CN110277563A - A kind of preparation method of N doping hollow carbon sphere elctro-catalyst - Google Patents
A kind of preparation method of N doping hollow carbon sphere elctro-catalyst Download PDFInfo
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- CN110277563A CN110277563A CN201910496935.6A CN201910496935A CN110277563A CN 110277563 A CN110277563 A CN 110277563A CN 201910496935 A CN201910496935 A CN 201910496935A CN 110277563 A CN110277563 A CN 110277563A
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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
- H01M4/90—Selection of catalytic material
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of methods for preparing N doping hollow carbon sphere elctro-catalyst using trioctylamine, belong to field of inorganic material preparing technology.Preparation method is that first trioctylamine is added in water/ethanol solution; by emulsion dispersion; adding ammonium hydroxide makes system that alkalinity be presented; Dopamine hydrochloride is added; carry out polymerization reaction; it is dried to obtain poly-dopamine hollow sphere by washing, it is subsequent to be calcined in protective atmosphere, obtain N doping hollow carbon sphere material.The material is carbonaceous hollow ball structure, and wall thickness and size are controllable, and nitrogen is evenly distributed.The hollow carbon material of N doping prepared by the present invention can be used as fuel cell as Cathodic oxygen reduction electrocatalysis material, there is good stability and catalytic performance.Preparation method is carbon source using biomass, reacts simple and quick, Product size structure-controllable, has the characteristics that easy industrialization promotion, energy-saving material-saving, green high-efficient, prepared material structure are stablized, the electro-catalysis effect having had in oxygen reduction reaction.
Description
Technical field
The invention belongs to technical field of new energy material preparation, and in particular to a kind of preparation method of N doping hollow carbon sphere material
And application.
Background technique
Fuel cell is a kind of current one of energy transformation technology worthy of expecting, it can turn the chemical energy in chemical substance
It changes electric energy into, there is the advantage that conventional Power Generation Mode is incomparable.But fuel battery negative pole oxygen reduction reaction invertibity is very low,
Exchange current density is small, is often accompanied by higher overpotential.It is fired so being improved using Cathodic oxygen reduction catalyst degradation overpotential
Expect that battery performance is a step very crucial to fuel cell industrialization.
The carbon material of existing document report xenogenesis element doping is that a kind of low cost, the hydrogen reduction of high conversion efficiency are anti-recently
Answer elctro-catalyst.Wherein, the carbon material of N doping possesses high conductivity, therefore has containing a large amount of active site simultaneously
Excellent oxygen reduction reaction catalytic activity, is expected to be widely applied to the fields such as fuel cell.
Hollow carbon material chemical stability height, hollow lumen structure, electric conductivity is good, large specific surface area, specific gravity are small, is being catalyzed
The fields such as agent, catalyst carrier, electrode material, sensing material show application prospect, become a big hot spot of research.Hard template
Method is to prepare the main method of hollow carbon material, but its process flow is relative complex, and the processes such as preparation and removal of template are not
It is only time-consuming, and will cause the waste of material, limit the industrialization large-scale promotion of this method.
Summary of the invention
The present invention is intended to provide a kind of N doping hollow carbon sphere material and preparation method thereof, material application has in a fuel cell
There is good Cathodic oxygen reduction catalytic activity.The method step is simple, low in cost, is suitble to industrialized production.
A kind of preparation method of N doping hollow carbon sphere material, it is characterised in that preparation step is as follows:
(1) template trioctylamine is added in solvent, template is dispersed in reaction system by way of physics concussion
In, and acid-base modifier is added and creates alkaline environment；
(2) Dopamine hydrochloride is added in the emulsion system of above-mentioned (1) preparation, reaction certain time length is sufficiently stirred, obtain poly- more
Bar amine product dispersion liquid；
(3) poly-dopamine hollow sphere is obtained after washing is dry in the poly-dopamine product of above-mentioned (2) preparation；
(4) it calcines to obtain N doping hollow carbon sphere material by certain technique in the poly-dopamine hollow sphere that above-mentioned (3) obtain.
Further, the quality proportioning of raw material of the present invention are as follows:
A, Dopamine hydrochloride: 1~50 part；
B, ammonium hydroxide: 2~50 parts；
C, trioctylamine: 3~100 parts；
D, dehydrated alcohol: 0~1400 part；
E, water: 1000~4000 parts.
Further, the trioctylamine is as the evenly dispersed using ultrasound, vibration, agitating procedure of template, when dispersing any
It is long.
Further, prepare poly-dopamine product dispersion liquid method be: the sequence of mixed raw material be first be added trioctylamine, water and
Dehydrated alcohol adds ammonium hydroxide.
Further, the mode of agitating solution is used in the poly-dopamine product dispersion liquid preparation process；Stirring rate is 500
~2000rpm, synthesis temperature be 1~50 DEG C, generated time be 0.25~for 24 hours.
Further, the cleaning solution used during the washing poly-dopamine product is water or dehydrated alcohol, passes through centrifugation
Mode separate synthetic product, centrifugal rotational speed is 5000~12000rpm, is washed until centrifugate is limpid；Using dry when drying
Dry case desciccate at 20~80 DEG C.
Further, the protective atmosphere that the calcination process uses is nitrogen, argon gas, helium or vacuum；Heating rate when calcining
For 0.05~10 DEG C/min, holding temperature is 600~1800 DEG C, and soaking time is 0.3~3h.
Product of the invention is a kind of hollow carbon material of N doping, and Nitrogen element, hollow structure, carbon ball wall graphitization is presented in inside
Degree is low, grain diameter size, boring structure-controllable, and polymolecularity is presented.
The hollow carbon material of the N doping of above-mentioned preparation, can be used as fuel cell as Cathodic oxygen reduction electrocatalysis material,
There are good stability and catalytic performance.
It is an advantage of the current invention that preparation method is carbon source using biomass, simple and quick, Product size structure-controllable is reacted,
For a kind of easy industrialization promotion, the hollow carbon preparation method of green high-efficient, energy-saving material-saving.
Detailed description of the invention
Fig. 1 schemes for the SEM of N doping hollow carbon sphere material obtained in the embodiment of the present invention 3.
Fig. 2 schemes for the TEM of N doping hollow carbon sphere material obtained in the embodiment of the present invention 3.
Specific embodiment
Below with reference to example, invention is further described in detail.Embodiments of the present invention are not limited thereto.
Embodiment 1:
It weighs 30mL deionized water and 5mL dehydrated alcohol is uniformly mixed and added into 0.2g trioctylamine, 0.05ml ammonium hydroxide is then added.
Mixed solution is put into ultrasonic cleaner, using 100W power ultrasound 20min, taking-up when solution is creamy white suspension
It is spare.It weighs 0.1g Dopamine hydrochloride to be added in the white emulsion prepared, adds magneton and put into magnetic stirring apparatus 20
DEG C at room temperature with the revolving speed agitating solution of 900rpm, reaction terminates when black is presented in 30min liquid to be mixed.Solution is taken out to put
3min is centrifuged with the revolving speed of 10000rpm into centrifuge tube, centrifugate is poured out and dehydrated alcohol is added and fully shake and be centrifuged again
Washing, repeat above washing process wait for centrifugate it is colorless and transparent it is limpid until.The poly-dopamine hollow sphere washed is put to drum
Dry 5h at 60 DEG C in wind baking oven, takes out powder and is transferred in alumina crucible in case calcining.Tube furnace is used in calcination process
Using argon gas as protective atmosphere, the heating rate of 5 DEG C/min is warming up to 1000 DEG C, keeps the temperature 2h, then natural cooling obtains N doping
Hollow carbon sphere material.The test of hydrogen reduction electrocatalysis characteristic is carried out to the N doping hollow carbon sphere material of preparation: being ginseng with Ag/AgCl
Than electrode, 0.1mol/L potassium hydroxide solution is electrolyte, by 5mg N doping hollow carbon sphere, 0.1mL Nafion solution and
0.9mL dehydrated alcohol uniformly mixes ultrasound, dries on the glass-carbon electrode that drop 0.01mL mixed solution to radius is 5mm, with 10mV/
cm2Scanning speed carries out linear sweep voltammetry curve in -0.8~0.2V voltage range.
Embodiment 2:
It weighs 32mL deionized water and 3mL dehydrated alcohol is uniformly mixed and added into 0.2g trioctylamine, 0.08ml ammonium hydroxide is then added.
Mixed solution is put into ultrasonic cleaner, using 100W power ultrasound 20min, taking-up when solution is creamy white suspension
It is spare.It weighs 0.15g Dopamine hydrochloride to be added in the white emulsion prepared, adds magneton and put into magnetic stirring apparatus 20
DEG C at room temperature with the revolving speed agitating solution of 1200rpm, reaction terminates when black is presented in 30min liquid to be mixed.Take out solution
Put into centrifuge tube and 3min be centrifuged with the revolving speed of 10000rpm, pour out centrifugate and be added dehydrated alcohol fully shake and again from
Heart washing, repeat above washing process wait for centrifugate it is colorless and transparent it is limpid until.By the poly-dopamine hollow sphere washed put to
Dry 5h at 60 DEG C in convection oven, takes out powder and is transferred in alumina crucible in case calcining.Tubular type is used in calcination process
For furnace using argon gas as protective atmosphere, the heating rate of 5 DEG C/min is warming up to 1000 DEG C, keeps the temperature 2h, and then natural cooling obtains nitrogen and mixes
Miscellaneous hollow carbon sphere material.The test of hydrogen reduction electrocatalysis characteristic is carried out to the N doping hollow carbon sphere material of preparation: being with Ag/AgCl
Reference electrode, 0.1mol/L potassium hydroxide solution be electrolyte, by 5mg N doping hollow carbon sphere, 0.1mL Nafion solution and
0.9mL dehydrated alcohol uniformly mixes ultrasound, dries on the glass-carbon electrode that drop 0.01mL mixed solution to radius is 5mm, with 10mV/
cm2Scanning speed carries out linear sweep voltammetry curve in -0.8~0.2V voltage range.
Embodiment 3:
It weighs 32mL deionized water and 3mL dehydrated alcohol is uniformly mixed and added into 0.12g trioctylamine, 0.05ml ammonia is then added
Water.Mixed solution is put into ultrasonic cleaner, using 420W power ultrasound 20min, when solution is creamy white suspension
It takes out spare.It weighs 0.05g Dopamine hydrochloride to be added in the white emulsion prepared, adds magneton and put into magnetic stirring apparatus
At 25 DEG C at room temperature with the revolving speed agitating solution of 1200rpm, reaction terminates when black is presented in 30min liquid to be mixed.It takes out
Solution, which is put into centrifuge tube, is centrifuged 3min with the revolving speed of 10000rpm, pours out centrifugate and dehydrated alcohol is added and fully shake and again
Secondary centrifuge washing, repeat above washing process wait for centrifugate it is colorless and transparent it is limpid until.The poly-dopamine hollow sphere that will have been washed
Dry 5h at 60 DEG C is put into convection oven, powder is taken out and is transferred in alumina crucible in case calcining.It is used in calcination process
For tube furnace using argon gas as protective atmosphere, the heating rate of 5 DEG C/min is warming up to 1000 DEG C, keeps the temperature 2h, then natural cooling obtains
N doping hollow carbon sphere material.The test of hydrogen reduction electrocatalysis characteristic is carried out to the N doping hollow carbon sphere material of preparation: with Ag/
AgCl is reference electrode, and 0.1mol/L potassium hydroxide solution is electrolyte, by 5mg N doping hollow carbon sphere, 0.1mL Nafion
Solution and 0.9mL dehydrated alcohol uniformly mix ultrasound, dry on the glass-carbon electrode that drop 0.01mL mixed solution to radius is 5mm,
With 10mV/cm2Scanning speed carries out linear sweep voltammetry curve in -0.8~0.2V voltage range.
Above embodiments are preferred embodiment of the present invention, but embodiment of the present invention are not limited by the above embodiments,
Other any any combination done for not having essential distinction with the present invention or simplification and the other technologies scheme that is formed is
Efficient transformation mode of the invention, it is within the scope of the present invention.
Claims (7)
1. a kind of preparation method of N doping hollow carbon sphere material, it is characterised in that preparation step is as follows:
(1) template trioctylamine is added in solvent, template is dispersed in reaction system by way of physics concussion
In, and acid-base modifier is added and creates alkaline environment；
(2) Dopamine hydrochloride is added in the emulsion system of above-mentioned (1) preparation, reaction certain time length is sufficiently stirred, obtain poly- more
Bar amine product dispersion liquid；
(3) poly-dopamine hollow sphere is obtained after washing is dry in the poly-dopamine product of above-mentioned (2) preparation；
(4) it calcines to obtain N doping hollow carbon sphere material by certain technique in the poly-dopamine hollow sphere that above-mentioned (3) obtain.
2. the preparation method of N doping hollow carbon sphere material according to claim 1, it is characterised in that:
The quality proportioning of raw material are as follows:
A, Dopamine hydrochloride: 1~50 part；
B, ammonium hydroxide: 2~50 parts；
C, trioctylamine: 3~100 parts；
D, dehydrated alcohol: 0~1400 part；
E, water: 1000~4000 parts.
3. the preparation method of N doping hollow carbon sphere material described in accordance with the claim 1, it is characterised in that: the trioctylamine is made
For the evenly dispersed using ultrasound, vibration, agitating procedure of template, disperse any duration.
4. the preparation method of N doping hollow carbon sphere material described in accordance with the claim 1, it is characterised in that: preparation poly-dopamine
The method of product dispersion liquid is: the sequence of mixed raw material is that trioctylamine, water and dehydrated alcohol is first added, and adds ammonium hydroxide.
5. the preparation method of N doping hollow carbon sphere material described in accordance with the claim 1, it is characterised in that: poly-dopamine product
The mode of agitating solution is used in dispersion liquid preparation process；Stirring rate is 500~2000rpm, and synthesis temperature is 1~50 DEG C,
Generated time be 0.25~for 24 hours.
6. the preparation method of N doping hollow carbon sphere material described in accordance with the claim 1, it is characterised in that: washing poly-dopamine
The cleaning solution used during product is water or dehydrated alcohol, synthetic product is separated by way of centrifugation, centrifugal rotational speed is
5000~12000rpm is washed until centrifugate is limpid；Drying box desciccate at 20~80 DEG C is used when drying.
7. the preparation method of N doping hollow carbon sphere material described in accordance with the claim 1, it is characterised in that: calcination process uses
Protective atmosphere be nitrogen, argon gas, helium or vacuum；Heating rate is 0.05~10 DEG C/min, holding temperature 600 when calcining
~1800 DEG C, soaking time is 0.3~3h.
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Cited By (4)
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| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111384407A (en) * | 2020-02-25 | 2020-07-07 | 电子科技大学 | Preparation method of metal monoatomic-dispersed ordered mesoporous carbon spheres |
| CN112403501A (en) * | 2020-10-20 | 2021-02-26 | 上海大学 | Porous nitrogen-doped carbon sphere material with ultralow cobalt atom content, and preparation method and application thereof |
| CN115558415A (en) * | 2022-11-03 | 2023-01-03 | 中海石油(中国)有限公司 | Novel marine antifouling coating based on polydopamine ball oil storage and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111250008B (en) * | 2020-02-08 | 2021-09-21 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
| CN111384407A (en) * | 2020-02-25 | 2020-07-07 | 电子科技大学 | Preparation method of metal monoatomic-dispersed ordered mesoporous carbon spheres |
| CN111384407B (en) * | 2020-02-25 | 2022-04-08 | 电子科技大学 | Preparation method of metal monoatomic-dispersed ordered mesoporous carbon spheres |
| CN112403501A (en) * | 2020-10-20 | 2021-02-26 | 上海大学 | Porous nitrogen-doped carbon sphere material with ultralow cobalt atom content, and preparation method and application thereof |
| CN115558415A (en) * | 2022-11-03 | 2023-01-03 | 中海石油(中国)有限公司 | Novel marine antifouling coating based on polydopamine ball oil storage and preparation method thereof |
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Application publication date: 20190924 |