CN108539217A - The preparation method and applications of nitrogen sulphur codope carbon nanotube - Google Patents
The preparation method and applications of nitrogen sulphur codope carbon nanotube Download PDFInfo
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- CN108539217A CN108539217A CN201810354535.7A CN201810354535A CN108539217A CN 108539217 A CN108539217 A CN 108539217A CN 201810354535 A CN201810354535 A CN 201810354535A CN 108539217 A CN108539217 A CN 108539217A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The present invention relates to a kind of using galapectite as the method for template controllable preparation nitrogen sulphur codope carbon nanotube, belongs to battery material science and technology field.Primary raw material is galapectite, thiophene and pyrroles, galapectite/polythiophene composite material is made in galapectite and thiophene by low temperature polymerization reaction, composite material and pyrroles are mixed and made into galapectite/conducting polymer composite material again, galapectite will be finally removed after composite material high-temperature heat treatment again and can be obtained nitrogen sulphur codope carbon nanotube.The present invention also provides a kind of applications of nitrogen sulphur codope carbon nanotube made from above-mentioned preparation method, are applied to fuel cell catalyst Cathodic oxygen reduction.
Description
Technical field
The present invention relates to a kind of using galapectite as the method for template controllable preparation nitrogen sulphur codope carbon nanotube, belongs to battery material
Expect science and technology field.
Background technology
Fuel cell technology is the outstanding person in new energy technology, but because its Cathodic oxygen reduction (ORR) is relatively slower,
A large amount of catalyst are needed to be catalyzed.For many years, platinum (Pt) base catalyst is considered as the only choosing of oxygen reduction catalyst,
But platinum based catalyst is generally of high cost, stability is poor.In recent years, metal-free carbon-supported catalysts are because it has hydrogen reduction work
Property site, cheap and good stability and be deemed likely to substitute Pt base catalyst.
Carbon nanotube having sp as a kind of2The carbon material of hybrid structure has good in terms of mechanics and thermodynamics
Architecture basics, have extremely excellent property in terms of electricity and magnetics, and carbon atom can be with the atomic bondings such as nitrogen phosphate and sulfur
Constitute miscellaneous carbon nano tube derivative.Therefore, carbon nanotube as electrode material in ultracapacitor, fuel cell etc.
Field shows huge development prospect, by the extensive concern of researcher.
For galapectite as a kind of natural minerals, abundance is cheap, and with unique tubular structure and higher
Specific surface area is to prepare the good hard mold plate material of carbon nanotube.Nitrogen-atoms is compared with carbon atom, the electronegativity with bigger,
The atomic and electronic structures that matrix can be changed in the graphite-structure of nitrogen infiltration carbon nanomaterial, change its electric conductivity, form sp2It is miscellaneous
The delocalization conjugated system for changing C, makes electrocatalysis characteristic be obviously improved.Polypyrrole as a kind of common nitrating presoma,
Itself there is good chemical property, while compared with other itrogenous organic substances such as polyaniline, polymerizing condition is more easy to control.
Although sulphur atom is similar to carbon atom electronegativity, its atomic radius is much larger than carbon atom, therefore can be beaten after being doped into sulphur atom
The balanced structure of broken carbon base body is to assign new characteristic, such as promotes catalytic activity.Polythiophene is as a kind of conducting polymer
Material, the existence form of sulphur wherein is single and monomer easily polymerize, and is the ideal presoma for preparing sulfur doping nano material.With angstrom
Lip river stone is the active site that the nitrogen sulphur codope carbon nanotube that template is prepared can not only improve nitrogen sulfur doping, but also is operated
Simplicity atom doped is not influenced by other.
Currently, the preparation method about nitrogen sulphur codope carbon nanomaterial is more and complex, such as Chinese patent CN
106082184A proposes a kind of method preparing nitrogen sulphur codope graphene：Using amino-containing sulfonate as nitrogen source and sulphur
Nitrogen sulphur codope graphene has successfully been prepared in source under the conditions of low-temp reaction.But this method is using inorganic sulfonate as sulphur
Its sulphur existence form of the presoma of doping is complicated, requires strictly, and without the inorganic of high temperature oxidation process experiment condition control
Specific surface area is smaller after sulfonate carbonization is unfavorable for promoting catalytic performance.Chinese patent CN105931855A proposes one kind in sulphur
Only it polymerize to obtain poly- (aniline-thiophene) composite material by single step reaction in acid solution, it is total that further high temperature pyrolysis obtains nitrogen sulphur
The method for adulterating carbon nanomaterial.But this method only by nitrogen source and sulphur source while polymerizeing acquisition to realize by single step reaction
The purpose of composite material selects ammonium persulfate to be reacted in sulfuric acid solution as oxidant.Thiophene is using water as the sulfuric acid of solvent
Solubility is very low in solution, is only capable of addition about 2.5g thiophene raw materials in the embodiment given in 200mL solution, greatly affected
Preparation efficiency.The scheme in patent CN105931855A does not prepare carbon nanomaterial using template simultaneously, obtained nitrogen sulphur
Codope carbon nanomaterial pattern is uncontrollable, can not further promote chemical property.
Invention content
In order to solve, prior art preparation nitrogen sulphur co-doped nano material technology is complicated, condition is harsh, preparation efficiency is low
Deficiency, the present invention provides a kind of preparation methods of simple and practicable nitrogen sulphur codope carbon nanotube, and utilize galapectite itself
Advantage is greatly promoted as the catalytic oxidation-reduction performance for the nitrogen sulphur codope carbon nanotube that template is prepared.
A kind of preparation method of nitrogen sulphur codope carbon nanotube, includes the following steps：
1. acidified galapectite and thiophene are dissolved in organic solvent simultaneously, wherein thiophene is with galapectite mass ratio
0.5~2:1, galapectite is 0.05~0.15 with organic solvent mass ratio:1,20~40min of magnetic agitation, then into system
Oxidant anhydrous ferric trichloride is added, the wherein mass ratio of anhydrous ferric trichloride and thiophene is 3~5:Continue at 1,0~5 DEG C into
Row 6~12h of magnetic agitation, filtering, is washed with detergent absolute ethyl alcohol, and drying obtains galapectite/polythiophene composite material；
2. step 1 gained composite material is mixed with deionized water, composite material and deionized water quality ratio be 0.05~
0.1:Pyrrole monomer, pyrroles and composite material matter are added into the mixed system after ultrasonic disperse by 1,20~40min of ultrasonic disperse
Amount is than being 0.25~1:1,30~60min of magnetic agitation, mixed liquor is transferred in ice bath be added dropwise molar concentration be 0.1~
The liquor ferri trichloridi of 0.5mol/L, reacts 30~60min in ice bath, and products therefrom washing is drying to obtain galapectite/conduction
Polymer composites；
3. the preparation-obtained composite material of step 2 is placed in tube furnace, it is passed through nitrogen, with the heating speed of 5 DEG C/min
Degree is warming up to 500~700 DEG C of progress high-temperature heat treatments, is down to room temperature after keeping 2~4h of reaction, obtained product is soaked with hydrofluoric acid
1~2h is steeped, it is washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
Chloroform, toluene or dimethylbenzene can be selected in the organic solvent.
Absolute ethyl alcohol can be selected in detergent in each step, and drying temperature is 40~60 DEG C.
The present invention also provides a kind of applications of nitrogen sulphur codope carbon nanotube made from above-mentioned preparation method, are applied to combustion
Expect cell catalyst Cathodic oxygen reduction.
The beneficial effects of the invention are as follows：
1, the present invention makees template using galapectite and provides good tubular morphology and larger ratio table for carbon nanomaterial
Area.Using the oxidation process of conducting polymer, can nitrogenous sulphur simply be synthesized by in-situ polymerization on galapectite surface
Polymer precursor, it is at low cost.The preparation-obtained nitrogen sulphur codope carbon nanotube that is further carbonized has excellent electrochemistry
Performance, application prospect are extensive.
2, the present invention selects ferric trichloride as polymer optimization, solves the common polymer oxidation such as ammonium persulfate
Agent is water solubility, the problem of being insoluble in organic solvent.Thiophene polymeric reacts in anhydrous conditions, will entirely prepare polymerization
The process of object presoma in two steps, first by ferric trichloride does oxidant polymeric thiophene in organic solvent, then pyrrole polymerization, can be with
Greatly improve preparation efficiency.
3, the present invention substitutes the nitrogen source of traditional N doping using pyrroles.The chemical property of product is improved, is made simultaneously
Polymerizing condition is more easy to control.
4, the present invention substitutes the sulphur source of traditional sulfur doping using thiophene, reduces the rigors for mixing sulphur technology to temperature,
Sulphur atom remains to be stabilized under the conditions of high temperature pyrolysis.
5, the present invention provides a kind of application directions of nitrogen sulphur codope carbon nanotube：Catalytic oxidation-reduction reacts.Utilize material
The abundant specific surface area of material, excellent tubular morphology provides abundant favorable activity site for hydrogen reduction and high nitrogen sulfur doping contains
Amount.
Description of the drawings
Fig. 1 is the transmission electron microscope image of the nitrogen sulphur codope carbon nanotube obtained by embodiment 1.
Fig. 2 is that gained nitrogen sulphur codope carbon nanomaterial is prepared into after electrode to test and obtains in embodiment 1 and comparative example 1
Linear sweep voltammetry curve graph.
Specific implementation mode
The present invention is further elaborated on reference to embodiment.
The preparation process of the nitrogen sulphur codope carbon nanotube of the present invention is specific as follows：
(1) modified galapectite：Pure galapectite is scattered in the hydrochloric acid of 0.1~0.5mol/L, continued mechanical stirring 8~for 24 hours,
Obtain acidified modified galapectite.
(2) galapectite/polythiophene composite material is synthesized：Modified galapectite and thiophene are dissolved in organic solvent (thiophene simultaneously
The mass ratio of thiophene monomer and galapectite is 0.5~2:1；The mass ratio 0.05~0.15 of galapectite and organic solvent:1) magnetic, is kept
Power stirs 20~40min, and the oxidant anhydrous ferric trichloride (mass ratio of anhydrous ferric trichloride and thiophene is then added into system
It is 3~5:1), continue to be stirred to react 6~12h at 0~5 DEG C, filter, absolute ethyl alcohol washing, drying obtains galapectite/thiophene
Composite material；
(3) galapectite/polythiophene/Pt/Polypyrrole composite material is synthesized：Composite material appropriate amount of deionized water in (2) is mixed
(composite material is 0.05~0.1 with deionized water quality ratio:1), 20~40min of ultrasonic disperse, to the mixing after ultrasonic disperse
Pyrrole monomer solution is added in system, and (pyrrole monomer is 0.25~1 with galapectite mass ratio:1), 30~60min of magnetic agitation is obtained
To mixed liquor.Mixed liquor is transferred in ice bath, magnetic agitation is kept, 0.1~0.5mol/L oxygen is added dropwise into mixed liquor
Agent liquor ferri trichloridi continues to react 30~60min in ice bath.Product washing is dry to obtain galapectite/polythiophene/poly-
Pyrroles's composite material.
(4) nitrogen sulphur codope carbon nanotube is prepared：Galapectite/polythiophene/Pt/Polypyrrole composite material that step (3) is obtained
It is placed in tube furnace, is warming up to 500~700 DEG C in a nitrogen atmosphere, room temperature is down to after keeping 2~4h reactions, obtain product use
Hydrofluoric acid dips and persistent oscillation 1~2h, it is washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
The nitrogen sulphur codope carbon nanotube that the present invention is prepared carries out hydrogen reduction performance test according to the following steps：
(1) 5mg nitrogen sulphur codope carbon nanotube ultrasonic disperses is molten in the mixing of 0.95mL isopropanols and 0.05mL naphthols
In liquid, weighs 6 microlitres of mixed liquors and be added drop-wise to glassy carbon electrode surface, the film of uniform fold is formed, after being dried in ethyl alcohol atmosphere
It is to be measured.
(2) at room temperature, electrode obtained is tested on electrochemical workstation.Electrolyte solution is 0.1mol/L
KOH aqueous solutions, in N2Or O2The cyclic voltammetry curve from 0.2~0.8V (opposite SCE), sweep speed 20mV/ are recorded under atmosphere
s；Using rotating disk electrode (r.d.e) (RDE) in O2The linear volt-ampere curve under different rotating speeds, sweep speed 5mV/ are recorded under atmosphere
s。
Below again with the preparation method of 1~2 pair of Examples 1 to 5 and comparative example nitrogen sulphur codope carbon nanotube of the invention
It is specifically described.
Embodiment 1
(1) modified galapectite：Pure galapectite is scattered in the hydrochloric acid of 0.2mol/L, continued mechanical stirs 16h, is acidified
Modified galapectite.
(2) galapectite/polythiophene composite material is synthesized：3g is modified galapectite and 0.5g thiophene and is dissolved in 20mL chloroforms simultaneously
In (mass ratio of thiophene monomer and galapectite be 0.5:1；The mass ratio 0.15 of galapectite and organic solvent:1), magnetic force is kept to stir
20min is mixed, 2g oxidants anhydrous ferric trichloride is then added into system, and (mass ratio of anhydrous ferric trichloride and thiophene is 4:
1), continue to be stirred to react 12h at 5 DEG C, filter, absolute ethyl alcohol washing, drying obtains galapectite/polythiophene composite material；
(3) galapectite/polythiophene/Pt/Polypyrrole composite material is synthesized：Composite material 1g in (2) and 20mL deionized waters is mixed
(composite material is 0.05 with deionized water quality ratio for conjunction:1), ultrasonic disperse 30min adds into the mixed system after ultrasonic disperse
Entering 0.5mL pyrrole monomers solution, (pyrrole monomer is 0.5 with galapectite mass ratio:1), magnetic agitation 30min obtains mixed liquor.It will
Mixed liquor is transferred in ice bath, keeps magnetic agitation, 0.1mol/L oxidant liquor ferri trichloridis are added dropwise into mixed liquor,
30min is reacted in continuation in ice bath.Product washing drying obtains galapectite/polythiophene/Pt/Polypyrrole composite material.
(4) nitrogen sulphur codope carbon nanotube is prepared：Galapectite/polythiophene/Pt/Polypyrrole composite material that step (3) is obtained
It is placed in tube furnace, is warming up to 600 DEG C in a nitrogen atmosphere, be down to room temperature after keeping 3h reactions, obtain product and soaked with hydrofluoric acid
Simultaneously persistent oscillation 1h is steeped, it is washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
Fig. 1 is the transmission electron microscope image of the nitrogen sulphur codope carbon nanotube obtained by embodiment 1, from image
It can be clearly seen that the tubular morphology that material obtained by template is done with galapectite.
Embodiment 2
(1) modified galapectite：Pure galapectite is scattered in the hydrochloric acid of 0.1mol/L, continued mechanical stirs 12h, is acidified
Modified galapectite.
(2) galapectite/polythiophene composite material is synthesized：3g is modified galapectite and 3g thiophene to be dissolved in 60mL toluene simultaneously
(mass ratio of thiophene monomer and galapectite is 1:1；The mass ratio 0.05 of galapectite and organic solvent:1) magnetic agitation, is kept
30min, 9g oxidants anhydrous ferric trichloride is then added into system, and (mass ratio of anhydrous ferric trichloride and thiophene is 3:1), 0
Continue to be stirred to react 9h at DEG C, filter, absolute ethyl alcohol washing, drying obtains galapectite/polythiophene composite material；
(3) galapectite/polythiophene/Pt/Polypyrrole composite material is synthesized：By composite material 1g in (2) and 12.5mL deionized waters
(composite material is 0.08 with deionized water quality ratio for mixing:1), ultrasonic disperse 20min, into the mixed system after ultrasonic disperse
0.25mL pyrrole monomers solution is added, and (pyrrole monomer is 0.25 with galapectite mass ratio:1), magnetic agitation 40min is mixed
Liquid.Mixed liquor is transferred in ice bath, magnetic agitation is kept, 0.2mol/L oxidant ferric trichlorides is added dropwise into mixed liquor
40min is reacted in solution, continuation in ice bath.Product washing drying obtains galapectite/polythiophene/Pt/Polypyrrole composite material.
(4) nitrogen sulphur codope carbon nanotube is prepared：Galapectite/polythiophene/Pt/Polypyrrole composite material that step (3) is obtained
It is placed in tube furnace, is warming up to 700 DEG C in a nitrogen atmosphere, be down to room temperature after keeping 2h reactions, obtain product and soaked with hydrofluoric acid
Simultaneously persistent oscillation 1h is steeped, it is washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
The present embodiment is only as the primary trial during preferred suitable preparation condition.Products therefrom nitrogen content and sulfur content
It is relatively low the possible reason is calcination temperature is excessively high.Temperature is excessively high so that foreign atom is lost in calcination process, to lead
Cause nitrogen content and sulfur content relatively low.
Embodiment 3
(1) modified galapectite：Pure galapectite is scattered in the hydrochloric acid of 0.3mol/L, continued mechanical stirs 8h, is acidified
Modified galapectite.
(2) galapectite/polythiophene composite material is synthesized：3g is modified galapectite and 4.5g thiophene and is dissolved in 30mL diformazans simultaneously
(mass ratio of thiophene monomer and galapectite is 1.5 in benzene:1；The mass ratio 0.1 of galapectite and organic solvent:1) magnetic force, is kept
40min is stirred, the 13.5g oxidants anhydrous ferric trichloride (mass ratio of anhydrous ferric trichloride and thiophene is then added into system
It is 3:1), continue to be stirred to react 12h at 5 DEG C, filter, absolute ethyl alcohol washing, drying obtains galapectite/polythiophene composite wood
Material；
(3) galapectite/polythiophene/Pt/Polypyrrole composite material is synthesized：Composite material 1g in (2) and 10mL deionized waters is mixed
(composite material is 0.1 with deionized water quality ratio for conjunction:1), ultrasonic disperse 40min adds into the mixed system after ultrasonic disperse
Entering 1mL pyrrole monomers solution, (pyrrole monomer is 1 with galapectite mass ratio:1), magnetic agitation 50min obtains mixed liquor.It will mixing
Liquid is transferred in ice bath, keeps magnetic agitation, 0.3mol/L oxidant liquor ferri trichloridis are added dropwise into mixed liquor, is continued
50min is reacted in ice bath.Product washing drying obtains galapectite/polythiophene/Pt/Polypyrrole composite material.
(4) nitrogen sulphur codope carbon nanotube is prepared：Galapectite/polythiophene/Pt/Polypyrrole composite material that step (3) is obtained
It is placed in tube furnace, is warming up to 500 DEG C in a nitrogen atmosphere, be down to room temperature after keeping 4h reactions, obtain product and soaked with hydrofluoric acid
Simultaneously persistent oscillation 2h is steeped, it is washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
Embodiment 4
(1) modified galapectite：Pure galapectite is scattered in the hydrochloric acid of 0.4mol/L, continued mechanical is stirred for 24 hours, is acidified
Modified galapectite.
(2) galapectite/polythiophene composite material is synthesized：3g is modified galapectite and 6g thiophene to be dissolved in 20mL chloroforms simultaneously
(mass ratio of thiophene monomer and galapectite is 2:1；The mass ratio 0.15 of galapectite and organic solvent:1) magnetic agitation, is kept
30min, 24g oxidants anhydrous ferric trichloride is then added into system, and (mass ratio of anhydrous ferric trichloride and thiophene is 4:1),
Continue to be stirred to react 6h at 0 DEG C, filter, absolute ethyl alcohol washing, drying obtains galapectite/polythiophene composite material；
(3) galapectite/polythiophene/Pt/Polypyrrole composite material is synthesized：Composite material 1g in (2) and 20mL deionized waters is mixed
(composite material is 0.05 with deionized water quality ratio for conjunction:1), ultrasonic disperse 30min adds into the mixed system after ultrasonic disperse
Entering 0.75mL pyrrole monomers solution, (pyrrole monomer is 0.75 with galapectite mass ratio:1), magnetic agitation 60min obtains mixed liquor.
Mixed liquor is transferred in ice bath, magnetic agitation is kept, it is molten that 0.4mol/L oxidant ferric trichlorides is added dropwise into mixed liquor
60min is reacted in liquid, continuation in ice bath.Product washing drying obtains galapectite/polythiophene/Pt/Polypyrrole composite material.
(4) nitrogen sulphur codope carbon nanotube is prepared：Galapectite/polythiophene/Pt/Polypyrrole composite material that step (3) is obtained
It is placed in tube furnace, is warming up to 700 DEG C in a nitrogen atmosphere, be down to room temperature after keeping 3h reactions, obtain product and soaked with hydrofluoric acid
Simultaneously persistent oscillation 2h is steeped, it is washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
Embodiment 5
(1) modified galapectite：Pure galapectite is scattered in the hydrochloric acid of 0.5mol/L, continued mechanical stirs 20h, is acidified
Modified galapectite.
(2) galapectite/polythiophene composite material is synthesized：3g is modified galapectite and 3g thiophene and is dissolved in 30mL dimethylbenzene simultaneously
In (mass ratio of thiophene monomer and galapectite be 1:1；The mass ratio 0.1 of galapectite and organic solvent:1) magnetic agitation, is kept
20min, 15g oxidants anhydrous ferric trichloride is then added into system, and (mass ratio of anhydrous ferric trichloride and thiophene is 5:1),
Continue to be stirred to react 6h at 3 DEG C, filter, absolute ethyl alcohol washing, drying obtains galapectite/polythiophene composite material；
(3) galapectite/polythiophene/Pt/Polypyrrole composite material is synthesized：Composite material 1g in (2) and 10mL deionized waters is mixed
(composite material is 0.1 with deionized water quality ratio for conjunction:1), ultrasonic disperse 20min adds into the mixed system after ultrasonic disperse
Entering 0.25mL pyrrole monomers solution, (pyrrole monomer is 0.25 with galapectite mass ratio:1), magnetic agitation 50min obtains mixed liquor.
Mixed liquor is transferred in ice bath, magnetic agitation is kept, it is molten that 0.5mol/L oxidant ferric trichlorides is added dropwise into mixed liquor
50min is reacted in liquid, continuation in ice bath.Product washing drying obtains galapectite/polythiophene/Pt/Polypyrrole composite material.
(4) nitrogen sulphur codope carbon nanotube is prepared：Galapectite/polythiophene/Pt/Polypyrrole composite material that step (3) is obtained
It is placed in tube furnace, is warming up to 600 DEG C in a nitrogen atmosphere, be down to room temperature after keeping 2h reactions, obtain product and soaked with hydrofluoric acid
Simultaneously persistent oscillation 1h is steeped, it is washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
Comparative example 1
It is removed galapectite is added in embodiment 1 as the step of template, other process conditions are constant, and specific steps are such as
Under：
(1) polythiophene composite material is synthesized：0.5g thiophene is dissolved in 20mL chloroforms, keeps magnetic agitation 20min, then
2g oxidants anhydrous ferric trichloride is added into system, and (mass ratio of anhydrous ferric trichloride and thiophene is 4:1), continue to stir at 5 DEG C
Reaction 12h, filtering are mixed, absolute ethyl alcohol washs, and drying obtains polythiophene；
(2) polythiophene/Pt/Polypyrrole composite material is synthesized：Polythiophene 1g in (2) is mixed into (composite wood with 20mL deionized waters
Material is 0.05 with deionized water quality ratio:1) 0.5mL pyrroles are added into the mixed system after ultrasonic disperse by, ultrasonic disperse 30min
Monomer solution is coughed up, magnetic agitation 30min obtains mixed liquor.Mixed liquor is transferred in ice bath, magnetic agitation is kept, to mixed liquor
In be added dropwise 0.1mol/L oxidant liquor ferri trichloridis, 30min is reacted in continuation in ice bath.Product washing drying obtains
Polythiophene/Pt/Polypyrrole composite material.
(3) nitrogen sulphur codope carbon nanomaterial is prepared：Polythiophene/Pt/Polypyrrole composite material that step (3) obtains is placed in
In tube furnace, it is warming up to 600 DEG C in a nitrogen atmosphere, is down to room temperature after keeping 3h reactions, the washed nitrogen sulphur that is dried to obtain is co-doped with
Miscellaneous carbon nano material.
Fig. 2 is that gained nitrogen sulphur codope carbon nanomaterial is prepared into after electrode to test and obtains in embodiment 1 and comparative example 1
Linear sweep voltammetry curve graph.The hydrogen reduction performance of 1 resulting materials of embodiment 1 and comparative example is compared, it can be found that real
The tubulose nitrogen sulphur codope carbon nanomaterial that example 1 is prepared with galapectite as template is applied, there is higher take-off potential and pole
It rations the power supply current density, it was demonstrated that there is good catalytic oxidation-reduction performance by nitrogen sulphur codope carbon nanotube prepared by this method.
Comparative example 2
Hydrofluoric acid in embodiment 1 is replaced with sodium hydroxide, to remove galapectite template, other process conditions are constant,
It is as follows：
(1) modified galapectite：Pure galapectite is scattered in the hydrochloric acid of 0.2mol/L, continued mechanical stirs 16h, is acidified
Modified galapectite.
(2) galapectite/polythiophene composite material is synthesized：3g is modified galapectite and 0.5g thiophene and is dissolved in 20mL chloroforms simultaneously
In (mass ratio of thiophene monomer and galapectite be 0.5:1；The mass ratio 0.15 of galapectite and organic solvent:1), magnetic force is kept to stir
20min is mixed, 2g oxidants anhydrous ferric trichloride is then added into system, and (mass ratio of anhydrous ferric trichloride and thiophene is 4:
1), continue to be stirred to react 12h at 5 DEG C, filter, absolute ethyl alcohol washing, drying obtains galapectite/thiophene composite；
(3) galapectite/polythiophene/Pt/Polypyrrole composite material is synthesized：Composite material 1g in (2) and 20mL deionized waters is mixed
(composite material is 0.05 with deionized water quality ratio for conjunction:1), ultrasonic disperse 30min adds into the mixed system after ultrasonic disperse
Entering 0.5mL pyrrole monomers solution, (pyrrole monomer is 0.5 with galapectite mass ratio:1), magnetic agitation 30min obtains mixed liquor.It will
Mixed liquor is transferred in ice bath, keeps magnetic agitation, 0.1mol/L oxidant liquor ferri trichloridis are added dropwise into mixed liquor,
30min is reacted in continuation in ice bath.Product washing drying obtains galapectite/polythiophene/Pt/Polypyrrole composite material.
(4) nitrogen sulphur codope carbon nanotube is prepared：Galapectite/polythiophene/Pt/Polypyrrole composite material that step (3) is obtained
It is placed in tube furnace, is warming up to 600 DEG C in a nitrogen atmosphere, room temperature is down to after keeping 3h reactions, obtain product with a concentration of
The sodium hydroxide solution of 4mol/L impregnates simultaneously persistent oscillation 12h, washed to be dried to obtain nitrogen sulphur codope carbon nanotube.
Elemental composition point is carried out to nitrogen sulphur codope carbon nanotube obtained in above example 1~5 and comparative example 1~2
Analysis obtains the percent data of each essential element content as shown in table 1.The nano material obtained in each embodiment has different journeys
The nitrogen sulfur doping of degree.Wherein, embodiment 1 obtains nitrogen sulphur codope carbon nanotube nitrating, the content highest for mixing sulphur, to being catalyzed oxygen
Reduction reaction has most significant facilitation.
Table 1
Claims (9)
1. a kind of preparation method of nitrogen sulphur codope carbon nanotube, which is characterized in that include the following steps：
Step (1)：Acidified galapectite and thiophene are dissolved in organic solvent simultaneously, carry out 20~40min of magnetic agitation, so
Oxidant is added in backward system, continues 6~12h of magnetic agitation at 0~5 DEG C, filters, is washed with detergent, drying is
Galapectite/polythiophene composite material is made；
Step (2)：Composite material obtained by step (1) is mixed with deionized water, 20~40min of ultrasonic disperse is carried out, to ultrasound
Pyrrole monomer is added in mixed system after dispersion, carries out 30~60min of magnetic agitation, mixed liquor is transferred in ice bath dropwise
Oxidizing agent solution is added, 30~60min is reacted in ice bath, it is multiple that products therefrom washing is drying to obtain galapectite/conducting polymer
Condensation material；
Step (3)：Step (2) preparation-obtained composite material is placed in tube furnace, nitrogen is passed through, heating carries out high warm
Processing, is down to room temperature, products therefrom is post-processed, washed to be dried to obtain nitrogen sulphur codope carbon nanotube after reaction.
2. preparation method as described in claim 1, which is characterized in that the mass ratio of thiophene and galapectite in the step (1)
It is 0.5~2:1, the mass ratio of galapectite and organic solvent is 0.05~0.15:1.
3. preparation method as described in claim 1, which is characterized in that oxidant described in the step (1) is anhydrous trichlorine
The mass ratio of change iron, anhydrous ferric trichloride and thiophene is 3~5:1.
4. preparation method as described in claim 1, which is characterized in that composite material and deionized water in the step (2)
Amount is than being 0.05~0.1:1, pyrroles is 0.25~1 with composite material mass ratio:1.
5. preparation method as described in claim 1, which is characterized in that oxidizing agent solution is ferric trichloride in the step (2)
Solution, molar concentration are 0.1~0.5mol/L.
6. preparation method as described in claim 1, which is characterized in that heating rate is 5 DEG C/min in the step (3), high
It is 500~700 DEG C to warm treatment temperature, and the duration is 2~4h.
7. preparation method as described in claim 1, which is characterized in that post-processing is with hydrofluoric acid dips 1 in the step (3)
~2h.
8. preparation method as described in claim 1, which is characterized in that in the step (1) to (3) drying temperature be 40~
60℃。
9. a kind of application of the nitrogen sulphur codope carbon nanotube prepared such as any one of claim 1~8 the method, feature exist
In：The nitrogen sulphur codope carbon nanotube is used for fuel cell catalyst Cathodic oxygen reduction.
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