CN107572503A - A kind of N doping multi-walled carbon nanotube and its preparation method and application - Google Patents
A kind of N doping multi-walled carbon nanotube and its preparation method and application Download PDFInfo
- Publication number
- CN107572503A CN107572503A CN201710883525.8A CN201710883525A CN107572503A CN 107572503 A CN107572503 A CN 107572503A CN 201710883525 A CN201710883525 A CN 201710883525A CN 107572503 A CN107572503 A CN 107572503A
- Authority
- CN
- China
- Prior art keywords
- doping
- carbon nanotube
- walled carbon
- catalyst
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to field of material synthesis technology, and in particular to a kind of N doping multi-walled carbon nanotube and its preparation method and application.The preparation method comprises the following steps：1) NCSiAgMg Al are prepared2O3The mixed solution of catalyst and organic acid；2) the NCSiAgMg Al obtained to step 1)2O3The mixed solution of catalyst and organic acid adds organic matter, through catalytic reaction, obtains the reactant mixture of N doping carbon nanotubes；3) reactant mixture for the N doping carbon nanotubes that step 2) obtains is first passed through into HCl treatment, then separates, purifies and vacuum and heating drying, obtain N doping multi-walled carbon nanotube.Technical scheme provided by the present invention realizes room temperature liquid phase method and prepares N doping multi-walled carbon nanotube, and the N doping multi-walled carbon nanotube of preparation can be used as the association area such as lithium ion battery anode active material or cathode additive agent, catalyst, new material.
Description
Technical field
The invention belongs to field of material synthesis technology, and in particular to a kind of N doping multi-walled carbon nanotube and preparation method thereof
And application.
Background technology
CNT is generally divided into single-walled carbon nanotube and multi-walled carbon nanotube, is that there are one kind a diameter of several nanometers to arrive
The new carbon of the tubular structure of tens nanometers.CNT has high conductivity, high intensity, low-density, high-ratio surface
The advantages that product, higher chemical stability, have extensively in fields such as energy storage, composite, electronic device, catalyst, new materials
General application.
The more mature technology of synthesizing carbon nanotubes synthesis at present mainly has so-called " chemical vapour deposition technique ", " laser steams
Hair method ", " Laser vaporization ", " flame synthesis ", " catalystic pyrolysis ", " arc discharge method ", " electrochemical synthesis " etc..
It is well known that the synthesis of CNT, in addition to so-called method, principle are different, one of most crucial factor is exactly catalyst,
Same principle and catalyst is different, then efficiency, the characteristic of the CNT synthesized differ widely, and catalyst is synthesis carbon nanometer
One of key factor of pipe.The catalyst of synthesizing carbon nanotubes is generally all carried noble metal, rare metal or metal oxidation
Silica, the binary metal ternary metal oxide catalytic composite material of thing, system are various.Common synthesizing carbon nanotubes
Catalyst has NiO-SiO2System, MnO-SiO2System, Fe-Mo-Al2O3、Co-Mo-Al2O3System, Ni-Co- ferrocene, two cyclopentadienyls
Iron-dimethyl sulfoxide, ferrocene catalyst, W-Fe-MgO, W-Co-MgO, Mo-Fe-MgO, Mo-Co-MgO, CeO2-Ni-MgO、、
Binary metal oxide system such as Ni0.5Mg1.5O, MgO-Fe bases, AByOz (wherein A=W, B=V, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Rh, Ru, Pd, Pt, Au, Ag, Re, Os, Ir), Cu-Cr-O, Ho-Ni and Gd-Ni2Alloy, Er-Ni, Y-Ni catalyst
Deng.The technology synthesis that the synthesis of these catalyst is typically combined using Solid phase synthesis or liquid-solid synthesis, with respect to skill
Art difficulty is larger.Up to the present, suitable for synthesizing carbon nanotubes synthesis, simple non-metallic catalyst or relatively simple
The document and patent of invention of the liquid phase synthesis techniques of low cost are still rare or be disclosed, under lower temperature conditions or room temperature bar
Under part, the pertinent literature or patent of invention of synthesizing carbon nanotubes are also rare." it is less than carbon under room temperature condition such as document report
The synthesis (Synthesis of carbon nanotubes below room temperature) of nanotube " synthetic technology is
Electrochemically synthesizing carbon nanotubes under the conditions of 230~236K；In addition, patent document discloses a kind of " hydro-thermal legal system
The method of standby CNT or rod ", its disclosed technology is the hydro-thermal under the conditions of 100~240 DEG C in sulfuric acid or phosphoric acid solution
CNT or rod are prepared, and difficulty or ease realize efficient, large-scale production.
The technology of comprehensive existing synthesizing carbon nanotubes has the defects of notable, and first, equipment requirement is high, either chemical gas
Phase sedimentation, Laser synthesizing technology or electric arc synthetic technology, it is all high to the equipment requirement of synthesizing carbon nanotubes, and condition
Control is strict；Second, technical parameter control is strict, as chemical vapour deposition technique strictly controls vacuum, the reaction of reaction system
Temperature, atmosphere oxygen content etc.；3rd, reaction time length, high energy consumption, production cost are high；Such as hydro-thermal method high energy consumption, reaction time
It is long；4th, synthesizing carbon nanotubes poor selectivity, the more walls of single wall or or nanometer rods etc., nanotube caliber or length etc. be unsuitable for
Control.As hydro-thermal method synthesizes possible synthesizing carbon nanotubes and nanorod hybrid；5th, due to being lacked by energy consumption, technical conditions
Sunken limitation, prior art are all relatively difficult to efficient, large-scale production, do not meet the production requirement of energy-conserving and environment-protective.
The content of the invention
To solve the deficiencies in the prior art, the invention provides a kind of N doping multi-walled carbon nanotube and preparation method thereof and
Using.The present invention is to nitrogenize graphite dopping Nano-meter SiO_22Coat Ag-Mg doping Al2O3Nano material (NCSiAgMg-Al2O3Material)
For catalyst, room temperature liquid phase method prepares N doping multi-walled carbon nanotube, the N doping multi-walled carbon nanotube of preparation can be used as lithium from
Sub- GND active material or cathode additive agent, it can also be used for the association areas such as other catalyst, device new material.
Technical scheme provided by the present invention is as follows：
A kind of preparation method of N doping multi-walled carbon nanotube, comprises the following steps：
1) NCSiAgMg-Al is prepared2O3The mixed solution of catalyst and organic acid；
2) NCSiAgMg-Al obtained to step 1)2O3The mixed solution of catalyst and organic acid adds organic matter, through urging
Change reaction, obtain the reactant mixture of N doping carbon nanotubes；
3) reactant mixture for the N doping carbon nanotubes that step 2) obtains is first passed through into HCl treatment, then separates, be pure
Change and vacuum and heating drying, obtain N doping multi-walled carbon nanotube；
Wherein：
Any one of described organic acid in acetic acid, propionic acid, n-butyric acie, positive valeric acid or n-caproic acid；
Described organic matter is in soluble chitosan, ethylenediamine, 1,3- propane diamine, 1,4- butanediamine or melamine
Any one or any two kinds etc. mass mixing thing, organic matter selection is specific, i.e., has as nitrogen source while be used as carbon source；
Described NCSiAgMg-Al2O3Catalyst includes Ag-Mg doping Al2O3The kernel of nano material and it is coated on institute
State the nitridation graphite dopping Nano-meter SiO_2 of core surface2Clad, in the kernel, according to atomic ratio measuring, Ag:Mg:Al is
3.5~15:1~20:100；In the clad, according to atomic ratio measuring, the atomic ratio of nitrogen carbon and silicon is 1.3~4.6:13~
60:100；In the kernel and the clad, according to atomic ratio measuring, Al:Si is about 4.3~15:100.
The preparation method for the N doping multi-walled carbon nanotube that above-mentioned technical proposal is provided can be realized under normal temperature condition
The liquid phase synthesis of N doping multi-wall carbon nano-tube.
In above-mentioned technical proposal, step 3) uses HCl treatment, and similar water is reached in the case of on the one hand can not heating
The effect of thermal response, on the other hand it is beneficial to improve treatment effect so that nitrogen-doped carbon nanometer pipe and catalyst are easily layered, divided
From, and follow-up water washing effect is good.And if directly washed, layering and water washing effect are bad.
Specifically, NCSiAgMg-Al2O3Catalyst can be prepared by the following method to obtain：
1) aluminium salt for being under agitation, 0.5~2.5mol/L to Al ion concentrations, concentration are 0.05~0.15mol/
L silver nitrate solution and magnesium ion concentration be 0.015~0.35mol/L magnesium salts mixed solution in, be added dropwise concentration be 0.1~
2.5mol/L aqueous slkali, the pH value for controlling reaction system are 8.5~11.5, react 10~30 minutes, obtain grey or greyish black
Color Ag-Mg adulterates aluminum hydroxide sol, is dried 3~9 hours under the conditions of 85~105 DEG C, grinding, eluate is washed to distillation
PH=be 6.8~7.2, dry, obtain canescence or grey Ag-Mg doping gel aluminum hydroxide, 350~650 DEG C be calcined 4~
12 hours, that is, obtain canescence or grey Ag-Mg doping Al2O3Nanometer powder；
2) Ag-Mg for obtaining 30~150g step A adulterates Al2O3Nanometer powder is with containing quality equivalent to step 1)
Obtained Ag-Mg doping Al2O3The solution of organic compound of the quality 1~5% of nanometer powder and containing quality equivalent to step 1)
Ag-Mg doping Al2O3The silicate solutions mixing of nanometer powder quality 5~18%, stirring, into mixture, addition concentration is
0.1~1.0mol/L acid solutions are 3.5~5.5 to pH, obtain the Ag-Mg doping Al of the miserable miscellaneous silica sol parcel of organic matter2O3
Nanometer powder, dried 3~9 hours under the conditions of 85~105 DEG C, that is, obtain the Ag-Mg of the miserable miscellaneous silicic acid gel parcel of organic matter
Adulterate Al2O3Nanometer powder, it is 6.8~7.2 to be washed with distilled water to eluate pH=, is dried, 350~650 DEG C under nitrogen atmosphere
Roasting 4~12 hours, that is, obtain nitrogenizing graphite dopping Nano-meter SiO_22Coat Ag-Mg doping Al2O3Nano material.
Preferably, the preparation method of multi-walled carbon nanotube, comprises the following steps：
1) at ambient temperature, to 100~500mL, mass concentration be 25~65% organic acid soln in add 5~
20gNCSiAgMg-Al2O3Catalyst, stir 10~50 minutes, obtain the mixed solution of catalyst and organic acid；
2) 1~50g organic compound solid powders are added to catalyst and organic acid mixed solution obtained by step 1)
In, stirring, reaction 15~55 minutes, obtain the reactant mixture of N doping carbon nanotubes；
3) it is 5~30% hydrochloric acid solutions that the reactant mixture for obtaining step 2), which is added to 500~1000mL mass concentrations,
In, stir 10~50 minutes, stand 10~50 minutes, upper suspension is filtrated to get atrament, obtained by filtering
Atrament is washed with deionized to without chlorion and detected, and 45~65 DEG C are dried in vacuo 30~90 minutes, that is, obtain N doping
Multi-walled carbon nanotube.
Present invention also offers the N doping multi-walled carbon nanotube being prepared according to the above method.
N doping multi-walled carbon nanotube provided by the present invention can be used as lithium ion battery anode active material or lithium ion
GND additive.
Specifically, the Diameter distribution scope of multi-walled carbon nanotube is 25~80nm；Form the single wall carbon of multi-walled carbon nanotube
Nanotube pipe range is 0.1~2.0 μm.
Present invention also offers the application of N doping multi-walled carbon nanotube provided by the present invention, born as lithium ion battery
Pole active material or negative electrode of lithium ion battery additive
The present invention compared with prior art, has the following advantages that and beneficial effect：
1st, the N doping multi-walled carbon nanotube Diameter distribution that synthesizes of the present invention is more uniform, and its Diameter distribution scope is about 25~
(description of the invention accompanying drawing 1, accompanying drawing 2 are referred between 80nm)；
2nd, the N doping multi-wall carbon nano-tube length of tube length that the present invention synthesizes, and be easier to control, N doping multi-wall carbon nano-tube
Pipe pipe range (refers to description of the invention accompanying drawing 3, accompanying drawing 4) between 0.1~2.0 μm；
3rd, the nitrogen of N doping multi-walled carbon nanotube (NMWCNTs) material provided by the present invention and carbon atomic ratio 1.9~
6.1:Between 100, nitrogen percent content is about 1.9~5.7%, and N doping amount is easier to control；
4th, the preparation method of N doping multi-wall carbon nano-tube tube material provided by the present invention, can close quickly, with high selectivity
It is high into N doping multi-walled carbon nanotube (NMWCNTs), combined coefficient；
5th, the Fast back-projection algorithm technical step of N doping multi-wall carbon nano-tube tube material provided by the invention is more succinct, easy,
Energy consumption is low, good, the green non-pollution, it is easy to accomplish large-scale industrial production of selectivity；
6th, N doping multi-walled carbon nanotube negative material prepared by the present invention, can be widely used in chemical catalyst, electricity
The fields such as chemical catalyst, energy storage material, organic synthesis, fine product chemical industry additive, there is good economic benefit and society
Benefit.
Brief description of the drawings
Fig. 1 is the TEM photos (× 85,000 times) for the N doping multi-walled carbon nanotube that the embodiment of the present invention 1 is provided.
Fig. 2 is the TEM photos (× 85,000 times) for the N doping multi-walled carbon nanotube that the embodiment of the present invention 3 is provided.
Fig. 3 is the TEM photos (× 85,000 times) for the N doping multi-walled carbon nanotube that the embodiment of the present invention 4 is provided.
Fig. 4 is the TEM photos (× 85,000 times) for the N doping multi-walled carbon nanotube that the embodiment of the present invention 6 is provided.
Embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
Limit the scope of the present invention.
NCSiAgMg-Al is prepared in following methods2O3Catalyst：
Step 1, under agitation, the silver nitrate that the aluminium chloride and concentration for being 1.0mol/L to concentration are 0.15mol/L
In solution, 0.2mol/L magnesium chloride mixture solutions, the sodium bicarbonate solution that concentration is 1.0mol/L is added dropwise, controls reaction system
PH value is 10.5, is reacted 15 minutes, obtains grey or grey black Ag-Mg doping aluminum hydroxide sols, is dried under the conditions of 105 DEG C
3 hours, grinding, it was about 7.2 to be washed to eluate pH with distillation, was dried, and obtained canescence or grey Ag-Mg doping aluminium hydroxides
Gel, it is calcined 8 hours at 550 DEG C, that is, obtains canescence or grey Ag-Mg doping Al2O3Nanometer powder；
Step 2, the Ag-Mg for obtaining 100g step 2 adulterate Al2O3Nanometer powder containing quality equivalent to Ag-Mg with mixing
Miscellaneous Al2O3The 1,3- propane diamine solution of nanometer powder quality 2% and containing quality equivalent to Ag-Mg adulterate Al2O3Nanometer powder matter
The sodium silicate solution mixing of amount 10%, stirring, it is 0.5mol/L hydrochloric acid solutions to add concentration into mixture, is about 4.5 to pH,
Obtain the Ag-Mg doping Al of the parcel of silica sol containing organic matter2O3Nanopowder mixtures, dried 6 hours under the conditions of 105 DEG C,
The Ag-Mg doping Al of the silicic acid gel parcel of the propane diamine contained2O3Nanometer powder, it is washed with distilled water to eluate
PH is about 7.2, is dried, and lower 450 DEG C of nitrogen atmosphere is calcined 8 hours, that is, obtains NCSiAgMg-Al2O3Catalyst.
Embodiment 1:
A kind of fast synthesis method of N doping multi-walled carbon nanotube, it comprises the following steps：
A, at ambient temperature, 3g catalyst, stirring 10 are added into 100mL, the n-caproic acid acid solution that concentration is 25%
Minute, obtain catalyst and caproic acid mixed solution；
B, in the catalyst and caproic acid mixed solution that 1g Chitosan powders are added to obtained by step A, stirring, 15 points of reaction
Clock, obtain the reactant mixture of the multi-walled carbon nanotube containing N doping；
C, the reactant mixture for obtaining step B is added to 500mL concentration in 5% hydrochloric acid solution, to stir 10 minutes, quiet
Put 10 minutes, upper suspension be filtrated to get atrament, will filter obtained by atrament be washed with deionized to
Detected without chlorion, 45 DEG C are dried in vacuo 90 minutes, that is, obtain a kind of N doping multi-walled carbon nanotube；
The features such as the pattern of synthesizing carbon nanotubes, caliber are analyzed with transmission electron microscope (TEM), EDS determines nitrogen carbon atom
Than the caliber scope of resultant multi-wall CNT is about 25~80nm, and pipe range is about 0.2~2.0 μm (referring to accompanying drawing 1)；Nitrogen carbon
Atomic ratio is about 1.9:100, nitrogen percent content is about 1.9%.
Embodiment 2:
A kind of fast synthesis method of N doping multi-wall carbon nano-tube tube material, it comprises the following steps：
A, at ambient temperature, 8g catalyst, stirring 20 are added into 200mL, the positive valeric acid acid solution that concentration is 35%
Minute, obtain catalyst and valeric acid mixed solution；
B, in the catalyst and valeric acid mixed solution that 8g ethylenediamine solids are added to obtained by step A, stirring, 25 points of reaction
Clock, obtain the reactant mixture of carbon nanotubes；
C, the reactant mixture for obtaining step B is added to 600mL concentration in 12% hydrochloric acid solution, to stir 20 minutes,
20 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized
Detected to without chlorion, 55 DEG C are dried in vacuo 60 minutes, that is, obtain a kind of N doping multi-walled carbon nanotube；
The features such as the pattern of synthesizing carbon nanotubes, caliber are analyzed with transmission electron microscope (TEM), EDS determines nitrogen carbon atom
Than the caliber scope of resultant multi-wall CNT is about 25~80nm, and pipe range is about 0.2~2.0 μm (referring to accompanying drawing 2)；Nitrogen carbon
Atomic ratio is about 2.3:100, nitrogen percent content is about 2.2%.
Embodiment 3:
A kind of fast synthesis method of N doping multi-wall carbon nano-tube tube material, it comprises the following steps：
A, at ambient temperature, 12g catalyst is added into 300mL, the n-butyric acie solution that concentration is 45%, stirs 30 points
Clock, obtain catalyst and butyric acid mixed solution；
B, in the catalyst and organic acid mixed solution that 15g organic matters 1,3- propane diamine powder are added to obtained by step A,
Stirring, reaction 35 minutes, obtain the reactant mixture of the multi-walled carbon nanotube containing N doping；
C, the reactant mixture for obtaining step B is added to 700mL concentration in 20% hydrochloric acid solution, to stir 30 minutes,
30 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized
Detected to without chlorion, 65 DEG C are dried in vacuo 30 minutes, that is, obtain a kind of N doping multi-walled carbon nanotube；
The features such as the pattern of synthesizing carbon nanotubes, caliber are analyzed with transmission electron microscope (TEM), EDS determines nitrogen/carbon atom
Than the caliber scope of resultant multi-wall CNT is about 25~80nm, and pipe range is about 0.2~2.0 μm (referring to accompanying drawing 2)；Nitrogen/carbon
Atomic ratio is about 3.5:100, nitrogen percent content is about 3.4%.
Embodiment 4:
A kind of fast synthesis method of N doping multi-wall carbon nano-tube tube material, it comprises the following steps：
A, at ambient temperature, 16g catalyst is added into 400mL, the n Propanoic acid solution that concentration is 55%, stirs 40 points
Clock, obtain catalyst and propionic acid mixed solution；
B, in the catalyst and propionic acid mixed solution that 35g ethylenediamine solids are added to obtained by step A, stirring, reaction 55
Minute, obtain the reactant mixture of the multi-walled carbon nanotube containing N doping；
C, the reactant mixture for obtaining step B is added to 1000mL concentration in 30% hydrochloric acid solution, to stir 30 minutes,
30 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized
Detected to without chlorion, 65 DEG C are dried in vacuo 60 minutes, that is, obtain a kind of N doping multi-walled carbon nanotube；
The features such as the pattern of synthesizing carbon nanotubes, caliber are analyzed with transmission electron microscope (TEM), EDS determines nitrogen carbon atom
Than the caliber scope of gained N doping multi-walled carbon nanotube is about 25~80nm, and pipe range is about 0.2~2.0 μm and (refers to accompanying drawing
3)；Nitrogen carbon atomic ratio is about 4.3:100, nitrogen percent content is about 4.1%.
Embodiment 5:
A kind of fast preparation method of N doping multi-wall carbon nano-tube tube material, it comprises the following steps：
A, at ambient temperature, 20g catalyst is added into 500mL, the acetic acid solution that concentration is 65%, stirs 50 points
Clock, obtain catalyst and acetic acid mixed solution；
B, the ethylenediamine of the mass mixings such as 50g and 1,3- propane diamine powder are added to the catalyst obtained by step A and had
In machine acid mixed solution, stirring, reaction 45 minutes, the reactant mixture of the multi-walled carbon nanotube containing N doping is obtained；
C, the reactant mixture for obtaining step B is added to 1000mL concentration in 5% hydrochloric acid solution, to stir 30 minutes,
30 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized
Detected to without chlorion, 45 DEG C are dried in vacuo 90 minutes, that is, obtain a kind of N doping multi-walled carbon nanotube；
The features such as the pattern of synthesizing carbon nanotubes, caliber are analyzed with transmission electron microscope (TEM), EDS determines nitrogen carbon atom
Than the caliber scope of gained N doping multi-walled carbon nanotube is about 25~80nm, and pipe range is about 0.2~2.0 μm；Nitrogen carbon atomic ratio
About 5.1:100, nitrogen percent content is about 4.8%.
Embodiment 6:
A kind of fast synthesis method of N doping multi-wall carbon nano-tube tube material, it comprises the following steps：
A, at ambient temperature, 5g catalyst is added into 300mL, the acetic acid solution that concentration is 45%, stirred 20 minutes,
Obtain catalyst and acetic acid mixed solution；
B, the ethylenediamine of the mass mixings such as 1g and melamine powder are added to catalyst obtained by step A and acetic acid mixes
Close in solution, stirring, reaction 35 minutes, obtain the reactant mixture of more CNTs containing N doping；
C, the reactant mixture for obtaining step B is added to 800mL concentration in 12% hydrochloric acid solution, to stir 40 minutes,
40 minutes are stood, upper suspension is filtrated to get atrament, the atrament obtained by filtering is washed with deionized
Detected to without chlorion, 65 DEG C are dried in vacuo 30 minutes, that is, obtain a kind of N doping multi-walled carbon nanotube；
The features such as the pattern of synthesizing carbon nanotubes, caliber are analyzed with transmission electron microscope (TEM), EDS determines nitrogen/carbon atom
Than the caliber scope of resultant multi-wall CNT is about 25~80nm, and pipe range is about 0.2~2.0 μm (referring to accompanying drawing 4)；Nitrogen/carbon
Atomic ratio is about 6.1:100, nitrogen percent content is about 5.7%.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (8)
1. a kind of preparation method of N doping multi-walled carbon nanotube, it is characterised in that comprise the following steps：
1) NCSiAgMg-Al is prepared2O3The mixed solution of catalyst and organic acid；
2) NCSiAgMg-Al obtained to step 1)2O3The mixed solution of catalyst and organic acid adds organic matter, anti-through being catalyzed
Should, obtain the reactant mixture of N doping carbon nanotubes；
3) reactant mixture for the N doping carbon nanotubes that step 2) obtains is first passed through into HCl treatment, then separate, purify and
Vacuum and heating drying, obtain N doping multi-walled carbon nanotube；
Wherein：
Any one of described organic acid in acetic acid, propionic acid, n-butyric acie, positive valeric acid or n-caproic acid；
Described organic matter appointing in soluble chitosan, ethylenediamine, 1,3- propane diamine, 1,4- butanediamine or melamine
Anticipate it is a kind of or any two kinds etc. mass mixing thing；
Described NCSiAgMg-Al2O3Catalyst includes Ag-Mg doping Al2O3The kernel of nano material and be coated on it is described in
The nitridation graphite dopping Nano-meter SiO_2 on core surface2Clad, in the kernel, according to atomic ratio measuring, Ag:Mg:Al be 3.5~
15:1~20:100；In the clad, according to atomic ratio measuring, N：C：Si is 1.3~4.6:13~60：100；The kernel with
In the clad, according to atomic ratio measuring, Al:Si is about 4.3~15:100.
2. the preparation method of multi-walled carbon nanotube according to claim 1, it is characterised in that：In step 1), NCSiAgMg-
Al2O3The mass ratio of catalyst and organic acid is 25~325：5~20；10~50 minutes reaction time.
3. the preparation method of multi-walled carbon nanotube according to claim 1, it is characterised in that：In step 2), organic matter with
The NCSiAgMg-Al added in step 1)2O3The mass ratio of catalyst is 1~50：5~20；Reaction time is 15~55 minutes.
4. the preparation method of multi-walled carbon nanotube according to claim 1, it is characterised in that：Acid treatment is hydrochloric acid with acid,
Mass concentration is 5~30%；Vacuum drying temperature is 45~65 DEG C, and the time is 30~90 minutes.
5. the preparation method of N doping multi-walled carbon nanotube according to any one of claims 1 to 4, it is characterised in that including
Following steps：
1) at ambient temperature, to 100~500mL, mass concentration be 25~65% organic acid soln in add 5~
20gNCSiAgMg-Al2O3Catalyst, stir 10~50 minutes, obtain the mixed solution of catalyst and organic acid；
2) in the catalyst and organic acid mixed solution that 1~50g organic compound solid powders are added to obtained by step 1), stir
Mix, react 15~55 minutes, obtain the reactant mixture of N doping carbon nanotubes；
3) reactant mixture for obtaining step 2) is added to 500~1000mL mass concentrations in 5~30% hydrochloric acid solutions, to stir
Mix 10~50 minutes, stand 10~50 minutes, upper suspension is filtrated to get atrament, by the black thing obtained by filtering
Matter is washed with deionized to without chlorion and detected, and 45~65 DEG C are dried in vacuo 30~90 minutes, that is, obtain the more wall carbon of N doping
Nanotube.
A kind of 6. N doping multi-walled carbon nanotube that preparation method according to any one of claims 1 to 5 is prepared.
7. N doping multi-walled carbon nanotube according to claim 6, it is characterised in that：The Diameter distribution of multi-walled carbon nanotube
Scope is 25~80nm；The single-walled carbon nanotube pipe range for forming multi-walled carbon nanotube is 0.1~2.0 μm.
A kind of 8. application of N doping multi-walled carbon nanotube according to claim 6 or 7, it is characterised in that：As lithium from
Sub- GND active material or negative electrode of lithium ion battery additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710883525.8A CN107572503A (en) | 2017-09-26 | 2017-09-26 | A kind of N doping multi-walled carbon nanotube and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710883525.8A CN107572503A (en) | 2017-09-26 | 2017-09-26 | A kind of N doping multi-walled carbon nanotube and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107572503A true CN107572503A (en) | 2018-01-12 |
Family
ID=61038610
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710883525.8A Pending CN107572503A (en) | 2017-09-26 | 2017-09-26 | A kind of N doping multi-walled carbon nanotube and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107572503A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386408A (en) * | 2008-10-17 | 2009-03-18 | 北京大学 | Semi-conductor type single-walled carbon nano tube and preparation method thereof |
| CN101718732A (en) * | 2009-12-09 | 2010-06-02 | 黑龙江大学 | Carbon doped boron-nitrogen nanotube/semiconductor oxide composite and preparation method and application thereof |
| CN102060284A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Method for preparing nitrogen-phosphorus codoped multi-walled carbon nanotube |
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN103381369A (en) * | 2013-07-10 | 2013-11-06 | 清华大学 | Nitrogen doped carbon material loaded catalyst |
| CN103449403A (en) * | 2013-08-26 | 2013-12-18 | 中国科学院上海硅酸盐研究所 | Method for manufacturing nitrogen-doped multi-wall carbon nano tube |
-
2017
- 2017-09-26 CN CN201710883525.8A patent/CN107572503A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386408A (en) * | 2008-10-17 | 2009-03-18 | 北京大学 | Semi-conductor type single-walled carbon nano tube and preparation method thereof |
| CN101718732A (en) * | 2009-12-09 | 2010-06-02 | 黑龙江大学 | Carbon doped boron-nitrogen nanotube/semiconductor oxide composite and preparation method and application thereof |
| CN102060284A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Method for preparing nitrogen-phosphorus codoped multi-walled carbon nanotube |
| CN102826538A (en) * | 2012-09-17 | 2012-12-19 | 辽宁科技大学 | Method for preparing nitrogen-doped carbonaceous material by modifying polymer |
| CN103381369A (en) * | 2013-07-10 | 2013-11-06 | 清华大学 | Nitrogen doped carbon material loaded catalyst |
| CN103449403A (en) * | 2013-08-26 | 2013-12-18 | 中国科学院上海硅酸盐研究所 | Method for manufacturing nitrogen-doped multi-wall carbon nano tube |
Non-Patent Citations (2)
| Title |
|---|
| 沈自才 等: "《航天材料工程学》", 31 August 2016, 国防工业出版社 * |
| 高峰 主编: "《药用高分子材料学》", 31 October 2014 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | N-doped carbon nanotubes supported CoSe2 nanoparticles: A highly efficient and stable catalyst for H2O2 electrosynthesis in acidic media | |
| Liang et al. | A two-dimensional MXene-supported metal–organic framework for highly selective ambient electrocatalytic nitrogen reduction | |
| Wang et al. | Templating synthesis of ZnO hollow nanospheres loaded with Au nanoparticles and their enhanced gas sensing properties | |
| Zhou et al. | Metal-free carbon nanotube–SiC nanowire heterostructures with enhanced photocatalytic H 2 evolution under visible light irradiation | |
| Pan et al. | Nanophotocatalysts via microwave-assisted solution-phase synthesis for efficient photocatalysis | |
| Pang et al. | Design of NiCo2O4 nanoparticles decorated N, S co-doped reduced graphene oxide composites for electrochemical simultaneous detection of trace multiple heavy metal ions and hydrogen evolution reaction | |
| Eder et al. | Carbon–inorganic hybrid materials: the carbon‐nanotube/TiO2 interface | |
| He et al. | Controllable synthesis, characterization, and CO oxidation activity of CeO2 nanostructures with various morphologies | |
| CN102934265A (en) | Active material for secondary lithium battery, manufacturing method thereof, and secondary lithium battery comprising the same | |
| Sun et al. | Coating carbon nanotubes with metal oxides in a supercritical carbon dioxide–ethanol solution | |
| Huang et al. | Well-dispersive Pt nanoparticles grown on 3D nitrogen-and sulfur-codoped graphene nanoribbon architectures: highly active electrocatalysts for methanol oxidation | |
| Li et al. | Programmed synthesis of magnetic mesoporous silica nanotubes with tiny Au nanoparticles: a highly novel catalyst system | |
| CN102161498B (en) | Preparation method of uniformly dispersed nano lanthanum oxide | |
| CN103143717A (en) | Platinoid bimetallic nanometer material and preparation method and application thereof | |
| Wei et al. | Hierarchically tubular nitrogen-doped carbon structures for the oxygen reduction reaction | |
| Liang et al. | Preparation of a shell nanostructure for highly selective photocatalytic oxidation of organic compounds by wrapping on NiO nanorods exposed {110} facets with ultrathin g-C3N4 nanosheets | |
| CN107694580A (en) | A kind of nano combined selenides and preparation method thereof | |
| Seifi et al. | Preparation of copper oxide/oak-based biomass nanocomposite for electrochemical hydrogen storage | |
| Roodbari et al. | Synthesis, characterization and performance of a novel Ni–Co/GO-TiO2 for electrooxidation of methanol and ethanol | |
| Du et al. | Construction of PdO-decorated double-shell ZnSnO 3 hollow microspheres for n-propanol detection at low temperature | |
| CN113336221B (en) | Preparation method of porous graphene dispersion liquid attached with oxygen-containing group | |
| Deng et al. | Synthesis and characterization of highly efficient and stable Pr6O11/Ag3PO4/Pt ternary hybrid structure | |
| CN107601459A (en) | A kind of multi-walled carbon nanotube and its preparation method and application | |
| CN110180523A (en) | A kind of non-metal porous carbon nanocatalyst and preparation method thereof | |
| Mahajan et al. | Synthesis of grape-like carbon nanospheres and their application as photocatalyst and electrocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180112 |
|
| RJ01 | Rejection of invention patent application after publication |