CN108039500A - A kind of preparation method of iron nitrogen codope carbon nanometer micro ball and oxygen reduction application - Google Patents
A kind of preparation method of iron nitrogen codope carbon nanometer micro ball and oxygen reduction application Download PDFInfo
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- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
A kind of preparation method the present invention provides iron nitrogen codope carbon nanometer micro ball and the application in hydrogen reduction.Nitrogen source supply thing poly-dopamine is synthesized with Dopamine hydrochloride in alkaline conditions first, is then coated on the surface of ferroso-ferric oxide microballoon.The ferroso-ferric oxide microballoon of poly-dopamine cladding is with glucose response in autoclave, and under a nitrogen atmosphere, high-temperature calcination obtains iron nitrogen-doped carbon nanoparticle.The synthesis of iron nitrogen-doped carbon nanoparticle is realized as erodent template and nitrogen source at the same time using glucose as raw material, using the ferroso-ferric oxide microballoon of poly-dopamine cladding.Iron nitrogen-doped carbon nanoparticle is applied to electro-catalysis redox reactions（ORR）In have good result and there is good durability, it is 0.949V that it, which reduces the take-off potential relative standard hydrogen electrode of oxygen, it still can reach more than 85% by durability test behind efficiency and remain to maintain 94% service efficiency after methanol is added, there is good methanol tolerance effect.
Description
Technical field
A kind of preparation method of iron nitrogen codope carbon nanometer micro ball of the present invention and its application in oxygen reduction, belong to and receive
The technical fields such as rice material, catalysis technique.
Background technology
With the drastically consumption and the aggravation of problem of environmental pollution of fossil energy, seek the new energy of clean and effective into
For the hot spot studied at present.High-effect, low emission fuel cell energy has attracted the common concern of people.But in fuel electricity
Because the oxygen reduction kinetics of cathode slowly much cause fuel cell not as good as anode hydrogen oxidation reaction during the reaction of pond
Efficiency be limited by very large.Therefore the oxygen reduction catalyst agent of synthesizing efficient is designed, the hair for promoting fuel cell
Exhibition is of great significance.
Due to unique dimensional effect, nano material often has many novel physicochemical properties, and in multiple necks
Domain shows good application.Nano material has important application in energy stores and the fields such as conversion, catalysis, particularly
Application in terms of redox reactions, novel catalysis material is provided for the utilization of fuel cell.Nano material because
Its good result in terms of catalytic oxygen reduction, the design of various nanocatalysts become the weight of Solid-state Chemistry research with synthesis
Want field, wherein carbon-based material has good electric conductivity, while has an excellent carrier specific surface area big again and heat endurance
The characteristics of high, therefore show the advantage as catalyst carrier.Document 1 has synthesized carbon group compound PANI_O2_800
(Carbon., 2017,119,62-71.), there is larger specific surface area 584m2/g.As people are to carbon-based material
What matter understood further gos deep into, and benefits from many nano ZnO control measures of current development, and carbon-based material is answered
It will significantly be widened with field and application mode, produce significant Social benefit and economic benefit.
Modification regulation and control are carried out to nano material using effective chemical means, can often realize changing for its intrinsic performance
It is kind, there is practical operation value and research significance for optimizing its function.In many means, Heteroatom doping be it is a kind of effectively and
Most commonly seen performance control measures, can be realized to the property such as material conductivity, catalytic activity, stability by Heteroatom doping
The optimization of energy.Such as document 2（Electrochimica Acta, 2017,224,47-53）Carbon materials are realized by doping iron, nitrogen
Expect structural change, the electric conductivity current density for lifting carbon material reaches 4.96 mA/cm2, realize the excellent of catalytic performance
Change, the take-off potential relative standard hydrogen electrode for reducing oxygen is 0.919V；Document 3（Energy & Environmental
Science, 2016, 9(4):1320-1326.）By doping of the cobalt sulphur compound in graphene, leading for carbon material is lifted
Electrical current density reaches 4.23 mA/cm2, the optimization of catalytic performance is realized, reduces take-off potential relative standard's hydrogen of oxygen
Electrode is 0.84V.The present invention significantly improves the specific surface area of carbon material by doping of the iron nitrogen to material, current density with
And catalytic activity, improve material hydrogen reduction catalytic performance of the present invention.
The content of the invention
One of technical assignment of the present invention is in order to make up for the deficiencies of the prior art, there is provided a kind of iron nitrogen codope carbon nanometer
The preparation method of the preparation method of microballoon, the raw materials used cost of this method is low, and preparation process is simple, and energy consumption of reaction is low, has work
Industry application prospect.
The purposes that the two of the technical assignment of the present invention are to provide the iron nitrogen codope carbon nanometer micro ball, will the iron nitrogen it is double-doped
Application of the miscellaneous carbon nanometer micro ball as oxygen reduction catalyst agent, take-off potential relative standard's hydrogen electrode of its reduction oxygen are
0.949V, durability test behind efficiency still can reach more than 85%, and remain to maintain 94% use after methanol is added
Efficiency, has good methanol tolerance effect.
Technical scheme is as follows：
1. a kind of preparation method of iron nitrogen codope carbon nanometer micro ball, comprises the following steps：
(1) 10mmol FeCl3 are dispersed in 100mL ethylene glycol, 30min are stirred at room temperature, add 40mmol CH3COONa,
Continue to stir 2h, be transferred in reaction kettle and heat, washed through deionized water, 50oC vacuum drying, ferroso-ferric oxide microballoon is made
Powder；200mg Dopamine hydrochlorides are added in the Tris buffer solutions and 60mL isopropanol mixed liquors of 200mL, room under the conditions of lucifuge
Temperature stirring 24h, washs, 50oC vacuum drying by deionized water, poly-dopamine powder is made；By 75mg ferroso-ferric oxide microballoons
Powder stirs 12 ~ 36h with 150mg poly-dopamines powder in the Tris solution of 100mL, is washed through deionized water, 50oC vacuum
Black solid powder is dried to obtain, is the ferroso-ferric oxide microballoon of poly-dopamine cladding；
(2) it is the ferroso-ferric oxide microsphere powder that 100mg poly-dopamines coat and 50mL, 0.2 ~ 0.5mol/L glucose is water-soluble
Liquid is blended, and stirs 15 ~ 30min, is transferred in autoclave and heats, be cooled to room temperature, be centrifugally separating to obtain solid, by solid
Washed 3 times with water and ethanol respectively, 50oC is dried in vacuo to obtain brownish black solid powder；The powder is placed in tube furnace, in
Calcined under nitrogen atmosphere, obtain black solid powder, i.e. iron nitrogen codope carbon nanometer micro ball；
Step（2）Heated in the autoclave, temperature is 100 ~ 200oC, and the reaction time is 6 ~ 14h；
Step（2）Calcined under the nitrogen atmosphere, temperature 700-1000oC, calcination time is 30 ~ 80min.
2. iron nitrogen codope carbon nanometer micro ball prepared by above-described preparation method should as oxygen reduction catalyst agent
With step is as follows：
Using three-electrode system, electro-catalysis reduction oxygen performance test is carried out on electrochemical workstation, it is double-doped with load iron nitrogen
The glass-carbon electrode of miscellaneous carbon nanometer micro ball is working electrode, and using carbon-point as to electrode, Hg/Hg2Cl2 electrodes are reference electrode；With 0.1
Mol/L potassium hydroxide solutions are electrolyte；Using glass electrolytic cell as reaction unit, it is reduced, and the take-off potential of oxygen is opposite to be marked
Quasi- hydrogen electrode is 0.949V, and durability test behind efficiency still can reach more than 85%, and remain to maintain after methanol is added
94% service efficiency, has good methanol tolerance effect；
The glass-carbon electrode of the load iron nitrogen codope carbon nanometer micro ball, carrying method are as follows：
Weigh 5mg iron nitrogen codope carbon nanometer micro ball powder, be added to the in the mixed solvent of 1mL isopropanols and water, isopropanol with
The volume ratio of water is 1:3,50 μ L Nafion solutions are continuously added, ultrasonic 30min, obtains black dispersion liquid, takes 10 μ L black points
Dispersion liquid, drop coating is in glassy carbon electrode surface, ambient temperature overnight, i.e., the glass-carbon electrode of obtained load iron nitrogen codope carbon nanometer micro ball.
The useful achievement of the present invention:
The present invention provides a kind of iron nitrogen codope carbon nanometer micro ball and preparation method, and its application in hydrogen reduction.With
Existing oxygen reduction catalyst agent is compared, and has following advantage：
（1）Iron nitrogen codope carbon nanometer micro ball is synthesized using hydro-thermal method, and preparation method is simple.Iron nitrogen codope carbon nanometer micro ball is gathered around
There are 760 m2Specific surface area larger/g, good electric conductivity, current density reach 7 mA/cm2, possess as catalyst material
Excellent properties；
（2）The iron nitrogen codope carbon nanometer micro ball of the present invention, the specific surface area of its material, current density and catalytic activity are superior to
The grapheme material for the cobalt sulphur compound doping that document 3 is reported；
（3）Iron nitrogen codope carbon nanometer micro ball of the present invention is that have cheap, abundance raw material, is existed as catalyst
Fuel battery negative pole reduces oxygen.Of low cost compared with traditional commercialization Pt/C catalyst, catalytic effect has reached business
The level of catalyst, it is 0.949V that it, which reduces the take-off potential relative standard hydrogen electrode of oxygen, the 0.951V bases with business Pt/C
This maintains an equal level；Business Pt/C durability tests behind efficiency is 40% after durability test（Battery, 2009,39 (1):44-
46.）, the catalytic efficiency of iron nitrogen codope carbon nanometer micro ball material of the present invention remained to more than 85%；After adding methanol, business Pt/
The catalytic efficiency of C catalyst is 85%（It is catalyzed journal, 2013,34 (6):1105-1111.）, iron nitrogen codope carbon of the present invention receives
Rice micro-sphere material still maintains 94% catalytic efficiency, has good methanol tolerance effect.
Iron nitrogen codope carbon nanometer micro ball realizes the situ iron nitrogen codope to carbon nanometer micro ball material by in-situ reducing,
It is applied when electro-catalysis reduces oxygen reaction, shows to be substantially better than nitrogen-doped carbon nanospheres, Fe2O3 doping carbon nanometer
The excellent properties of micro-sphere material, this benefits most from regulation and control of the iron nitrogen codope to the electronic structure of base material carbon ball and its leads
Electrical optimization.With traditional single dopant material, such as N doping carbon ball, Fe2O3 doping carbon ball is compared, and is improving initial reduction
Current potential, improves the beneficial effect in terms of the service life of whole material mainly by the doping of iron nitrogen to whole carbon ball material
Regulation and control.Contrasted by each side, iron nitrogen codope carbon nanometer micro ball performance in terms of catalysis reduces oxygen has obvious
The effect of raising, is beneficial to fuel cell development and application and further industrialized developing uses.
Embodiment
The present invention provides a kind of iron nitrogen codope carbon nanometer micro ball and preparation method, and its application in electrolysis water,
Comprise the following steps：
Embodiment 1
The first step, the synthesis of the ferroso-ferric oxide microballoon of poly-dopamine cladding：The ferroso-ferric oxide microballoon of poly-dopamine cladding leads to
Crossing ferroso-ferric oxide, the long agitation in Tris solution obtains with poly-dopamine.First, Fe3O4Synthesized, had by hydro-thermal reaction
Body process：10mmol FeCl3By ultrasonic power, it is dispersed in 100mL ethylene glycol, after stirring 30min, the Huang clarified
Color solution.Then 40 mmol CH are added3Above-mentioned solution, after again passing by 2h stirrings, is transferred to the reaction kettle of 50mL by COONa
In, 200o12h is reacted under C.After being cooled to room temperature, with deionized water and ethanol washing sample and centrifuge, obtained after dry respectively
Black magnetic solid is Fe3O4.Secondly, poly-dopamine is as obtained by polymerisation, idiographic flow：200mg Dopamine hydrochlorides add
In the mixed liquor of 200mL Tris buffer solutions and 60mL isopropanols, 24h is stirred under the conditions of lucifuge, is carried out repeatedly with deionized water
Wash and centrifuge.It is poly-dopamine that sediment obtains black solid after freeze-drying.Finally, 75mg Fe are taken3O4、150mg
Poly-dopamine and 120mgTris are dispersed in the water of 100mL, and 36h is stirred at ambient temperature after 10min is ultrasonically treated,
Finally by filtering, and repeatedly washed with deionized water, obtain the ferroso-ferric oxide microballoon of poly-dopamine cladding.
Second step, the synthesis of iron nitrogen codope carbon nanometer micro ball：Iron nitrogen codope carbon nanometer micro ball is anti-by hydro-thermal first
The ferroso-ferric oxide that poly-dopamine coats should be evenly distributed in carbon nanometer micro ball.The 100mg that upper step synthesizes is gathered more
The ferroso-ferric oxide microballoon of bar amine cladding is scattered in 0.3 mol/L glucose solutions of 50mL, is obtained after stirring 20min
Even dispersion liquid.Then the solution is transferred in the reaction kettle of 50mL, 160oC heating reactions 8h.After being cooled to room temperature, spend
Ionized water washing sample simultaneously centrifuges, and brownish black solid powder is obtained after dry.Then the powder is placed in tube furnace, 1000 DEG C
After lower calcining 60min, black solid is obtained, is iron nitrogen codope carbon nanometer micro ball.
3rd step, iron nitrogen codope carbon nanometer micro ball and the application for reducing oxygen：
1. weighing 5mg iron nitrogen codope carbon nanometer micro ball powder, the in the mixed solvent of 1mL isopropanols and water is added to（Isopropyl
The volume ratio of alcohol and water is 1:3）, while 50 μ L Nafion solutions are added, ultrasonic 30min, obtains black dispersion liquid.Take 10 μ L
Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, a diameter of 5mm of glass-carbon electrode.Ambient temperature overnight, is made load iron nitrogen codope carbon
The glass-carbon electrode of nanoparticle；
2. using three-electrode system, electro-catalysis reduction oxygen performance test is carried out on occasion China 660E electrochemical workstations.With negative
The glass-carbon electrode for carrying the glass-carbon electrode of iron nitrogen codope carbon nanometer micro ball material is working electrode, using carbon-point as to electrode, Hg/
Hg2Cl2Electrode is reference electrode.Using 0.1 mol/L potassium hydroxide solutions as electrolyte, using glass electrolytic cell as reaction unit；
3. respectively using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, in three-electrode system
Cyclic voltammetry is carried out, activates sample.Cyclic voltammetry voltage range is -1.0 ~ 0.2V, maximum potential 0.2V, minimum
Current potential -1.0V, beginning current potential are 0.2V, and termination current potential is -1V.Sweep speed is 0. 5V/s.Sampling interval is 0.001.Stand
Time is 2s.It is 400 to scan hop count；
4. after cyclic voltammetry, using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode,
Linear voltage sweep test is carried out in three-electrode system, voltage range is -1 ~ 0.2V.Initial potential is 0.2V, terminate current potential for-
1V.Sweep speed is 5mV/s.Sampling interval is 0.001V.Time of repose is 2s；
5. using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, catalyst is carried out respectively resistance to
Long property and methanol tolerant performance test, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is -0.2V, between sampling
It is divided into 0.1 second, run time is 4000 seconds.Time of repose is 20 seconds.After data processing and calculating, iron nitrogen codope carbon nanometer
Microballoon has excellent effect being applied to ORR, and it is 0.949V that it, which reduces the take-off potential of oxygen,（Relative standard's hydrogen electrode）, process is resistance to
The behind efficiency of property test long still can reach more than 85% while remain to maintain 94% service efficiency after adding methanol, have well
Methanol tolerance effect.
Embodiment 2
The first step, the synthesis of the ferroso-ferric oxide microballoon of poly-dopamine cladding：The ferroso-ferric oxide microballoon of poly-dopamine cladding leads to
Crossing ferroso-ferric oxide, long agitation obtains under air with poly-dopamine.First, Fe3O4Synthesized by hydro-thermal reaction, specific mistake
Journey：10mmol FeCl3By ultrasonic power, it is dispersed in 100mL ethylene glycol, after stirring 30min, the yellow clarified is molten
Liquid.Then 40mmol CH are added3COONa, after again passing by 2h stirrings, above-mentioned solution is transferred in the reaction kettle of 50mL,
200 o12h is reacted under C.After being cooled to room temperature, with deionized water and ethanol washing sample and centrifuge, obtained after dry black respectively
Color magnetic retention is Fe3O4.Secondly, poly-dopamine is as obtained by polymerisation, idiographic flow：200mg Dopamine hydrochlorides add
In the mixed liquor of 200mL Tris buffer solutions and 60mL isopropanols, 24h is stirred under the conditions of lucifuge, is carried out repeatedly with deionized water
Wash and centrifuge.It is poly-dopamine that sediment obtains black solid after freeze-drying.Finally, 75mg Fe are taken3O4、150mg
Poly-dopamine and 120mgTris are dispersed in the water of 100mL, and 24h is stirred at ambient temperature after 10min is ultrasonically treated,
Finally by filtering, and repeatedly washed with deionized water, obtain the ferroso-ferric oxide microballoon of poly-dopamine cladding.
Second step, the synthesis of iron nitrogen codope carbon nanometer micro ball：Iron nitrogen codope carbon nanometer micro ball is anti-by hydro-thermal first
The ferroso-ferric oxide that poly-dopamine coats should be evenly distributed in carbon nanometer micro ball.The 100mg that upper step synthesizes is gathered more
The ferroso-ferric oxide microballoon of bar amine cladding is scattered in 50mL 0.2mol/L glucose solutions, is obtained uniformly after stirring 15min
Dispersion liquid.Then the solution is transferred in the reaction kettle of 50mL, 120oC heating reactions 6h.After being cooled to room temperature, spend from
Sub- water washing sample simultaneously centrifuges, and brownish black solid powder is obtained after dry.Then the powder is placed in tube furnace, at 700 DEG C
After calcining 30min, black solid is obtained, is iron nitrogen codope carbon nanometer micro ball.
3rd step, iron nitrogen codope carbon nanometer micro ball and the application for reducing oxygen：
1. weighing 5mg iron nitrogen codope carbon nanometer micro ball powder, the in the mixed solvent of 1mL isopropanols and water is added to（Isopropyl
The volume ratio of alcohol and water is 1:3）, while 50 μ L Nafion solutions are added, ultrasonic 30min, obtains black dispersion liquid.Take 10 μ L
Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, a diameter of 5mm of glass-carbon electrode.Ambient temperature overnight, is made load iron nitrogen codope carbon
The glass-carbon electrode of nanoparticle；
2. using three-electrode system, electro-catalysis reduction oxygen performance test is carried out on occasion China 660E electrochemical workstations.With negative
The glass-carbon electrode for carrying the glass-carbon electrode of iron nitrogen codope carbon nanometer micro ball material is working electrode, using carbon-point as to electrode, Hg/
Hg2Cl2 electrodes are reference electrode.Using 0.1 mol/L potassium hydroxide solutions as electrolyte, using glass electrolytic cell as reaction unit；
3. respectively using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, in three-electrode system
Cyclic voltammetry is carried out, activates sample.Cyclic voltammetry voltage range is -0.9 ~ 0.2V, maximum potential 0.2V, minimum
Current potential -0.9V, beginning current potential are 0.2V, and termination current potential is -0.9V.Sweep speed is 0. 2V/s.Sampling interval is 0.001.It is quiet
It is 2s to put the time.It is 400 to scan hop count；
4. after cyclic voltammetry, using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode,
Linear voltage sweep test is carried out in three-electrode system, voltage range is -0.9 ~ 0.2V.Initial potential is 0.2V, terminates current potential
For -0.9V.Sweep speed is 2mV/s.Sampling interval is 0.001V.Time of repose is 2s；
5. using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, catalyst is carried out respectively resistance to
Long property and methanol tolerant performance test, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is -0.15V, sampling
At intervals of 0.1 second, run time was 4000 seconds.Time of repose is 20 seconds.After data processing and calculating, iron nitrogen codope carbon is received
Meter Wei Qiu has excellent effect being applied to ORR, and it is 0.913V that it, which reduces the take-off potential of oxygen,（Relative standard's hydrogen electrode）, pass through
Durability test behind efficiency still can reach more than 80% while remain to maintain 87% service efficiency after adding methanol, have good
Methanol tolerance effect.
Embodiment 3
The first step, the synthesis of the ferroso-ferric oxide microballoon of poly-dopamine cladding：The ferroso-ferric oxide microballoon of poly-dopamine cladding leads to
Crossing ferroso-ferric oxide, long agitation obtains under air with poly-dopamine.First, Fe3O4Synthesized by hydro-thermal reaction, specific mistake
Journey：10mmol FeCl3By ultrasonic power, it is dispersed in 100mL ethylene glycol, after stirring 30min, the yellow clarified is molten
Liquid.Then 40mmol CH are added3COONa, after again passing by 2h stirrings, above-mentioned solution is transferred in the reaction kettle of 50mL,
200 o12h is reacted under C.After being cooled to room temperature, with deionized water and ethanol washing sample and centrifuge, obtained after dry black respectively
Color magnetic retention is Fe3O4.Secondly, poly-dopamine is as obtained by polymerisation, idiographic flow：200mg Dopamine hydrochlorides add
In the mixed liquor of 200mLTris buffer solutions and 60mL isopropanols, 24h is stirred under the conditions of lucifuge, is carried out repeatedly with deionized water
Wash and centrifuge.It is poly-dopamine that sediment obtains black solid after freeze-drying.Finally, 75mg Fe are taken3O4、150mg
Poly-dopamine and 120mgTris are dispersed in the water of 100mL, and 24h is stirred at ambient temperature after 10min is ultrasonically treated,
Finally by filtering, and repeatedly washed with deionized water, obtain the ferroso-ferric oxide microballoon of poly-dopamine cladding.
Second step, the synthesis of iron nitrogen codope carbon nanometer micro ball：Iron nitrogen codope carbon nanometer micro ball is anti-by hydro-thermal first
The ferroso-ferric oxide that poly-dopamine coats should be evenly distributed in carbon nanometer micro ball.The 100mg that upper step synthesizes is gathered more
The ferroso-ferric oxide microballoon of bar amine cladding is scattered in 50mL 0.4mol/L glucose solutions, is obtained uniformly after stirring 25min
Dispersion liquid.Then the solution is transferred in the reaction kettle of 50mL, 130oC heating reactions 12h.After being cooled to room temperature, spend
Ionized water washing sample simultaneously centrifuges, and brownish black solid powder is obtained after dry.Then the powder is placed in tube furnace, 800 DEG C
After lower calcining 50min, black solid is obtained, is iron nitrogen codope carbon nanometer micro ball.
3rd step, iron nitrogen codope carbon nanometer micro ball and the application for reducing oxygen：
1. weighing 5mg iron nitrogen codope carbon nanometer micro ball powder, the in the mixed solvent of 1mL isopropanols and water is added to（Isopropyl
The volume ratio of alcohol and water is 1:3）, while 50 μ L Nafion solutions are added, ultrasonic 30min, obtains black dispersion liquid.Take 10 μ L
Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, a diameter of 5mm of glass-carbon electrode.Ambient temperature overnight, is made load iron nitrogen codope carbon
The glass-carbon electrode of nanoparticle；
2. using three-electrode system, electro-catalysis reduction oxygen performance test is carried out on occasion China 660E electrochemical workstations.With negative
The glass-carbon electrode for carrying the glass-carbon electrode of iron nitrogen codope carbon nanometer micro ball material is working electrode, using carbon-point as to electrode, Hg/
Hg2Cl2 electrodes are reference electrode.Using 0.1 mol/L potassium hydroxide solutions as electrolyte, using glass electrolytic cell as reaction unit；
3. respectively using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, in three-electrode system
Cyclic voltammetry is carried out, activates sample.Cyclic voltammetry voltage range is -1.0 ~ 0.1V, maximum potential 0.1V, minimum
Current potential -1.0V, beginning current potential are 0.1V, and termination current potential is -1V.Sweep speed is 0. 3V/s.Sampling interval is 0.001.Stand
Time is 2s.It is 400 to scan hop count；
4. after cyclic voltammetry, using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode,
Linear voltage sweep test is carried out in three-electrode system, voltage range is -1 ~ 0.1V.Initial potential is 0.1V, terminate current potential for-
1V.Sweep speed is 3mV/s.Sampling interval is 0.001V.Time of repose is 2s；
5. using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, catalyst is carried out respectively resistance to
Long property and methanol tolerant performance test, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is -0.25V, sampling
At intervals of 0.1 second, run time was 4000 seconds.Time of repose is 20 seconds.After data processing and calculating, iron nitrogen codope carbon is received
Meter Wei Qiu has excellent effect being applied to ORR, and it is 0.919V that it, which reduces the take-off potential of oxygen,（Relative standard's hydrogen electrode）, pass through
Durability test behind efficiency still can reach more than 82% while remain to maintain 90% service efficiency after adding methanol, have good
Methanol tolerance effect.
Embodiment 4
The first step, the synthesis of the ferroso-ferric oxide microballoon of poly-dopamine cladding：The ferroso-ferric oxide microballoon of poly-dopamine cladding leads to
Crossing ferroso-ferric oxide, long agitation obtains under air with poly-dopamine.First, Fe3O4Synthesized by hydro-thermal reaction, specific mistake
Journey：10mmol FeCl3By ultrasonic power, it is dispersed in 100mL ethylene glycol, after stirring 30min, the yellow clarified is molten
Liquid.Then 40mmol CH are added3COONa, after again passing by 2h stirrings, above-mentioned solution is transferred in the reaction kettle of 50mL,
200 o12h is reacted under C.After being cooled to room temperature, with deionized water and ethanol washing sample and centrifuge, obtained after dry black respectively
Color magnetic retention is Fe3O4.Secondly, poly-dopamine is as obtained by polymerisation, idiographic flow：200mg Dopamine hydrochlorides add
In the mixed liquor of 200mLTris buffer solutions and 60mL isopropanols, 24h is stirred under the conditions of lucifuge, is carried out repeatedly with deionized water
Wash and centrifuge.It is poly-dopamine that sediment obtains black solid after freeze-drying.Finally, 75mg Fe are taken3O4、150mg
Poly-dopamine and 120mgTris are dispersed in the water of 100mL, and 30h is stirred at ambient temperature after 10min is ultrasonically treated,
Finally by filtering, and repeatedly washed with deionized water, obtain the ferroso-ferric oxide microballoon of poly-dopamine cladding.
Second step, the synthesis of iron nitrogen codope carbon nanometer micro ball：Iron nitrogen codope carbon nanometer micro ball is anti-by hydro-thermal first
The ferroso-ferric oxide that poly-dopamine coats should be evenly distributed in carbon nanometer micro ball.The 100mg that upper step synthesizes is gathered more
The ferroso-ferric oxide microballoon of bar amine cladding is scattered in 50mL 0.5mol/L glucose solutions, is obtained uniformly after stirring 30min
Dispersion liquid.Then the solution is transferred in the reaction kettle of 50mL, 180oC heating reactions 14h.After being cooled to room temperature, spend
Ionized water washing sample simultaneously centrifuges, and brownish black solid powder is obtained after dry.Then the powder is placed in tube furnace, 900 DEG C
After lower calcining 80min, black solid is obtained, is iron nitrogen codope carbon nanometer micro ball.
3rd step, iron nitrogen codope carbon nanometer micro ball and the application for reducing oxygen：
1. weighing 5mg iron nitrogen codope carbon nanometer micro ball powder, the in the mixed solvent of 1mL isopropanols and water is added to（Isopropyl
The volume ratio of alcohol and water is 1:3）, while 50 μ L Nafion solutions are added, ultrasonic 30min, obtains black dispersion liquid.Take 10 μ L
Above-mentioned dispersion liquid, drop coating is in glassy carbon electrode surface, a diameter of 5mm of glass-carbon electrode.Ambient temperature overnight, is made load iron nitrogen codope carbon
The glass-carbon electrode of nanoparticle；
2. using three-electrode system, electro-catalysis reduction oxygen performance test is carried out on occasion China 660E electrochemical workstations.With negative
The glass-carbon electrode for carrying the glass-carbon electrode of iron nitrogen codope carbon nanometer micro ball material is working electrode, using carbon-point as to electrode, Hg/
Hg2Cl2Electrode is reference electrode.Using 0.1 mol/L potassium hydroxide solutions as electrolyte, using glass electrolytic cell as reaction unit；
3. respectively using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, in three-electrode system
Cyclic voltammetry is carried out, activates sample.Cyclic voltammetry voltage range is -0.8 ~ 0.2V, maximum potential 0.2V, minimum
Current potential -0.8V, beginning current potential are 0.2V, and termination current potential is -0.8V.Sweep speed is 0. 4V/s.Sampling interval is 0.001.It is quiet
It is 2s to put the time.It is 400 to scan hop count；
4. after cyclic voltammetry, using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode,
Linear voltage sweep test is carried out in three-electrode system, voltage range is -0.8 ~ 0.2V.Initial potential is 0.2V, terminates current potential
For -0.8V.Sweep speed is 4mV/s.Sampling interval is 0.001V.Time of repose is 2s；
5. using the glass-carbon electrode of load iron nitrogen codope carbon nanometer micro ball material as working electrode, catalyst is carried out respectively resistance to
Long property and methanol tolerant performance test, to carry out kinetic Process Analysis.Parameter setting is as follows, and initial potential is -0.3V, between sampling
It is divided into 0.1 second, run time is 4000 seconds.Time of repose is 20 seconds.After data processing and calculating, iron nitrogen codope carbon nanometer
Microballoon has excellent effect being applied to ORR, and it is 0.927V that it, which reduces the take-off potential of oxygen,（Relative standard's hydrogen electrode）, process is resistance to
The behind efficiency of property test long still can reach more than 82% while remain to maintain 92% service efficiency after adding methanol, have well
Methanol tolerance effect.
Claims (6)
1. a kind of preparation method of iron nitrogen codope carbon nanometer micro ball, it is characterised in that comprise the following steps：
(1) by 10mmol FeCl3It is dispersed in 100mL ethylene glycol, 30min is stirred at room temperature, adds 40mmol CH3COONa, after
Continuous stirring 2h, is transferred in reaction kettle and heats, and is washed through deionized water, 50oC is dried in vacuo, and ferroso-ferric oxide microballoon powder is made
End；200mg Dopamine hydrochlorides are added in the Tris buffer solutions and 60mL isopropanol mixed liquors of 200mL, the room under the conditions of lucifuge
Temperature stirring 24h, is washed, 50 through deionized wateroC is dried in vacuo, and poly-dopamine powder is made；By 75mg ferroso-ferric oxide microballoon powder
12 ~ 36h is stirred in end with 150mg poly-dopamines powder in the Tris solution of 100mL, is washed through deionized water, 50oC vacuum is done
It is dry to obtain black solid powder, it is the ferroso-ferric oxide microballoon of poly-dopamine cladding；
(2) it is the ferroso-ferric oxide microsphere powder that 100mg poly-dopamines coat and 50mL, 0.2 ~ 0.5 mol/L glucose is water-soluble
Liquid is blended, and stirs 15 ~ 30min, is then transferred into autoclave and heats, after being cooled to room temperature, be centrifugally separating to obtain solid,
Solid is washed 3 times with water and ethanol respectively, 50oC is dried in vacuo to obtain brownish black solid powder；The powder is placed in tube furnace
In, calcined under nitrogen atmosphere, obtain black solid powder, i.e. iron nitrogen codope carbon nanometer micro ball.
2. according to a kind of preparation method of iron nitrogen codope carbon nanometer micro ball described in claim 1, it is characterised in that step
（2）Heated in the autoclave, temperature is 100 ~ 200oC, reaction time are 6 ~ 14 h.
3. according to a kind of preparation method of iron nitrogen codope carbon nanometer micro ball described in claim 1, it is characterised in that step
（2）Calcined under the nitrogen atmosphere, temperature 700-1000oC, calcination time are 30 ~ 80min.
4. iron nitrogen codope carbon nanometer micro ball prepared by the preparation method described in claim 1 is as oxygen reduction catalyst agent
Using.
5. application of the iron nitrogen codope carbon nanometer micro ball according to claim 4 as oxygen reduction catalyst agent, its feature
It is, step is as follows：
Using three-electrode system, electro-catalysis reduction oxygen performance test is carried out on electrochemical workstation, it is double-doped with load iron nitrogen
The glass-carbon electrode of miscellaneous carbon nanometer micro ball is working electrode, using carbon-point as to electrode, Hg/Hg2Cl2Electrode is reference electrode；With 0.1
Mol/L potassium hydroxide solutions are electrolyte；Using glass electrolytic cell as reaction unit, it is reduced, and the take-off potential of oxygen is opposite to be marked
Quasi- hydrogen electrode is 0.949V, and durability test behind efficiency still can reach more than 85%, and remain to maintain after methanol is added
94% service efficiency, has good methanol tolerance effect.
6. application of the iron nitrogen codope carbon nanometer micro ball according to claim 4 as oxygen reduction catalyst agent, its feature
It is, the glass-carbon electrode of the load iron nitrogen codope carbon nanometer micro ball, carrying method is as follows：
Weigh 5mg iron nitrogen codope carbon nanometer micro ball powder, be added to the in the mixed solvent of 1mL isopropanols and water, isopropanol with
The volume ratio of water is 1:3,50 μ L Nafion solutions are continuously added, ultrasonic 30min, obtains black dispersion liquid, takes 10 μ L black points
Dispersion liquid, drop coating is in glassy carbon electrode surface, ambient temperature overnight, i.e., the glass-carbon electrode of obtained load iron nitrogen codope carbon nanometer micro ball.
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