CN102757643B - Preparation method for nitrogen substituted graphene oxide/polypyrrole composite material - Google Patents

Preparation method for nitrogen substituted graphene oxide/polypyrrole composite material Download PDF

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CN102757643B
CN102757643B CN201110105711.1A CN201110105711A CN102757643B CN 102757643 B CN102757643 B CN 102757643B CN 201110105711 A CN201110105711 A CN 201110105711A CN 102757643 B CN102757643 B CN 102757643B
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nitrogen
graphene oxide
composite material
replaces
polypyrrole composite
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CN102757643A (en
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周明杰
刘大喜
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses a preparation method for a nitrogen substituted graphene oxide/polypyrrole composite material. The preparation method comprises the following steps: preparing nitrogen substituted graphene oxide; and adding the nitrogen substituted graphene oxide into a dispersing agent, mixing, adding pyrrole monomer to form mixed liquid, adding oxidant dropwise, reacting and filtering to obtain the nitrogen substituted graphene oxide/polypyrrole composite material. The preparation method is simple. The nitrogen substituted graphene oxide/polypyrrole composite material prepared by the method has stable performance and high electrochemical performance and can be applied to high-electrochemical-capacity supercapacitors and lithium ion battery electrode materials.

Description

A kind of nitrogen replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material
[technical field]
The present invention relates to a kind of nitrogen and replace graphene oxide material, particularly relate to the preparation method that a kind of nitrogen replaces graphene oxide and polymer composite.
[background technology]
Since the strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, because being subject to people, its unique structure and photoelectric property pay attention to widely.Graphene is called " nova " that is rising in Materials science and Condensed Matter Physics field, many novelties that it has and unique character and potential application are just attracting many scientific workers.
Single-layer graphene has large specific surface area, good conduction, heat conductivility and low thermal expansivity.As: 1. high strength, Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2. high heat conductance, (5,000W/mK); 3. high conductivity, carrier transport rate, (200,000cm 2/ V*s); 4. high specific surface area, (calculated value: 2,630m 2/ g).Especially its high conductivity matter, the textural property of large specific surface character and the nanoscale of its unimolecular layer two dimension, makes it in fields such as Materials science and electronics, have broad application prospects.
At present, the preparation method of Graphene has: mechanically peel method, chemical Vapor deposition process, graft process and oxidation-reduction method.The Graphene that wherein first two method obtains yields poorly, and the Graphene that the product of graft process contains a large amount of multilayers, these have all limited it to a certain extent in each field, particularly the application aspect matrix material.Oxidation-reduction method is to take natural flake graphite as raw material, from preparing graphene oxide, is that starting point is prepared Graphene.On graphene oxide, also contain a large amount of-OH and-COOH group, can carry out at an easy rate various chemical modifications, be expected to become the high quality filler of polymer nanocomposites.But just because of contain in graphite oxide-C-OH ,-C-O-C, the groups such as-COOH, thus show stronger polarity.The aerial less stable of dry graphite oxide, is easy to the moisture absorption and forms aquation graphite oxide.But when graphite oxide replaces after graphite oxide by generating nitrogen with ammonia gas react, stability can obviously strengthen.
Polypyrrole (PPy) has the electrochemical redox characteristic of higher room-temperature conductivity and completely reversibility, and charge storage ability is stronger, is easy to synthesize, and has the advantages such as good stability in air.Polypyrrole (PPy) is used to make biological inductor, functional molecular film, secondary cell and nonlinear optical device etc.
[summary of the invention]
The technical problem to be solved in the present invention is to provide the preparation method that a kind of nitrogen replaces graphene oxide/Pt/Polypyrrole composite material.
The technical scheme solving the problems of the technologies described above is as follows:
Nitrogen replaces a preparation method for graphene oxide/Pt/Polypyrrole composite material, mainly comprises the following steps:
(1) dry graphite oxide is packed in reactor, pass into successively the gas mixture of dry ammonia and ammonia thereof and argon gas, under 300-1000 ℃ (most preferably being 700 ℃), carry out nitrogen substitution reaction 0.5-6h (most preferably being 1h), obtain nitrogen and replace graphite oxide;
(2) nitrogen that obtains in step (1) is replaced to graphite oxide and add in dispersion agent, ultrasonic it is uniformly dispersed, make nitrogen and replace graphene oxide;
(3) in the nitrogen replacement graphene oxide of step (2), add pyrrole monomer, continue ultrasonic dispersion, make it form nitrogen and replace graphene oxide and pyrrole monomer mixed solution;
(4) under 0 ℃ of-25 ℃ of condition, in the mixed solution of step (3), slowly drip oxygenant, stirring reaction 3～24h, filtering reacting liquid obtains described nitrogen and replaces graphene oxide/Pt/Polypyrrole composite material.
Preferably, described nitrogen replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, also comprises the steps:
(5) nitrogen obtaining in described step (4) is replaced to graphene oxide/Pt/Polypyrrole composite material and wash, dry, obtain pure nitrogen and replace graphene oxide/Pt/Polypyrrole composite material.
Preferably, above-mentioned steps (1), graphite oxide is adopted with the following method and is made:
The Graphite Powder 99 that is 2: 1: 1 by mass ratio, Potassium Persulphate and Vanadium Pentoxide in FLAKES add in the vitriol oil of 80 ℃, stir, and more than cooling 6h, washing is to neutral, dry, obtains mixture; Then mixture is joined in the vitriol oil of 0 ℃, add again potassium permanganate, and in the oil bath of 35 ℃ after insulation reaction 2h, slowly add deionized water, adding subsequently concentration is the hydrogen peroxide solution of 30wt%, then carry out suction filtration, washing, suction filtration and drying treatment again, obtain graphite oxide.
Preferably, in step (1), in argon gas and ammonia gas mixture, ammonia accounts for 5%～30% (more preferably 10%) of gas mixture volume ratio.
Preferably, in step (2), the volume number that the nitrogen of every 100mg replaces the required dispersion agent of graphite oxide is 300～6000ml.
Preferably, described dispersion agent is any in water, methyl alcohol or ethanol.
Preferably, in step (3), the volume number that the nitrogen of every 100mg replaces the required pyrrole monomer of graphene oxide is 0.01～3ml.
Preferably, in step (4), the total mass number that the nitrogen of every 100mg replaces graphene oxide requisite oxygen agent is 0.04～12g.
Preferably, described oxygenant is FeCl 36H 2o, K 2s 2o 8, (NH 4) 2s 2o 8or KMnO 4in any.
Compared with prior art, the present invention has following beneficial effect:
The present invention first replaces graphite oxide to generate nitrogen replacement graphite oxide by nitrogen, strengthen its stability, then by nitrogen, replacing graphene oxide and pyrrole monomer in-situ polymerization obtains nitrogen and replaces graphene oxide/Pt/Polypyrrole composite material, preparation method is simple, the nitrogen preparing replaces the stable performance of graphene oxide/Pt/Polypyrrole composite material, has very high chemical property, can be applicable in high electrochemistry capacitance ultracapacitor and lithium ion battery electrode material.
[accompanying drawing explanation]
Fig. 1 is that nitrogen of the present invention replaces graphene oxide/Pt/Polypyrrole composite material preparation technology schema;
Fig. 2 is the SEM Electronic Speculum picture that in embodiment 1, nitrogen replaces graphene oxide/Pt/Polypyrrole composite material.
[embodiment]
A kind of nitrogen provided by the invention replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, as shown in Figure 1, comprises the following steps:
(1) the 500 order Graphite Powder 99s, Potassium Persulphate and the Vanadium Pentoxide in FLAKES that by purity, are 99.5% add in the vitriol oil of 80 ℃, stir, and more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 35 ℃, keep after 2h, slowly add 920mL deionized water; After 15min, add 2.8L deionized water, then adding 50mL concentration is the hydrogen peroxide solution of 30wt% again, and mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, at 60 ℃ of vacuum-drying 48h, obtain graphite oxide with the hydrochloric acid that 5L concentration is 10%; Wherein, Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES mass ratio are 2: 1: 1;
(2) dry graphite oxide is packed in reactor, pass into successively the gas mixture of dry ammonia and ammonia thereof and argon gas, under 300-1000 ℃ (most preferably being 700 ℃), carry out nitrogen substitution reaction 0.5-6h (most preferably being 1h), obtain nitrogen and replace graphite oxide;
(3) nitrogen that obtains in step (2) is replaced to graphene oxide and add in dispersion agent, ultrasonic it is uniformly dispersed, make nitrogen and replace graphene oxide;
(4) in step (3), add pyrrole monomer, continue ultrasonic dispersion, make it form nitrogen and replace graphene oxide and pyrrole monomer mixed solution;
(5) under 0 ℃ of-25 ℃ of condition, in step (4) mixed solution, slowly drip oxygenant, stirring reaction 3～24h, filtering reacting liquid obtains described nitrogen and replaces graphene oxide/Pt/Polypyrrole composite material;
(6) nitrogen obtaining in described step (5) is replaced to graphene oxide/Pt/Polypyrrole composite material and wash, dry, obtain pure nitrogen and replace graphene oxide/Pt/Polypyrrole composite material.
By the following examples nitrogen of the present invention being replaced to graphene oxide/Pt/Polypyrrole composite material preparation method is further elaborated.
Embodiment 1
Nitrogen replaces graphene oxide/Pt/Polypyrrole composite material preparation method, and its technical process is as follows:
(1) the 500 order Graphite Powder 99s, 10g Potassium Persulphate and the 10g Vanadium Pentoxide in FLAKES that by 20g purity, are 99.5% add in the vitriol oil of 80 ℃, stir, and more than cooling 6h, washing is to neutral, dry.Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on below 20 ℃, then in the oil bath of 35 ℃, keep after 2h, slowly add 920mL deionized water.After 15min, add 2.8L deionized water, then adding 50mL concentration is 30% hydrogen peroxide solution again, and mixture color becomes glassy yellow afterwards, suction filtration while hot, then wash, suction filtration, at 60 ℃ of vacuum-drying 48h, obtain graphite oxide with the hydrochloric acid that 5L concentration is 10%;
(2) after the graphite oxide obtaining in step (1) is dry, pack in reactor, pass into dry ammonia 0.5h, then pass into the gas mixture of ammonia and argon gas, described gas mixture reacts 1h with graphite oxide under 700 ℃ of left and right, obtains nitrogen and replaces graphite oxide; Wherein, in described gas mixture, ammonia accounts for 10% of mixed gas volume ratio, and argon gas is as the diluent gas of ammonia;
(3) nitrogen obtaining in step (2) is replaced to graphite oxide 100mg and join ultrasonic dispersion 10min in 1000mL methyl alcohol, so that it is uniformly dispersed, obtain nitrogen and replace graphene oxide, and the total mass number of this graphene oxide is about 100mg;
(4) in the described nitrogen replacement of step (3) graphene oxide, add the pyrrole monomer of 3mL through heavily steaming, and continue ultrasonic dispersion 10min formation nitrogen replacement graphene oxide and pyrrole monomer mixed solution;
(5), at 0 ℃, in step (4) mixed solution, be slowly added dropwise to FeCl 36H 2the aqueous solution that O (content 6g) concentration is 0.5mol/L, and stir 3h, make pyrrole monomer polymerization reaction take place.By reacting liquid filtering, the reaction product then filtration being obtained is used deionized water 200mL and acetone 200mL repetitive scrubbing successively, until filtrate is colourless; Finally, the black powder that washing is obtained is through 50 ℃ of vacuum-drying 48h in vacuum drying oven, and the nitrogen obtaining described in the present embodiment replaces graphene oxide/Pt/Polypyrrole composite material.
Utilize Na 2sO 4the nitrogen making as the three-electrode system test implementation example 1 of electrolytic solution replaces graphene oxide/Pt/Polypyrrole composite material electrochemical specific capacity.Nickel foam is cut into square electric pole piece, at 120 ℃, after dry 12h, weigh.Get nitrogen and replace graphene oxide/Pt/Polypyrrole composite material 3mg, at 80 ℃, dry 6h, then adds respectively 0.3mg acetylene black and splashes into 0.3mg ptfe emulsion, adds 6mL ethanol, ultrasonic dispersion 30min.Then with dropper, above-mentioned dispersant liquid drop is added on foam nickel electrode sheet, then, by the electrode slice dripping off dry 12h at 100 ℃, the weight that deducts foam nickel electrode after weighing show that effective nitrogen replaces the quality of graphene oxide/polypyrrole combination electrode material.By ready-made electrode slice at Na 2sO 4after soaking 12h in solution, measure its capacitive property.
Test result: the charge ratio capacity of ultracapacitor prepared by nitrogen replacement graphene oxide/Pt/Polypyrrole composite material that employing embodiment 1 makes is 335F/g, and specific discharge capacity is 326F/g, and efficiency for charge-discharge is 97.3%.
Fig. 2 is the SEM Electronic Speculum picture that in embodiment 1, nitrogen replaces graphene oxide/Pt/Polypyrrole composite material.As shown in the figure, the surface that nitrogen replaces graphene oxide lamella is coated by polypyrrole, has formed the matrix material of sandwich structure.
Embodiment 2
Nitrogen replaces graphene oxide/Pt/Polypyrrole composite material preparation method, and its technical process is as follows:
(1) preparation of graphite oxide, identical with (1) in embodiment 1;
(2) after the graphite oxide obtaining in step (1) is dry, pack in reactor, pass into dry ammonia 0.45h, then pass into the gas mixture of ammonia and argon gas, described gas mixture reacts 6h with graphite oxide at 300 ℃, obtain nitrogen and replace graphite oxide, in described gas mixture, ammonia accounts for 5% of mixed gas volume ratio, and argon gas is as the diluent gas of ammonia;
(3) nitrogen obtaining in step (2) is replaced to graphite oxide 100mg and add ultrasonic dispersion 60min in 300mL water to, so that it is uniformly dispersed, make nitrogen and replace graphene oxide, and the total mass number of this graphene oxide is about 100mg;
(4) then to step (3) nitrogen, replace in graphene oxide and add 0.01mL through the pyrrole monomer (analytical pure) of heavily steaming and continue ultrasonic dispersion 50min formation nitrogen replacement graphene oxide and pyrrole monomer mixed solution;
(5), at 25 ℃, in above-mentioned mixed solution, be slowly added dropwise to K 2s 2o 8the aqueous solution of (content 0.04g), and stir 24h, make pyrrole monomer polymerization reaction take place.By reacting liquid filtering, the reaction product then filtration being obtained is used deionized water 200mL and acetone 200mL repetitive scrubbing successively, until filtrate is colourless; Finally, the black powder that washing is obtained is through 50 ℃ of vacuum-drying 48h in vacuum drying oven, and the nitrogen obtaining described in the present embodiment replaces graphene oxide/Pt/Polypyrrole composite material.
Utilize Na 2sO 4the nitrogen making as the three-electrode system test implementation example 2 of electrolytic solution replaces graphene oxide/Pt/Polypyrrole composite material electrochemical specific capacity.Concrete operations are with embodiment 1.
Test result: the charge ratio capacity of ultracapacitor prepared by nitrogen replacement graphene oxide/Pt/Polypyrrole composite material that employing embodiment 2 makes is 278F/g, and specific discharge capacity is 260F/g, and efficiency for charge-discharge is 93.5%.
Embodiment 3
Nitrogen replaces graphene oxide/Pt/Polypyrrole composite material preparation method, and its technical process is as follows:
(1) preparation of graphite oxide, identical with (1) in embodiment 1;
(2) after the graphite oxide obtaining in step (1) is dry, pack in reactor, pass into dry ammonia 0.55h, then pass into the gas mixture of ammonia and argon gas, described gas mixture reacts 0.5h with graphite oxide at 1000 ℃, obtain nitrogen and replace graphite oxide, in described gas mixture, ammonia accounts for 30% of mixed gas volume ratio, and argon gas is as the diluent gas of ammonia;
(3) nitrogen obtaining in step (2) is replaced to graphite oxide 100mg and add ultrasonic dispersion 30min in 6000mL ethanol to, so that it is uniformly dispersed, obtain nitrogen and replace graphene oxide, and the total mass number of this graphene oxide is about 100mg;
(4) then to step (3) nitrogen, replace in graphene oxide and add 1.5mL through the pyrrole monomer of heavily steaming and continue ultrasonic dispersion 25min formation nitrogen replacement graphene oxide and pyrrole monomer mixed solution;
(5), at 15 ℃, in above-mentioned mixed solution, be slowly added dropwise to (NH 4) 2s 2o 8the aqueous solution that (content 5.5g) concentration is 0.5mol/L, and stir 15h, make pyrrole monomer polymerization reaction take place; By reacting liquid filtering, the reaction product then filtration being obtained is used deionized water 200mL and acetone 200mL repetitive scrubbing successively, until filtrate is colourless.Finally, the black powder that washing is obtained through 50 ℃ of vacuum-drying 48h, obtains nitrogen of the present invention and replaces graphene oxide/polymer composites in vacuum drying oven.
Utilize Na 2sO 4the nitrogen making as the three-electrode system test implementation example 3 of electrolytic solution replaces graphene oxide/Pt/Polypyrrole composite material electrochemical specific capacity.Concrete operations are with embodiment 1.
Test result: the charge ratio capacity of ultracapacitor prepared by nitrogen replacement graphene oxide/Pt/Polypyrrole composite material that employing embodiment 3 makes is 312F/g, and specific discharge capacity is 300F/g, and efficiency for charge-discharge is 96.1%.
Embodiment 4
Nitrogen replaces graphene oxide/Pt/Polypyrrole composite material preparation method, and its technical process is as follows:
(1) preparation of graphite oxide, identical with (1) in embodiment 1;
(2) after the graphite oxide obtaining in step (1) is dry, pack in reactor, pass into dry ammonia 0.5h, then pass into the gas mixture of ammonia and argon gas, described gas mixture reacts 1h with graphite oxide under 700 ℃ of left and right, obtain nitrogen and replace graphite oxide, in described gas mixture, ammonia accounts for 10% of mixed gas volume ratio, and argon gas is as the diluent gas of ammonia;
(3) nitrogen obtaining in step (2) is replaced to graphite oxide 100mg and join ultrasonic dispersion 10min in 1000mL methyl alcohol, so that it is uniformly dispersed, obtain nitrogen and replace graphene oxide, and the total mass number of this graphene oxide is about 100mg;
(4) then to step (3) nitrogen, replace in graphene oxide and add 3mL through the pyrrole monomer (analytical pure) of heavily steaming and continue ultrasonic dispersion 10min formation nitrogen replacement graphene oxide and pyrrole monomer mixed solution;
(5) at 0 ℃, in above-mentioned mixed solution, be slowly added dropwise to the aqueous solution that potassium permanganate (content 12g) concentration is 0.5mol/L, and stir 3h, make pyrrole monomer polymerization reaction take place; By reacting liquid filtering, the reaction product then filtration being obtained is used deionized water 200mL and acetone 200mL repetitive scrubbing successively, until filtrate is colourless; Finally, the black powder that washing is obtained is through 50 ℃ of vacuum-drying 48h in vacuum drying oven, and the nitrogen obtaining described in the present embodiment replaces graphene oxide/Pt/Polypyrrole composite material.
Utilize Na 2sO 4the nitrogen making as the three-electrode system test implementation example 4 of electrolytic solution replaces graphene oxide/Pt/Polypyrrole composite material electrochemical specific capacity.Concrete operations are with embodiment 1.
Test result: the charge ratio capacity of ultracapacitor prepared by nitrogen replacement graphene oxide/Pt/Polypyrrole composite material that employing embodiment 1 makes is 341F/g, and specific discharge capacity is 329F/g, and efficiency for charge-discharge is 96.5%.
Be more than for the illustrating of possible embodiments of the present invention, but this embodiment is not in order to limit the scope of the claims of the present invention, allly do not depart from the equivalence that skill spirit of the present invention does and implement or change, all should be contained in the scope of the claims of the present invention.

Claims (9)

1. nitrogen replaces a preparation method for graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, mainly comprises the following steps:
(1) dry graphite oxide is packed in reactor, pass into successively the gas mixture of dry ammonia and ammonia and argon gas, at 300-1000 ℃, carry out nitrogen substitution reaction 0.5-6h, obtain nitrogen and replace graphite oxide;
(2) nitrogen that obtains in step (1) is replaced to graphite oxide and add in dispersion agent, ultrasonic it is uniformly dispersed, make nitrogen and replace graphene oxide;
(3) to the described nitrogen of step (2), replace in graphene oxide and add pyrrole monomer, continue ultrasonic dispersion, make it form mixed solution;
(4) under 0 ℃ of-25 ℃ of condition, in step (3) mixed solution, slowly drip oxygenant, stirring reaction 3～24h, filtering reacting liquid obtains described nitrogen and replaces graphene oxide/Pt/Polypyrrole composite material;
In described step (1), in described argon gas and ammonia gas mixture, ammonia accounts for 5%～30% of mixed gas volume ratio.
2. nitrogen according to claim 1 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, also comprises the steps:
(5) nitrogen obtaining in described step (4) is replaced to graphene oxide/Pt/Polypyrrole composite material and wash, dry, obtain pure nitrogen and replace graphene oxide/Pt/Polypyrrole composite material.
3. nitrogen according to claim 1 and 2 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, the graphite oxide in described step (1) is to be made by following step:
The Graphite Powder 99 that is 2:1:1 by mass ratio, Potassium Persulphate and Vanadium Pentoxide in FLAKES add in the vitriol oil of 80 ℃, stir, and more than cooling 6h, washing is to neutral, dry, obtains mixture; Then mixture is joined in the vitriol oil of 0 ℃, then add potassium permanganate, and in the oil bath of 35 ℃ after insulation reaction 2h, slowly add deionized water, add subsequently hydrogen peroxide solution, then carry out suction filtration, washing, suction filtration and drying treatment again, obtain graphite oxide.
4. nitrogen according to claim 3 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, in described step (1), temperature of reaction during nitrogen substitution reaction is 700 ℃, and the reaction times is 1h.
5. nitrogen according to claim 1 and 2 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, in described step (2), the volume number that the nitrogen of every 100mg replaces the required dispersion agent of graphite oxide is 300～6000ml.
6. nitrogen according to claim 5 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, described dispersion agent is any in water, methyl alcohol or ethanol.
7. nitrogen according to claim 1 and 2 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, in described step (3), the volume number that the nitrogen of every 100mg replaces the required pyrrole monomer of graphene oxide is 0.01～3ml.
8. nitrogen according to claim 1 and 2 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, in described step (4), the total mass number that the nitrogen of every 100mg replaces graphene oxide requisite oxygen agent is 0.04～12g.
9. nitrogen according to claim 8 replaces the preparation method of graphene oxide/Pt/Polypyrrole composite material, it is characterized in that, described oxygenant is FeCl 36H 2o, K 2s 2o 8, (NH 4) 2s 2o 8or KMnO 4in any.
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CN103848988B (en) * 2014-02-27 2017-02-15 南京理工大学 Nitrogen-doped graphene/nickel ferrite/polyaniline nanometer composite material and preparation method for same
CN105253876A (en) * 2015-11-07 2016-01-20 合肥国轩高科动力能源有限公司 Preparation method of high-dispersion nitrogen-doped graphene
CN108841382A (en) * 2018-05-25 2018-11-20 江苏大学 A kind of carbon dots/polypyrrole composite fluorescence probe system and its preparation method and application
CN113926397B (en) * 2020-07-14 2022-11-01 厦门大学 Graphene pyrrole aerogel and preparation method and application thereof
CN113813889B (en) * 2021-09-29 2023-03-03 四川大学 Nitrogen-doped graphene aerogel microsphere as well as preparation method and application thereof

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