-doped carbon material
The method of the nitrogen-doped carbon material containing pure pyridine nitrogen, belongs to fuel cell catalyst field of material technology.
Background technology
In recent years, the rapid reduction of traditional energy with to energy demand it is increasing brought to the mankind and society it is very big
Challenge, exploitation and the focus also paid close attention into Many researchers of research of new energy.Fuel cell technology, as Hydrogen Energy profit
Effective means, is one of TRT of the renewable sources of energy, it is considered to be the Energy Star of 21 century, with wide application
Prospect.Be classified as fuel cell technology and be related to one of technology of national security by the U.S., by the U.S.《Epoch》Weekly is chosen as 21
Century has one of ten big technologies of most significant impact to human lives.Although fuel cell has power density high, reaction temperature
Degree is low, starts soon, many advantages, such as environment-friendly, yet with technologies such as its expensive Pt/C catalyst price and stability differences
Immature and not yet mass industrialized production.Therefore, we need badly and find new catalyst, reach reduces cost, and add
Fast response speed, the purpose for reducing electrode reaction activation energy, improving energy content of battery conversion ratio.
Since the sixties in last century, the research of non-platinum catalyst just turns into study hotspot.From initial Ag, Pb parts substitute
Platinum, nonmetallic (N, B, S etc.) doping carbon nanomaterial finally.Sanjeev Mukerjee et al. have studied bianry alloy Pt
The catalysis activity of+Ni, Pt+Cr, Pt+Co, research is thought, in alloying process, characterization of adsorption and the electronics knot of material surface
Structure there occurs change, and then show catalysis activity and stability higher.And in nonmetal doping, N is unique due to it
Electronic structure become the study hotspot of people, in nitrogen-doped carbon material, be mainly shown as graphite nitrogen, pyridine nitrogen, pyrroles's nitrogen
And four kinds of existence forms of nitrogen oxide.The doping method of nitrogen-doped nanometer carbon material mainly has three kinds:1. doping in situ, i.e., in nanometer
Direct in-situ doping nitrogen in the preparation process of carbon material;2. post processing doping, i.e., after nano-carbon material is synthesized, then use nitrogen source
Nano-carbon material post processing is doped;3. itrogenous organic substance is directly pyrolyzed, i.e., directly itrogenous organic substance is pyrolyzed.
Ruguang Ma et al. employ bottom-to-top method and are prepared for nitrogen-doped graphene, its by after annealing, with height
Specific surface and hierarchical porous structure, show excellent electro catalytic activity in bronsted lowry acids and bases bronsted lowry solution.Nitrogen-doped nanometer carbon material is lived
Property site research also turning into focal issue of concern, Many researchers think that pyridine nitrogen contributes to oxygen reduction reaction
(ORR) formation of active site, but their viewpoint can not be completely convincing, because the catalysis synthesized at them
In agent, the mixing of the type of nitrogen always graphite nitrogen, pyridine nitrogen, pyrroles's nitrogen and nitrogen oxide.
In recent years, researchers attempt to study itself and the relation between ORR catalysis activities by preparing pure pyridine nitrogen,
Donghui Guo devise the highly oriented pyrolytic graphite (HOPG) of a kind of " edge-patterned " as the base of pure pyridine nitrogen
Bottom, Zhiqiang Luo successfully prepare pure pyridine nitrogen-doped graphene by CVD, and obtaining technique yet with them will to equipment
Ask higher, preparation process is excessively complicated, therefore this new is urged still can not on a large scale to prepare pure pyridine nitrogen-doped carbon material at present
Agent.
Up to the present, pure pyridine nitrogen-doped carbon material is still a novelty and has the work of challenge, and not only doping rate is low
And energy consumption is big, so this patent discloses one kind simply, it is easy, effectively, the pure pyridine nitrogen-doped carbon material that can be prepared on a large scale
Method.
The content of the invention
For the defect that nitrogen-doped carbon material of the prior art is present, it is to provide a kind of nitrogen to mix that the purpose of the present invention is
Miscellaneous amount is high, doping is controllable, and the nitrogen-doped carbon material containing pure pyridine nitrogen preparation method, the method is simple, low cost, pair set
It is low for requiring, it is easy to accomplish large-scale production.
In order to realize above-mentioned technical purpose, prepared containing pure pyridine nitrogen based on chemical vapor deposition the invention provides a kind of
The method of nitrogen-doped carbon material, the method is comprised the following steps:
1) carbon nano-fiber is generated in substrate surface by chemical gaseous phase depositing process;
2) carbon nano-fiber is used into hydrofluoric acid corrosion treatment;
3) N doping is carried out to the carbon nano-fiber after corrosion treatment, is obtained final product.
Technical scheme prepares carbon nano-fiber (CNFs) by CVD method first, is prepared by the method
Nano carbon fiber has unique texture, and it is internal with complete graphene sheet layer, but edge is five-membered ring, hexatomic ring and defect
" loop " structure of composition, if directly being carried out N doping, pyridine nitrogen, pyrroles's nitrogen, graphite nitrogen and oxidation can simultaneously occurs
The nitrogen-doped carbon structure such as nitrogen.Technical scheme it is critical only that and nano carbon fiber is cut out using hydrofluoric acid dexterously
(corrosion treatment), is cut by HF to " loop " structure, and does not destroy carbon atom complete inside carbon nano-fiber simultaneously
Rotating fields, so as to produce exposed, avtive spot " medelling " border high, these borders are easy to the formation and raising of pyridine nitrogen
The content of pyridine nitrogen.
Preferred scheme, the process for generating carbon nano-fiber in substrate by chemical gaseous phase depositing process is:A) by base
Basal surface roughening pretreatment;B) in the substrate surface load transitions race slaine;C) area load there is into transition metal salt
Substrate be placed in CVD deposition stove, successively under inert atmosphere and/or nitrogen atmosphere, in 300~600 DEG C (preferably 400~
550 DEG C) heat treatment;Under hydrogen atmosphere, in 300~600 DEG C (preferably 450~550 DEG C) heat treatment, in carbonaceous sources atmosphere
Under, in 500~900 DEG C (preferably 600~800 DEG C) heat treatment, i.e., generate carbon nano-fiber in substrate surface.
More preferably scheme, substrate is carbon material, ceramic material or metal material.
More preferably scheme, magnesium-yttrium-transition metal salt includes at least one in nickel, iron, the slaine of chromium.Such as Ni (NO3)3、
Fe(NO3)3、Co(NO3)2Deng magnesium-yttrium-transition metal salt is supported on matrix surface by infusion process, and the magnesium-yttrium-transition metal salt of use is molten
The concentration of liquid is 0.1~20wt.% (preferably 5~15wt.%).After slaine is through Overheating Treatment, by hydrogen reducing, as
The catalyst of growing nano carbon fiber.
More preferably scheme, carbonaceous sources atmosphere is the gas comprising at least one of methane, propylene, acetylene, ethene, propine
Atmosphere.Atmosphere containing nitrogen source also includes nitrogen and/or inert atmosphere as vector gas, and this is the common knowledge of this area.
More preferably scheme, substrate surface roughening preprocessing process is:Substrate is carried out at dipping with strong acid or highly basic
Reason.Such as HNO3, NaOH etc., its concentration can be in the range of 0.1~8M (preferably 3~6M).
More preferably scheme, the substrate that area load has transition metal salt is placed in CVD deposition stove, successively in inert atmosphere
And/or under nitrogen atmosphere, 0.5~5h (preferably 1~3h) is heat-treated in 300~600 DEG C;Under hydrogen atmosphere, in 300~
600 DEG C of 0.5~5h of heat treatments (preferably 1~3h);Under carbonaceous sources atmosphere, 0.1~5h is heat-treated (preferably in 500~900 DEG C
It is 0.3~2h).
Preferred scheme, the carbon nano-fiber use time of hydrofluoric acid corrosion treatment for 0.5~5h (preferably 1~
2h)。
More preferably scheme, hydrofluoric acid concentration is 10~33mol L-1(preferably 15~25mol L-1)。
More preferably scheme, be to the process that the carbon nano-fiber after corrosion treatment carries out N doping:After corrosion treatment
Carbon nano-fiber be placed in atmosphere containing nitrogen source, 400~800 DEG C (preferably 650~750 DEG C) heat treatment, obtain final product containing pure pyrrole
The nitrogen-doped carbon material of pyridine nitrogen.
More preferably scheme, nitrogen source includes at least one of ammonia, polypyridine, pyridine, melamine, polypyrrole, pyrroles.
More preferably scheme, heat treatment time is 0.3~10h.
The method for preparing the nitrogen-doped carbon material containing pure pyridine nitrogen based on chemical vapor deposition of the invention includes following tool
Body step:
The preparation of A, CNFs:In substrate (carbon, ceramics or metal etc.), with strong acid or highly basic, (such as concentration is 0.1~8M
HNO3Or NaOH etc.) roughening substrate surface, it is washed to neutral and dries;By the substrate after drying be put in concentration for 0.1~
(such as Ni (NO in the magnesium-yttrium-transition metal salting liquid of 20wt.%3)3、Fe(NO3)3、Co(NO3)2Deng) 0.1~10h of middle dipping, take out
After be put in baking oven and dry;The substrate that area load has magnesium-yttrium-transition metal salt is put in CVD deposition stove, inert gas and/
Or (gas flow is 0.1~10Lmin under nitrogen protection atmosphere-1), it is warming up to 300~600 DEG C and is incubated 0.5~5h, then is passed through
Reducibility gas H2(flow is 0.3~5L min-1), after soaking time is 0.5~5h, protected in inert gas and/or nitrogen
(gas flow is 0.1~10Lmin under atmosphere-1) 500~900 DEG C of insulations are warming up to, while being passed through carbon-source gas during incubation
(such as methane, propylene, acetylene gas, flow are 0.3~5L min-1) with carrier gas (such as nitrogen, argon gas and/or hydrogen, gas
Body flow is 0.1~6L min-1) mixed atmosphere, 0.1~5h of soaking time;Finally in inert gas and/or nitrogen protection atmosphere
Under (gas flow be 0.1~10Lmin-1) be down to room temperature, i.e., CNFs is generated in substrate;
B, CNFs are 10~33mol L in concentration-1HF solution in impregnate 0.1~5h, after be washed to neutral and be put in baking
Dried in case, obtain the CNFs after HF " cutting ";
C, by the CNFs after " cutting ", under inert gas and/or nitrogen protection atmosphere (gas flow be 0.1~
10Lmin-1) it is warming up to 400~800 DEG C, and (such as ammonia, pyridine, melamine etc., gas flow is 0.1 under nitrogen source atmosphere
~5L min-1, or the material such as polypyridine, polypyrrole etc. for producing nitrogenous gas can be cracked under the high temperature conditions) insulation 0.1
After~10h, (gas flow is 0.1~10Lmin under inert gas and/or nitrogen protection atmosphere-1) it is cooled to room temperature, you can
Obtain the CNFs containing pure pyridine N doping.
Compared with the prior art, the Advantageous Effects that technical scheme is brought:
1) nitrogen-doped carbon material prepared by technical scheme has that N doping amount is high, N doping amount is controllable and contains
Pure pyridine N structure, N doping amount is more than 7at.%, and without dephasigns such as pyrroles's nitrogen, graphite nitrogen and nitrogen oxides.
2) technical scheme is based on ripe vapour deposition process and prepares, with simple to operate, equipment requirement it is low, into
The characteristics of this is low, is suitable to large-scale production.
Brief description of the drawings
【Fig. 1】It is the nitrogen XPS collection of illustrative plates of the nitrogen-doped carbon material containing pure pyridine nitrogen prepared by embodiment 1;
【Fig. 2】Be embodiment 1 prepare containing four kinds of nitrogen XPS collection of illustrative plates of the carbon nano-fiber of nitrogen type.
Specific embodiment
Following examples are intended to further illustrate present invention, rather than the protection model of limitation the claims in the present invention
Enclose.
Embodiment 1
With carbon paper as substrate, 1M HNO are used3After to carbon paper surface coarsening 2h, it is washed to neutral and dries 6h at 80 DEG C, so
The carbon paper after drying is put in 6wt.%Ni (NO afterwards3)36h in solution, dries 6h, and then area load is had after taking-up at 80 DEG C
Ni(NO3)3Carbon paper be put in CVD deposition stove, in N2(6L min-1, 99.9%) 500 DEG C are warming up under protective atmosphere and are incubated
A period of time 4h, preceding 2h is passed through N during insulation2(3L min-1, 99.9%), rear 2h is passed through reducibility gas H2(3L min-1,
99.9%), then in N2(6L min-1, 99.9%) and 700 DEG C are warming up under protective atmosphere, and in C3H6With N2Mixed atmosphere (C3H6:
3L min-1;N2:4L min-1) middle insulation 40min;Finally in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.Choosing
Select 20mol L-1HF carry out " cutting " 30min to CNFs, distilled water is washed to neutral and dries 6h at 80 DEG C.This is dried
CNFs is put in tube furnace, in N2(6L min-1, 99.9%) and 700 DEG C are warming up under inert gas shielding, it is passed through NH3(3L min-1, 99.9%) insulation 3h after, in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.In the N-CNFs samples for obtaining, N
Atom content is 12.59at.% and is pure pyridine nitrogen.The CNFs that contrast is not corroded by HF adulterates under identical condition
3h, nitrogen content is only 3.28at.%, and nitrogen species is four kinds of pyridine nitrogen, pyrroles's nitrogen, graphite nitrogen and nitrogen oxide, illustrates this hair
It is bright to have good pure pyridine N doping effect.Wherein XPS is characterized and is referred to Fig. 1 (nitrogen units of the carbon nano-fiber containing pure pyridine nitrogen
Plain XPS collection of illustrative plates) and Fig. 2 (containing four kinds of nitrogen XPS collection of illustrative plates of the carbon nano-fiber of nitrogen type).
Embodiment 2
With carbon paper as substrate, 1M HNO are used3After to carbon paper surface coarsening 2h, it is washed to neutral and dries 6h at 80 DEG C, so
The carbon paper after drying is put in 6wt.%Ni (NO afterwards3)36h in solution, dries 6h, and then area load is had after taking-up at 80 DEG C
Ni(NO3)3Carbon paper be put in CVD deposition stove, in N2(6L min-1, 99.9%) 350 DEG C are warming up under protective atmosphere and are incubated
A period of time 4h, preceding 2h is passed through N during insulation2(3L min-1, 99.9%), rear 2h is passed through reducibility gas H2(3L min-1,
99.9%), then in N2(6L min-1, 99.9%) and 600 DEG C are warming up under protective atmosphere, and in C3H6With N2Mixed atmosphere (C3H6:
3L min-1;N2:4L min-1) middle insulation 40min;Finally in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.Choosing
Select 20mol L-1HF carry out " cutting " 30min to CNFs, distilled water is washed to neutral and dries 6h at 80 DEG C.This is dried
CNFs is put in tube furnace, in N2(6L min-1, 99.9%) and 750 DEG C are warming up under inert gas shielding, it is passed through NH3(3L min-1, 99.9%) insulation 3h after, in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.In the N-CNFs samples for obtaining, N
Atom content is 6.42at.% and is pure pyridine nitrogen.Contrast is not adulterated 3h under identical condition by the CNFs of HF corrosion,
Nitrogen content is only 1.76at.%, and nitrogen species is four kinds of pyridine nitrogen, pyrroles's nitrogen, graphite nitrogen and nitrogen oxide, illustrates that the present invention has
Good pure pyridine N doping effect.
Embodiment 3
With carbon paper as substrate, 1M HNO are used3After to carbon paper surface coarsening 2h, it is washed to neutral and dries 6h at 80 DEG C, so
The carbon paper after drying is put in 6wt.%Ni (NO afterwards3)36h in solution, dries 6h, and then area load is had after taking-up at 80 DEG C
Ni(NO3)3Carbon paper be put in CVD deposition stove, in N2(6L min-1, 99.9%) 600 DEG C are warming up under protective atmosphere and are incubated
A period of time 4h, preceding 2h is passed through N during insulation2(3L min-1, 99.9%), rear 2h is passed through reducibility gas H2(3L min-1,
99.9%), then in N2(6L min-1, 99.9%) and 800 DEG C are warming up under protective atmosphere, and in C3H6With N2Mixed atmosphere (C3H6:
3L min-1;N2:4L min-1) middle insulation 40min;Finally in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.Choosing
Select 15mol L-1HF carry out " cutting " 30min to CNFs, distilled water is washed to neutral and dries 6h at 80 DEG C.This is dried
CNFs is put in tube furnace, in N2(6L min-1, 99.9%) and 700 DEG C are warming up under inert gas shielding, it is passed through NH3(3L min-1, 99.9%) insulation 3h after, in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.In the N-CNFs samples for obtaining, N
Atom content is 5.86at.% and is pure pyridine nitrogen.Contrast is not adulterated 3h under identical condition by the CNFs of HF corrosion,
Nitrogen content is only 1.65at.%, and nitrogen species is four kinds of pyridine nitrogen, pyrroles's nitrogen, graphite nitrogen and nitrogen oxide, illustrates that the present invention has
Good pure pyridine N doping effect.
Embodiment 4
With carbon paper as substrate, 1M HNO are used3After to carbon paper surface coarsening 2h, it is washed to neutral and dries 6h at 80 DEG C, so
The carbon paper after drying is put in 6wt.%Ni (NO afterwards3)36h in solution, dries 6h, and then area load is had after taking-up at 80 DEG C
Ni(NO3)3Carbon paper be put in CVD deposition stove, in N2(6L min-1, 99.9%) 500 DEG C are warming up under protective atmosphere and are incubated
A period of time 4h, preceding 2h is passed through N during insulation2(3L min-1, 99.9%), rear 2h is passed through reducibility gas H2(3L min-1,
99.9%), then in N2(6L min-1, 99.9%) and 700 DEG C are warming up under protective atmosphere, and in C3H6With N2Mixed atmosphere (C3H6:
3L min-1;N2:4L min-1) middle insulation 40min;Finally in N2(6Lmin-1, 99.9%) and protective atmosphere drops to room temperature.Selection
20mol L-1HF carry out " cutting " 30min to CNFs, distilled water is washed to neutral and dries 6h at 80 DEG C.This is dried
CNFs is put in tube furnace, in N2(6L min-1, 99.9%) and 750 DEG C are warming up under inert gas shielding, it is passed through NH3(3L min-1, 99.9%) insulation 3h, after in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.In the N-CNFs samples for obtaining, N
Atom content is 9.25at.% and is pure pyridine nitrogen.Contrast is not adulterated 2h under identical condition by the CNFs of HF corrosion,
Nitrogen content is only 2.24at.%, and nitrogen species is four kinds of pyridine nitrogen, pyrroles's nitrogen, graphite nitrogen and nitrogen oxide, illustrates that the present invention has
Good pure pyridine N doping effect.
Embodiment 5
With carbon paper as substrate, 1M HNO are used3After to carbon paper surface coarsening 2h, it is washed to neutral and dries 6h at 80 DEG C, so
The carbon paper after drying is put in 6wt.%Ni (NO afterwards3)36h in solution, dries 6h, and then area load is had after taking-up at 80 DEG C
Ni(NO3)3Carbon paper be put in CVD deposition stove, in N2(6L min-1, 99.9%) 550 DEG C are warming up under protective atmosphere and are incubated
A period of time 4h, preceding 2h is passed through N during insulation2(3Lmin-1, 99.9%), rear 2h is passed through reducibility gas H2(3L min-1,
99.9%), then in N2(6L min-1, 99.9%) and 650 DEG C are warming up under protective atmosphere, and in C3H6With N2Mixed atmosphere (C3H6:
3L min-1;N2:4Lmin-1) middle insulation 40min;Finally in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.Selection
22molL-1HF carry out " cutting " 30min to CNFs, distilled water is washed to neutral and dries 6h at 80 DEG C.This is dried
CNFs is put in tube furnace, in N2(6L min-1, 99.9%) and 650 DEG C are warming up under inert gas shielding, it is passed through NH3(3L min-1, 99.9%) insulation 3h after, in N2(6L min-1, 99.9%) and protective atmosphere drops to room temperature.In the N-CNFs samples for obtaining, N
Atom content is 7.56at.% and is pure pyridine nitrogen.Contrast is not adulterated 1h under identical condition by the CNFs of HF corrosion,
Nitrogen content is only 1.25at.%, and nitrogen species is four kinds of pyridine nitrogen, pyrroles's nitrogen, graphite nitrogen and nitrogen oxide, illustrates that the present invention has
Good pure pyridine N doping effect.
Claims (10)
1. it is a kind of based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method, it is characterised in that:Including
Following steps:
1) carbon nano-fiber is generated in substrate surface by chemical gaseous phase depositing process;
2) carbon nano-fiber is used into hydrofluoric acid corrosion treatment;
3) N doping is carried out to the carbon nano-fiber after corrosion treatment, obtains final product the nitrogen-doped carbon material containing pure pyridine nitrogen.
2. it is according to claim 1 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:The process for generating carbon nano-fiber in substrate by chemical gaseous phase depositing process is:
A) substrate surface is roughened and is pre-processed;
B) in the substrate surface load transitions race slaine;
C) substrate that area load has transition metal salt is placed in CVD deposition stove, successively under protective atmosphere, in 300~600
DEG C heat treatment;Under hydrogen atmosphere, in 300~600 DEG C of heat treatments;Under carbonaceous sources atmosphere, it is heat-treated in 500~900 DEG C,
Carbon nano-fiber is generated in substrate surface.
3. it is according to claim 2 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:
Described substrate is carbon material, ceramic material or metal material;
Described magnesium-yttrium-transition metal salt includes at least one of nickel, iron, slaine of chromium;
Described carbonaceous sources atmosphere is the atmosphere comprising at least one of methane, propylene, acetylene, ethene, propine.
4. it is according to claim 2 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:Described substrate surface is roughened preprocessing process:Impregnation process is carried out to substrate with strong acid or highly basic.
5. it is according to claim 2 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:The substrate that area load has transition metal salt is placed in CVD deposition stove, successively in inert atmosphere and/or nitrogen
Under atmosphere, 0.5~5h is heat-treated in 300~600 DEG C;Under hydrogen atmosphere, 0.5~5h is heat-treated in 300~600 DEG C;
Under carbonaceous sources atmosphere, 0.1~5h is heat-treated in 500~900 DEG C.
6. it is according to claim 1 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:It is 0.5~5h that the carbon nano-fiber uses the time of hydrofluoric acid corrosion treatment.
7. according to claim 1 or 6 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material side
Method, it is characterised in that:Described hydrofluoric acid concentration is 10~33mol L-1。
8. it is according to claim 1 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:It is to the process that the carbon nano-fiber after corrosion treatment carries out N doping:To the Nano carbon fibers after corrosion treatment
Dimension is placed in atmosphere containing nitrogen source, in 400~800 DEG C of heat treatments, obtains final product the nitrogen-doped carbon material containing pure pyridine nitrogen.
9. it is according to claim 8 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:Described nitrogen source includes at least one of ammonia, polypyridine, pyridine, melamine, polypyrrole, polypyrrole.
10. it is according to claim 8 based on chemical vapor deposition prepare containing pure pyridine nitrogen nitrogen-doped carbon material method,
It is characterized in that:Heat treatment time is 0.1~10h.
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CN113422082A (en) * | 2021-07-06 | 2021-09-21 | 中国科学技术大学 | Nitrogen-doped carbon five-membered ring structure-containing graphene-like carbon material electrocatalyst and preparation method and application thereof |
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