CN108615906A - A kind of preparation method of nitrogen-doped graphene catalyst - Google Patents
A kind of preparation method of nitrogen-doped graphene catalyst Download PDFInfo
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- CN108615906A CN108615906A CN201810517353.7A CN201810517353A CN108615906A CN 108615906 A CN108615906 A CN 108615906A CN 201810517353 A CN201810517353 A CN 201810517353A CN 108615906 A CN108615906 A CN 108615906A
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- nitrogen
- catalyst
- electrocatalytic oxidation
- oxidation reduction
- reduction reaction
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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
- H01M4/88—Processes of manufacture
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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
A kind of preparation method of nitrogen-doped graphene catalyst, belong to carbon material field, it is while graphite is removed into limbic function graphite alkene that nitrogenous compound and graphene sheet layer progress is compound by way of mechanical force and chemical, it is prepared for that there is fabulous electron transport ability and efficient oxygen reduction activity site nitrogen-doped graphene catalyst, realize the extensive efficient production of efficient oxygen reduction catalyst, the material can be applied to electrocatalytic oxidation reduction process, be of great significance to the low cost production of fuel cell.
Description
Technical field
The invention belongs to carbon material fields, are related to a kind of preparation method of nitrogen-doped graphene catalyst, it is particularly applicable to
Efficient catalytic oxidation-reduction reactive applications.
Background technology
Serious deficient and its caused environmental pollution in view of conventional petroleum resource is increasingly prominent, develops new and effective clear
The clean energy has become national strategy demand.The fuel cell famous using no pollution, energy conversion efficiency turns as clean energy resource
The representative of changing device is extensively studied by global related scientific research personnel.Fuel cell can the fuel that is externally supplied and
Oxidant is directly translated into electric energy by electrochemical reaction, is not required to directly burn, therefore it is not limited by Carnot cycle, energy
Transformation efficiency can reach 40-60%, hardly discharge nitrogenous, sulfur-containing oxide, green non-pollution.However, in fuel cell
Key reaction oxygen reduction reaction rate it is slow, need using Pt as catalyst.But Pt costs are higher, scarcity of resources and presence are easy
To the problems such as catalysis reaction intermediate is poisoned (such as CO), stability is poor, the large-scale application of fuel cell is constrained.
To solve problems, researcher develops base metal and non-metallic catalyst, the wherein carbon materials of N doping
Expect that the efficient oxygen reduction catalyst of catalyst preparation, the progress of acquirement are especially pronounced.
There is graphene fabulous electron transport ability, the doping of nitrogen can effectively provide efficient hydrogen reduction and live
Property site, therefore, the present invention propose it is a kind of by mechanochemical method prepare for electrocatalytic oxidation reduction reaction N doping
The method of graphen catalyst.Small molecule nitrogenous compound and graphene sheet layer are answered by way of mechanical force and chemical
It closes, is prepared for nitrogen-doped graphene catalyst, it is intended to realize the extensive efficient production of efficient oxygen reduction catalyst.
Invention content
The present invention in view of the above problems, provides a kind of prepared by mechanochemical method and is used for electrocatalytic oxidation also
The method of the nitrogen-doped graphene catalyst of original reaction.
The present invention to achieve the above object, takes following technical scheme to be achieved:
The present invention proposes a kind of N doping graphite prepared by mechanochemical method for electrocatalytic oxidation reduction reaction
The method of alkene catalyst.Small molecule nitrogenous compound is subjected to compound, system with graphene sheet layer by way of mechanical force and chemical
For nitrogen-doped graphene catalyst, it is intended to realize the extensive efficient production of efficient oxygen reduction catalyst.It is characterized in that,
Include the following steps：
(1) graphite powder and nitrogenous compound are placed in reaction mill equipment, will reaction mill equipment sealing, then by protective gas
It is flushed in reaction mill equipment, starts reaction mill equipment, reaction mill obtains unreduced nitrogen-doped graphene after 24-72 hours；
(2) unreduced nitrogen-doped graphene is taken out after reacting, impregnated, washed 2 hours with methanol, wait for unreacted contain
Nitrogen compound filters after being dissolved in methanol, removes unreacted nitrogenous compound, is freeze-dried 24 hours；
(3) by the nitrogen-doped graphene after drying, 500 DEG C of -1500 DEG C of high-temperature process 0.5 hour -5 are small under protection of argon gas
Shi Hou, room temperature to be down to are taken out.
The protective gas is including but not limited to the gases such as carbon dioxide, nitrogen, argon gas, gas pressure range
0.1MPa-25MPa。
The nitrogenous compound is including but not limited to melamine, porphyrin, phthalocyanine etc..
It is 1 by the mass ratio of graphite powder and nitrogenous compound:(0.5-5).
The reaction mill equipment is selected from planetary ball mill, horizontal ball mill, sand mill, rod mill.Reaction mill equipment is ground
The material of abrading-ball or stick and tank body is wear-resistant material, such as zirconium oxide material, agate material and other wear-resistant materials.
Reaction is consumed time：It is reacted 3-72 hours with the rotating speed continuously grinding of 100-5000rpm.
Graphite powder is natural flake graphite or amorphous graphite.
Graphite powder amount of fill is to react the 1/4-1/2 of grinding jar body total volume, preferably 1/3.
The high-temperature process temperature is 500 DEG C -1500 DEG C.
The high-temperature process temperature time is -5 hours 0.5 hour.
The present invention is beneficial to as follows：
The present invention proposes a kind of N doping graphite prepared by mechanochemical method for electrocatalytic oxidation reduction reaction
The method of alkene catalyst.It is by way of mechanical force and chemical that nitrogenous compound and graphene sheet layer progress is compound, it is prepared for nitrogen
Doped graphene catalyst realizes the extensive efficient production of efficient oxygen reduction catalyst.
The present invention has gone out a kind of prepared by mechanochemical method and has been urged for the nitrogen-doped graphene of catalytic oxidation-reduction reaction
The method of agent, prepared catalyst take-off potential in electrocatalytic oxidation reduction reaction is 0.88ev, carrying current 4.1mA/
cm2, prepared catalyst is with good stability, and catalytic performance does not wane substantially after 5000 circle cyclic voltammetry scannings
Subtract.
Description of the drawings
Nitrogen-doped graphene catalyst linear scan curve graph is made in Fig. 1 present examples 1.
Nitrogen-doped graphene catalyst circulation volt-ampere curve figure is made in Fig. 2 present examples.
Fig. 3 present examples are made nitrogen-doped graphene catalyst 5000 and enclose the front and back linear scan song of cyclic voltammetry scanning
Line comparison diagram.
Nitrogen-doped graphene catalyst scanning electron microscope (SEM) photograph is made in Fig. 4 present examples.
Specific implementation mode
With reference to embodiment, the invention will be further described, and the present invention is not limited to following embodiments for computer.
Embodiment 1
1, planetary ball mill ball grinder is taken out, the zirconium oxide bead of 1/3 volume of ball grinder is added, according to 1:3 ratios after
The natural flake graphite powder and melamine of 200 mesh of continuous addition, until zirconium oxide bead and total powder volume reach tank body total volume
1/2, ball grinder is sealed, protective gas is poured into ball grinder, until pressure reaches 0.2MPa, then releases gas, so
It repeats five times.Protective gas is filled with into ball grinder again, until pressure reaches 2MPa, fastens air valve, ball grinder is mounted on ball
On grinding machine.
2, setting drum's speed of rotation is 500rpm, starts ball mill, continuous operation 48 hours.Air valve is opened, sample is screened out
Product are not to get restoring nitrogen-doped graphene.
3, nitrogen-doped graphene taking-up is not restored after reacting, impregnated, washed 2 hours with methanol, wait for unreacted nitrogen
It closes after object is dissolved in methanol and filters, remove unreacted nitrogenous compound, be freeze-dried 24 hours.4, by the N doping after drying
Graphene under protection of argon gas after two hours, take out 900 DEG C of high-temperature process by room temperature to be down to.
Prepared catalyst take-off potential in electrocatalytic oxidation reduction reaction is 0.88eV, carrying current 4.1mA/cm2,
And catalytic performance is substantially unattenuated after 5000 circle cyclic voltammetry scannings.
Embodiment 2
1, planetary ball mill ball grinder is taken out, the zirconium oxide bead of 1/3 volume of ball grinder is added, according to 1:2 ratios after
The natural flake graphite powder and melamine of 200 mesh of continuous addition, until zirconium oxide bead and total powder volume reach tank body total volume
1/2, ball grinder is sealed, protective gas is poured into ball grinder, until pressure reaches 0.2MPa, then releases gas, so
It repeats five times.Protective gas is filled with into ball grinder again, until pressure reaches 2MPa, fastens air valve, ball grinder is mounted on ball
On grinding machine.
2, setting drum's speed of rotation is 500rpm, starts ball mill, continuous operation 48 hours.Air valve is opened, sample is screened out
Product are not to get restoring nitrogen-doped graphene.
3, nitrogen-doped graphene takes out after reacting, and is impregnated, is washed 2 hours with methanol, waits for that unreacted nitrogenous compound is molten
Solution filters after methanol, removes unreacted nitrogenous compound, is freeze-dried 24 hours.
4, nitrogen-doped graphene will not be restored under protection of argon gas after 900 DEG C of high-temperature process two hours after drying, wait dropping
It is taken out to room temperature.
Prepared catalyst take-off potential in electrocatalytic oxidation reduction reaction is 0.83eV, carrying current 3.6mA/cm2,
And catalytic performance is substantially unattenuated after 5000 circle cyclic voltammetry scannings.
Embodiment 3
1, planetary ball mill ball grinder is taken out, the zirconium oxide bead of 1/3 volume of ball grinder is added, according to 1:1 ratio after
The natural flake graphite powder and melamine of 200 mesh of continuous addition, until zirconium oxide bead and total powder volume reach tank body total volume
1/2, ball grinder is sealed, protective gas is poured into ball grinder, until pressure reaches 0.2MPa, then releases gas, so
It repeats five times.Protective gas is filled with into ball grinder again, until pressure reaches 2MPa, fastens air valve, ball grinder is mounted on ball
On grinding machine.
2, setting drum's speed of rotation is 500rpm, starts ball mill, continuous operation 48 hours.Air valve is opened, sample is screened out
Product are not to get restoring nitrogen-doped graphene.
3, nitrogen-doped graphene taking-up is not restored after reacting, impregnated, washed 2 hours with methanol, wait for unreacted nitrogen
It closes after object is dissolved in methanol and filters, remove unreacted nitrogenous compound, be freeze-dried 24 hours.
4, nitrogen-doped graphene will not be restored under protection of argon gas after 900 DEG C of high-temperature process two hours after drying, wait dropping
It is taken out to room temperature.
Prepared catalyst take-off potential in electrocatalytic oxidation reduction reaction is 0.83eV, carrying current 2.45mA/
cm2, and catalytic performance is substantially unattenuated after 5000 circle cyclic voltammetry scannings.
Claims (9)
1. a kind of method preparing the nitrogen-doped graphene catalyst for electrocatalytic oxidation reduction reaction by mechanochemical method,
It is characterized by comprising the following steps：
(1) graphite powder and nitrogenous compound are placed in reaction mill equipment, are flushed to by reaction mill equipment sealing, then by protective gas
In reaction mill equipment, start reaction mill equipment, reaction mill obtains unreduced nitrogen-doped graphene after 24-72 hours；
(2) unreduced nitrogen-doped graphene is taken out after reacting, impregnated, washed 2 hours with methanol, wait for unreacted nitrogen
It closes after object is dissolved in methanol and filters, remove unreacted nitrogenous compound, be freeze-dried 24 hours；
(3) by after the nitrogen-doped graphene after drying under protection of argon gas 500 DEG C of -1500 DEG C of high-temperature process -5 hours 0.5 hour,
Room temperature to be down to is taken out.
2. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that the protective gas is including but not limited to gas such as carbon dioxide, nitrogen, argon gas
Body, gas pressure range 0.1MPa-25MPa.
3. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that the nitrogenous compound is including but not limited to melamine, porphyrin, phthalocyanine.
4. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that by the mass ratio of graphite powder and nitrogenous compound be 1:(0.5-5).
5. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that the reaction mill equipment is selected from planetary ball mill, horizontal ball mill, sand milling
Machine, rod mill.
6. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that reaction mill equipment mill ball or the material of stick and tank body are selected from zirconium oxide material
The wear-resistant materials such as matter, agate material.
7. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that reaction, which is consumed time, is：3- is reacted with the rotating speed continuously grinding of 100-5000rpm
72 hours.
8. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that graphite powder is natural flake graphite or amorphous graphite.
9. a kind of N doping prepared by mechanochemical method for electrocatalytic oxidation reduction reaction described in accordance with the claim 1
The method of graphen catalyst, which is characterized in that graphite powder amount of fill is to react the 1/4-1/2 of grinding jar body total volume, preferably 1/
3。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110208323A (en) * | 2019-05-30 | 2019-09-06 | 济南大学 | For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide |
| CN111215111A (en) * | 2020-01-13 | 2020-06-02 | 山西大学 | Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application thereof |
Citations (3)
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| CN103407989A (en) * | 2013-06-24 | 2013-11-27 | 温州医学院 | Low-temperature environmentally-friendly preparation method of nitrogen edge doped graphene |
| CN103785466A (en) * | 2013-11-14 | 2014-05-14 | 温州医科大学 | Novel preparation method of edge functionalized graphene catalyst |
| CN105032469A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军国防科学技术大学 | Biomass base nitrogen-doped graphene/carbon fiber electrocatalyst and preparation method thereof |
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2018
- 2018-05-25 CN CN201810517353.7A patent/CN108615906A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103407989A (en) * | 2013-06-24 | 2013-11-27 | 温州医学院 | Low-temperature environmentally-friendly preparation method of nitrogen edge doped graphene |
| CN103785466A (en) * | 2013-11-14 | 2014-05-14 | 温州医科大学 | Novel preparation method of edge functionalized graphene catalyst |
| CN105032469A (en) * | 2015-08-11 | 2015-11-11 | 中国人民解放军国防科学技术大学 | Biomass base nitrogen-doped graphene/carbon fiber electrocatalyst and preparation method thereof |
Non-Patent Citations (2)
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| DAN LIU等: ""High N-content holey few-layered graphene electrocatalysts:scalable solvent-less production"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| XIAOGANG FU等: ""Efficient Oxygen Reduction Electrocatalyst Based on Edge-Nitrogen-Rich Graphene Nanoplatelets:Toward a Large-Scale Synthesis"", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110208323A (en) * | 2019-05-30 | 2019-09-06 | 济南大学 | For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide |
| CN111215111A (en) * | 2020-01-13 | 2020-06-02 | 山西大学 | Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application thereof |
| CN111215111B (en) * | 2020-01-13 | 2022-07-19 | 山西大学 | Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application thereof |
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