CN105967176B - A kind of preparation method of cellular three-dimensional grapheme - Google Patents
A kind of preparation method of cellular three-dimensional grapheme Download PDFInfo
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- CN105967176B CN105967176B CN201610323080.3A CN201610323080A CN105967176B CN 105967176 B CN105967176 B CN 105967176B CN 201610323080 A CN201610323080 A CN 201610323080A CN 105967176 B CN105967176 B CN 105967176B
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Abstract
The invention discloses a kind of preparation method of cellular three-dimensional grapheme; graphene oxide is with phthalocyanine compound after ultrasonic disperse mixes; obtain graphene oxide/phthalocyanine composite precursor; with solid phase cracking process by graphene oxide/phthalocyanine composite precursor under inert gas shielding; the method sintered using temperature programming; cracking, the self assembly of raw material are carried out, cellular three-dimensional grapheme material is finally made.Present invention process flow is simple, and product purity is high, is easy to industrialization, prepared composite can apply to the fields such as new energy, heat sink material, catalyst.
Description
Technical field
The invention belongs to field of preparation of graphene, and in particular to a kind of preparation method of cellular three-dimensional grapheme.
Background technology
Graphene is the two-dimension plane structure of carbon atom hydridization in a manner of sp2, and this hybrid form causes carbon atom and phase
Three adjacent carbon atoms form stable C-C keys by σ keys, and such bonding pattern assigns graphene stable structure.However,
Graphene itself is a huge aromatic conjugated molecule, due to its hydrophobic structure and piece interlayer it is very strong π-π interaction and
Van der Waals force makes it easier to occur to stack and reunite, and in most practical applications, it usually needs graphene is assembled into
Macro object, reunion and stacking between graphene layer can greatly reduce the effective area of graphene, so that it is gradually lost
Graphene original excellent physical property.Overcome graphene to reunite in consideration of it, constructing three-dimensional grapheme and turning into, it is excellent to discharge its
A kind of extremely efficient method of different in nature energy.
At present, the preparation research of three-dimensional grapheme attracts wide attention, and on the whole, current preparation scheme mainly collects
In in template：That is two kinds of soft template method and hard template method.Such as：Publication No.：CN 104291329 A、CN 103496695
A, A, the CN 104319395 of CN 103663414 Chinese patent to graphene oxide handle using freeze-drying
To three-dimensional structure graphene, using the crystallization water as template porous three-dimensional structure can be made, but be freeze-dried the cycle in this method
It is longer；And Cai Dandan etc. is in Electrochimica Acta, 2014,139,96-103 report it is hard by etching silicon dioxide
The homogeneous three-dimensional structure graphene of shape is successfully made in the method for template.In addition, Publication No.：CN 104163421 A、CN
103332686A Chinese patent is then that the three dimensional skeletal structure for having borrowed nickel foam and polymeric foam carries out the negative of graphene
Carry, Publication No.：CN 102674321 Chinese patent is also equally using three-dimensional porous metal as carrier, utilizes chemical vapor deposition
Area method is grown, and then obtains three-dimensional structure graphene；Zhanwei Xu in J. Phys. Chem. Lett.2012,3,
2928 2933 methods reported are then using CNT as supporting construction.
In summary, existing three-dimensional grapheme preparation method needs to carry out structure establishment, Ran Houzai using template mostly
Template is removed, this not only adds the complexity of production process, while generates more waste liquid, it is difficult to produce in enormous quantities.Cause
And the method for the solid phase cracking self assembly that the application uses is by as one of optimal selection for preparing three-dimensional grapheme.
The content of the invention
It is an object of the present invention to provide a kind of low cost, the preparation method for the cellular three-dimensional grapheme that can largely prepare.
The technical scheme is that：A kind of preparation method of cellular three-dimensional grapheme, comprises the following steps：
（1）Phthalocyanine compound is stirred in deionized water with graphene oxide, it is multiple to obtain graphene oxide/phthalocyanine
Close presoma；
（2）Graphene oxide/phthalocyanine composite precursor is sintered under inert gas shielding using solid phase cracking process,
Obtain cellular three-dimensional grapheme.
Further, step（1）Specific method be：Phthalocyanine compound is placed in ultrasonic disperse in deionized water and obtains phthalein
Cyanine compound dispersion liquid, phthalocyanine compound dispersion liquid is mixed with graphene oxide water solution, at room temperature the h of mechanical agitation 12 ~ 36
After centrifuge, obtain blue tan precipitate, cleaned with deionized water to neutrality, that is, obtain graphene oxide/phthalocyanine it is compound before
Drive body, 24 ~ 48h dried in temperature is 40 ~ 60 DEG C of vacuum drying chambers, obtain final brown graphene oxide/phthalocyanine it is compound before
Drive body.
Further, step（2）In, inert gas is one kind in argon gas, nitrogen, argon gas+hydrogen or nitrogen+hydrogen,
Throughput is 10-50 cm3·min-1。
Further, step（2）In, the method for sintering is：The method of sintering is added successively according to certain programming rate
Heat passes through 300 DEG C, 350 DEG C, 400 DEG C, 500 DEG C, 800 DEG C, is incubated Temperature fall after 1h, 1h, 1h, 4h, 8h respectively.
Further, phthalocyanine compound is in metal-free phthalocyanine, Nickel Phthalocyanine, Phthalocyanine Zinc, Cobalt Phthalocyanine, CuPc or FePC
One or more.
Further, the part by weight of graphene oxide and phthalocyanine is 1 ︰ 0.5 ~ 2.
Further, graphene oxide uses improved Hummers methods, with crystalline graphite powder, the concentrated sulfuric acid, concentrated phosphoric acid, height
Potassium manganate, deionized water, hydrogen peroxide, watery hydrochloric acid are that raw material prepares graphene oxide.
Further, the preparation method of graphene oxide is：With crystalline graphite powder, the concentrated sulfuric acid, concentrated phosphoric acid, potassium permanganate,
Deionized water, hydrogen peroxide, watery hydrochloric acid are raw material, carry out weighing according to a certain ratio；Under the conditions of room-temperature water bath, in condenser pipe
Three-necked bottle in add the concentrated sulfuric acid and concentrated phosphoric acid nitration mixture, after mechanical agitation is back to room temperature to nitration mixture temperature；Divide within half an hour
Crystalline graphite powder is added three times, and room temperature mechanical stirs 1 ~ 3 hour；Potassium permanganate is slowly added to by several times, and control potassium permanganate adds
Speed makes system temperature be not higher than 40 DEG C；Treat that potassium permanganate charging finishes, obtain blackish green solution, raise temperature to 40 ~ 60 DEG C,
8 ~ 24h is stirred, obtains crystalline graphite powder oxidation stripper；Crystalline graphite powder is aoxidized and has slowly been poured under stripper mechanical agitation
In the deionized water of ice cube, sepia mixing liquid is obtained, continues stirring until system is back to room temperature；Then pipetted with pipette
Hydrogen peroxide, it is glassy yellow to be added dropwise to mixing liquid color by brown stain.
Further, crystalline graphite powder：The concentrated sulfuric acid：Concentrated phosphoric acid：The ratio of potassium permanganate is the mL ︰ 10 ~ 18 of 1g ︰ 90 ~ 150
ML 3 ~ 10g of ︰, hydrogen peroxide concentration are 18 ~ 35%.
The present invention has the following advantages that compared with prior art：
The present invention uses solid phase cracking process, handles to obtain three-dimensional grapheme structure by a step, the synthetic method is simply high
Effect, the complicated tediously long experimentation such as freeze-drying or chemical vapor deposition is avoided, and be easy to largely prepare.
Brief description of the drawings
Fig. 1 is that embodiment 1 is prepared into three-dimensional grapheme scanning electron microscope (SEM) photograph.
Fig. 2 is that embodiment 2 is prepared into three-dimensional grapheme scanning electron microscope (SEM) photograph.
Fig. 3 is that embodiment 3 is prepared into three-dimensional grapheme transmission electron microscope picture.
Fig. 4 is that embodiment 4 is prepared into three-dimensional grapheme transmission electron microscope picture.
Embodiment
Embodiment 1
Step A. prepares graphene oxide.
Step A1. using crystalline graphite powder, the concentrated sulfuric acid, concentrated phosphoric acid, potassium permanganate, deionized water, hydrogen peroxide, watery hydrochloric acid as
Raw material, carry out weighing；Wherein, crystalline graphite powder and concentrated sulfuric acid ratio are 1.5 g：180 mL, crystalline graphite powder and concentrated phosphoric acid
Ratio is 1.5 g：The ratio of 20 mL, graphite powder and potassium permanganate is 1.5 g：9 g, hydrogen peroxide concentration 35%；
Step A2. room-temperature water baths, the concentrated sulfuric acid and concentrated phosphoric acid nitration mixture, mechanical agitation to nitration mixture temperature are added in three-necked bottle
After being back to room temperature, crystalline graphite powder is added, is slowly added to potassium permanganate by several times, now system temperature slowly raises, and controls Gao Meng
Sour potassium, which adds speed, makes system temperature be not higher than 40 DEG C；Treat that potassium permanganate charging finishes, obtain blackish green solution, rise temperature is extremely
60 DEG C, 12h is stirred, obtains crystalline graphite powder oxidation stripper；
Crystalline graphite powder is aoxidized and is slowly poured under stripper mechanical agitation in the deionized water of ice cube by step A3., is obtained
To sepia mixing liquid, continue stirring until system is back to room temperature；Then hydrogen peroxide is pipetted with pipette, is added dropwise to mixed liquor
Body color is glassy yellow by brown stain；
Step B. prepares graphene oxide/phthalocyanine composite precursor：
Step B1. is by 1.5 g metal-free phthalocyanines ultrasonic disperses in 100ml deionized waters；
Step B2. pours into B1 dispersion liquids in A3, and room temperature mechanical stirs 48 h；
Step B2 is obtained mixed solution and is centrifuged by step B3., blue tan precipitate is obtained, with deionized water
Clean to neutrality, that is, obtain graphene oxide/phthalocyanine composite precursor, 24h is dried in temperature is 60 DEG C of vacuum drying chambers,
Obtain final brown graphene oxide/phthalocyanine composite precursor；
Step C. prepares three-dimensional grapheme：Graphene oxide/phthalocyanine composite precursor is placed in by pipe using solid phase cracking process
Heating calcining is carried out in formula stove；Specifically heating step is：
It is put into appropriate amount of sample is weighed after presoma grinding uniformly in porcelain boat, with copper foil-clad porcelain boat surface, is put into high temperature
In tube furnace, the cm of throughput 25 is passed through3·min-1Argon gas, using temperature programming method, add successively according to certain programming rate
Heat passes through 300 DEG C, 350 DEG C, 400 DEG C, 500 DEG C, 800 DEG C, is incubated Temperature fall after 1h, 1h, 1h, 4h, 8h respectively.Take out
Sample after sintering is cellular three-dimensional grapheme material, and its pattern is as shown in Figure 1.Prepared cellular three-dimensional graphite
The specific surface area of alkene is 229.7 m2·g-1。
Embodiment 2
Implement according in the method shown in embodiment 1, the addition of metal-free phthalocyanine is 0.5g only in B1 steps for difference, step
Rapid C inert gas is nitrogen+hydrogen, and its throughput is 50 cm3·min-1.After cracking self assembly by solid phase, obtain
The pattern of cellular three-dimensional grapheme is as shown in Fig. 2 its specific surface area is 298.2 m2·g-1。
Embodiment 3
Implement according in the method shown in embodiment 1, the addition of metal-free phthalocyanine is 3g only in B1 steps for difference, step
C inert gas is nitrogen, and its throughput is 10 cm3·min-1.After cracking self assembly by solid phase, what is obtained is cellular
The transmission electron microscope picture of three-dimensional grapheme such as Fig. 3, its specific surface area are 251.6 m2·g-1。
Embodiment 4
Implement according in the method shown in embodiment 1, distinguish the Nickel Phthalocyanine for 1.5g only added in being walked in B1, pass through
After solid phase cracking self assembly, the transmission electron microscope of obtained cellular three-dimensional grapheme is as shown in figure 4, its specific surface area is
313.9 m2·g-1。
Embodiment 5
Implement according in the method shown in embodiment 1, distinguish the FePC for 1.5g only added in being walked in B1, pass through
After solid phase cracking self assembly, obtained cellular three-dimensional grapheme, its specific surface area is 301.8 m2·g-1。
Embodiment 6
Implement according in the method shown in embodiment 1, distinguish the Cobalt Phthalocyanine for 1.5g only added in being walked in B1, pass through
After solid phase cracking, obtained cellular three-dimensional grapheme, its specific surface area is 364.2 m2·g-1。
Embodiment 7
Implement according in the method shown in embodiment 1, distinguish the CuPc for 1.5g only added in being walked in B1, pass through
After solid phase cracking, obtained cellular three-dimensional grapheme, its specific surface area is 271.5 m2·g-1。
It is described above, the embodiment of above-described embodiment only present invention, any spy disclosed in this specification
Sign, unless specifically stated otherwise, can alternative features equivalent by other or with similar purpose replaced；Disclosed all spies
Sign or all methods or during the step of, can group in any way in addition to mutually exclusive feature and/or step
Close.
Claims (8)
1. a kind of preparation method of cellular three-dimensional grapheme, it is characterised in that comprise the following steps：
(1) phthalocyanine compound is placed in ultrasonic disperse in deionized water and obtains phthalocyanine compound dispersion liquid, by phthalocyanine compound point
Dispersion liquid mixes with graphene oxide water solution, is centrifuged at room temperature after 12~36h of mechanical agitation, obtains blue tan precipitate,
Cleaned with deionized water to neutrality, that is, obtain graphene oxide/phthalocyanine composite precursor, be 40~60 DEG C of vacuum drying in temperature
24~48h is dried in case, obtains final brown graphene oxide/phthalocyanine composite precursor；
(2) graphene oxide/phthalocyanine composite precursor is sintered under inert gas shielding using solid phase cracking process, obtained
Cellular three-dimensional grapheme.
A kind of 2. preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that in step (2),
Inert gas is one kind in argon gas, nitrogen, argon gas+hydrogen or nitrogen+hydrogen, and throughput is 10~50cm3·min-1。
A kind of 3. preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that in step (2),
The method of sintering is：The method of sintering be according to certain programming rate heat successively by 300 DEG C, 350 DEG C, 400 DEG C, 500
DEG C, 800 DEG C, respectively be incubated 1h, 1h, 1h, 4h, 8h after Temperature fall.
A kind of 4. preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that in step (1),
Phthalocyanine compound is the one or more in metal-free phthalocyanine, Nickel Phthalocyanine, Phthalocyanine Zinc, Cobalt Phthalocyanine, CuPc or FePC.
A kind of 5. preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that in step (1),
The part by weight of graphene oxide and phthalocyanine compound is 1 ︰ 0.5~2.
A kind of 6. preparation method of cellular three-dimensional grapheme according to claim 1, it is characterised in that in step (1),
Graphene oxide uses improved Hummers methods, with the crystalline graphite powder, concentrated sulfuric acid, concentrated phosphoric acid, potassium permanganate, deionized water, double
Oxygen water, watery hydrochloric acid are that raw material prepares graphene oxide.
A kind of 7. preparation method of cellular three-dimensional grapheme according to claim 6, it is characterised in that graphene oxide
Preparation method be：Using crystalline graphite powder, the concentrated sulfuric acid, concentrated phosphoric acid, potassium permanganate, deionized water, hydrogen peroxide, watery hydrochloric acid as original
Material, carries out weighing according to a certain ratio；Under the conditions of room-temperature water bath, the concentrated sulfuric acid and dense phosphorus are added in the three-necked bottle with condenser pipe
Sour nitration mixture, after mechanical agitation is back to room temperature to nitration mixture temperature；Add crystalline graphite powder, room temperature mechanical in three times within half an hour
Stirring 1~3 hour；Potassium permanganate is slowly added to by several times, and control potassium permanganate, which adds speed, makes system temperature be not higher than 40 DEG C；Treat
Potassium permanganate charging finishes, and obtains blackish green solution, and rise temperature stirs 8~24h, obtain crystalline graphite powder to 40~60 DEG C
Aoxidize stripper；Crystalline graphite powder is aoxidized and is slowly poured under stripper mechanical agitation in the deionized water of ice cube, obtains palm fibre
Brown mixing liquid, continue stirring until system is back to room temperature；Then hydrogen peroxide is pipetted with pipette, is added dropwise to mixing liquid face
Color is glassy yellow by brown stain.
A kind of 8. preparation method of cellular three-dimensional grapheme according to claim 7, it is characterised in that crystalline flake graphite
Powder：The concentrated sulfuric acid：Concentrated phosphoric acid：The ratio of potassium permanganate is 1g ︰ 90~150mL ︰ 10~18mL, 3~10g of ︰, hydrogen peroxide concentration 18
~35%.
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| CN108439371A (en) * | 2016-12-13 | 2018-08-24 | 无锡格致新材料研发科技有限公司 | A kind of preparation method of three-dimensional (3D) graphene |
| CN107134574A (en) * | 2017-06-07 | 2017-09-05 | 信阳师范学院 | The method for preparing the cellular redox graphene stannic disulfide compounds of 3D |
| CN110078054B (en) * | 2019-05-10 | 2022-11-29 | 淮海工学院 | Preparation method and application of graphene-carbon nanotube three-dimensional compound |
| CN111013623A (en) * | 2019-12-13 | 2020-04-17 | 西北大学 | Nitrogen-doped graphene catalyst and preparation method thereof |
| CN111589465A (en) * | 2020-06-03 | 2020-08-28 | 浙江理工大学 | Preparation method and application of high-dispersity three-dimensional porous carbon-based metal catalyst |
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