CN105967176A - Preparation method of cellular three-dimensional graphene - Google Patents
Preparation method of cellular three-dimensional graphene Download PDFInfo
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- CN105967176A CN105967176A CN201610323080.3A CN201610323080A CN105967176A CN 105967176 A CN105967176 A CN 105967176A CN 201610323080 A CN201610323080 A CN 201610323080A CN 105967176 A CN105967176 A CN 105967176A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- C01—INORGANIC CHEMISTRY
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a preparation method of cellular three-dimensional graphene. The preparation method comprises the following steps: performing ultrasonic dispersion and mixing of graphene oxide and phthalocyanine compound to obtain a graphene oxide/phthalocyanine composite precursor; and sintering the graphene oxide/phthalocyanine composite precursor by a temperature programmed sintering method through a solid-phase cracking process under inert gas protection for cracking and self-assembly of the raw materials to finally obtain a cellular three-dimensional graphene material. The preparation method disclosed by the invention has the advantages of simple process, high product purity and industrialization promotion; and the prepared composite material can be applied to the fields such as new energy, radiating materials and catalysts.
Description
Technical field
The invention belongs to field of preparation of graphene, be specifically related to the preparation method of a kind of cellular three-dimensional grapheme.
Background technology
Graphene is the carbon atom two-dimension plane structure with sp2 mode hydridization, and this hybrid form makes carbon atom and adjacent three carbon atoms become stable C-C key by σ key-like, and such bonding pattern gives the structure that Graphene is stable.But, Graphene self is a huge aromatic conjugated molecule, interact due to its hydrophobic structure and the strongest π-π of sheet interlayer and Van der Waals force makes it easier to stacking occurs and reunites, and in most actual application, typically require and Graphene is assembled into macro object, reunion between graphene layer and stacking can greatly reduce the effective area of Graphene, so that it gradually loses the physical property of the original excellence of Graphene.Become overcome Graphene to reunite in consideration of it, construct three-dimensional grapheme, discharge the one extremely efficient method of its excellent properties.
At present, the preparation research of three-dimensional grapheme attracts wide attention, and on the whole, current preparation scheme is concentrated mainly on template: i.e. soft template method and hard template method two kinds.Such as: Publication No.: CN
104291329 A、CN 103496695 A、CN 103663414 A、CN
The Chinese patent of 104319395 all uses freeze-drying that graphene oxide carries out process to obtain three dimensional structure Graphene, and this method, with water of crystallization as template, can prepare the three dimensional structure of porous, but the lyophilization cycle is longer；And Cai Dandan etc. are at Electrochimica Acta, 2014,139,96 103 report the method by etching silicon dioxide hard template successfully prepares the three dimensional structure Graphene that shape is homogeneous.It addition, Publication No.: CN
The Chinese patent of 104163421 A, CN 103332686A is then to have used the three dimensional skeletal structure of nickel foam and polymeric foam to carry out the load of Graphene, the Chinese patent of Publication No.: CN 102674321 is also same with three-dimensional porous metal as carrier, utilize chemical vapour deposition technique to grow, and then obtain three dimensional structure Graphene；Zhanwei Xu is at J. Phys. Chem.
The method that Lett.2012,3,2928 2933 is reported is then with CNT as supporting construction.
In sum, existing three-dimensional grapheme preparation method needs to utilize template to carry out structure establishment mostly, removes template the most again, this not only adds the complexity of production process, create more waste liquid simultaneously, it is difficult to produce in enormous quantities.Thus, the method for the solid phase cracking self assembly that the application uses will become one of optimal choice preparing three-dimensional grapheme.
Summary of the invention
The preparation method of the cellular three-dimensional grapheme that it is an object of the present invention to provide a kind of low cost, can prepare in a large number.
The technical scheme is that the preparation method of a kind of cellular three-dimensional grapheme, comprise the following steps:
(1) phthalocyanine compound is stirred in deionized water with graphene oxide mix, obtain graphene oxide/phthalocyanine composite precursor；
(2) use solid phase cracking process to be sintered under inert gas shielding by graphene oxide/phthalocyanine composite precursor, obtain cellular three-dimensional grapheme.
Further, step (1) method particularly includes: phthalocyanine compound is placed in ultrasonic disperse in deionized water and obtains phthalocyanine compound dispersion liquid, phthalocyanine compound dispersion liquid is mixed with graphene oxide water solution, centrifugation after mechanical agitation 12 ~ 36 h under room temperature, obtain blue tan precipitate, clean to neutral with deionized water, i.e. obtain graphene oxide/phthalocyanine composite precursor, in temperature is 40 ~ 60 DEG C of vacuum drying ovens, it is dried 24 ~ 48h, obtains final brown graphene oxide/phthalocyanine composite precursor.
Further, in step (2), noble gas is the one in argon, nitrogen, argon+hydrogen or nitrogen+hydrogen, and throughput is 10-50 cm3·min-1。
Further, in step (2), the method for sintering is: the method for sintering is to heat successively through 300 DEG C, 350 DEG C, 400 DEG C, 500 DEG C, 800 DEG C according to certain programming rate, is incubated Temperature fall after 1h, 1h, 1h, 4h, 8h respectively.
Further, one or more during phthalocyanine compound is metal-free phthalocyanine, Nickel Phthalocyanine, Phthalocyanine Zinc, Cobalt Phthalocyanine, CuPc or FePC.
Further, graphene oxide is 1 0.5 ~ 2 with the part by weight of phthalocyanine.
Further, graphene oxide uses the Hummers method improved, and prepares graphene oxide with crystalline graphite powder, concentrated sulphuric acid, strong phosphoric acid, potassium permanganate, deionized water, hydrogen peroxide, dilute hydrochloric acid for raw material.
Further, the preparation method of graphene oxide is: with crystalline graphite powder, concentrated sulphuric acid, strong phosphoric acid, potassium permanganate, deionized water, hydrogen peroxide, dilute hydrochloric acid as raw material, carries out weighing according to a certain ratio；Under the conditions of room-temperature water bath, in the three-necked bottle with condensing tube, add concentrated sulphuric acid and strong phosphoric acid nitration mixture, after mechanical agitation is back to room temperature to nitration mixture temperature；Adding crystalline graphite powder within half an hour in three times, room temperature mechanical stirs 1 ~ 3 hour；It is slowly added to potassium permanganate by several times, controls potassium permanganate addition speed and make system temperature be not higher than 40 DEG C；Treating that potassium permanganate charging is complete, obtain blackish green solution, liter high-temperature, to 40 ~ 60 DEG C, stirs 8 ~ 24h, obtains crystalline graphite powder oxidation stripper；Crystalline graphite powder is aoxidized and is slowly poured in the deionized water of ice cube under stripper mechanical agitation, obtain sepia mixing liquid, continue stirring until system is back to room temperature；Then pipetting hydrogen peroxide with pipet, dropping to mix liquid color is glassy yellow by brown stain.
Further, crystalline graphite powder: concentrated sulphuric acid: strong phosphoric acid: the ratio of potassium permanganate is 1g 90 ~ 150
ML 10 ~ 18 mL 3 ~ 10g, hydrogen peroxide concentration is 18 ~ 35%.
The present invention compared with prior art has the advantage that
The present invention uses solid phase cracking process, is processed by a step and obtains three-dimensional grapheme structure, and this synthetic method is the most efficient, it is to avoid the complicated tediously long experimentation such as lyophilization or chemical gaseous phase deposition, and is prone to prepare in a large number.
Accompanying drawing explanation
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.
Detailed description of the invention
Embodiment 1
Step A. prepares graphene oxide.
Step A1., with crystalline graphite powder, concentrated sulphuric acid, strong phosphoric acid, potassium permanganate, deionized water, hydrogen peroxide, dilute hydrochloric acid as raw material, carries out weighing；Wherein, crystalline graphite powder and concentrated sulphuric acid ratio are 1.5 g:180 mL, and crystalline graphite powder is 1.5 g:20 mL with the ratio of strong phosphoric acid, and graphite powder is 1.5 g:9 g with the ratio of potassium permanganate, and hydrogen peroxide concentration is 35%；
Step A2. room-temperature water bath, adds concentrated sulphuric acid and strong phosphoric acid nitration mixture, after mechanical agitation is back to room temperature to nitration mixture temperature in three-necked bottle, add crystalline graphite powder, being slowly added to potassium permanganate by several times, now system temperature slowly raises, and controls potassium permanganate addition speed and makes system temperature be not higher than 40 DEG C；Treating that potassium permanganate charging is complete, obtain blackish green solution, liter high-temperature, to 60 DEG C, stirs 12h, obtains crystalline graphite powder oxidation stripper；
Crystalline graphite powder is aoxidized under stripper mechanical agitation and is slowly poured in the deionized water of ice cube by step A3., obtains sepia mixing liquid, continues stirring until system is back to room temperature；Then pipetting hydrogen peroxide with pipet, dropping to mix liquid color is glassy yellow by brown stain；
Step B. prepares graphene oxide/phthalocyanine composite precursor:
Step B1. by 1.5 g metal-free phthalocyanine ultrasonic disperse in 100ml deionized water；
B1 dispersion liquid is poured in A3 by step B2., and room temperature mechanical stirs 48 h；
Step B2 is obtained mixed solution and is centrifuged separating by step B3., obtain blue tan precipitate, clean to neutral with deionized water, i.e. obtain graphene oxide/phthalocyanine composite precursor, in temperature is 60 DEG C of vacuum drying ovens, it is dried 24h, obtains final brown graphene oxide/phthalocyanine composite precursor；
Step C. prepares three-dimensional grapheme: uses solid phase cracking process to be placed in tube furnace by graphene oxide/phthalocyanine composite precursor and carries out the calcining that heats up；Concrete heating step is:
Weigh appropriate amount of sample after being ground uniformly by presoma and put in porcelain boat, with copper foil-clad porcelain boat surface, put in high temperature process furnances, be passed through throughput 25 cm3·min-1Argon, uses temperature programming method, heats successively through 300 DEG C, 350 DEG C, 400 DEG C, 500 DEG C, 800 DEG C according to certain programming rate, be incubated Temperature fall after 1h, 1h, 1h, 4h, 8h respectively.Taking out the sample after sintering and be cellular three-dimensional grapheme material, its pattern is as shown in Figure 1.The specific surface area of prepared cellular three-dimensional grapheme is 229.7
m2·g-1。
Embodiment 2
Implement according to the method shown in embodiment 1, difference only in B1 walks the addition of metal-free phthalocyanine be 0.5g, the noble gas of step C is nitrogen+hydrogen, and its throughput is 50 cm3·min-1.After solid phase cracking self assembly, the pattern of the cellular three-dimensional grapheme obtained is as in figure 2 it is shown, its specific surface area is 298.2
m2·g-1。
Embodiment 3
Implement according to the method shown in embodiment 1, difference only in B1 walks the addition of metal-free phthalocyanine be 3g, the noble gas of step C is nitrogen, and its throughput is 10 cm3·min-1.After solid phase cracking self assembly, the transmission electron microscope picture such as Fig. 3 of the cellular three-dimensional grapheme obtained, its specific surface area is 251.6 m2·g-1。
Embodiment 4
Implementing according to the method shown in embodiment 1, the Nickel Phthalocyanine for 1.5g that difference only adds in walking at B1, after solid phase cracking self assembly, as shown in Figure 4, its specific surface area is 313.9 m to the transmission electron microscope of the cellular three-dimensional grapheme obtained2·g-1。
Embodiment 5
Implementing according to the method shown in embodiment 1, the FePC for 1.5g that difference only adds in walking at B1, after solid phase cracking self assembly, the cellular three-dimensional grapheme obtained, its specific surface area is 301.8
m2·g-1。
Embodiment 6
Implementing according to the method shown in embodiment 1, the Cobalt Phthalocyanine for 1.5g that difference only adds in walking at B1, after solid phase cracks, the cellular three-dimensional grapheme obtained, its specific surface area is 364.2
m2·g-1。
Embodiment 7
Implementing according to the method shown in embodiment 1, the CuPc for 1.5g that difference only adds in walking at B1, after solid phase cracks, the cellular three-dimensional grapheme obtained, its specific surface area is 271.5
m2·g-1。
The above, above-described embodiment is only the detailed description of the invention of the present invention, any feature disclosed in this specification, unless specifically stated otherwise, all can be by other equivalences or there is the alternative features of similar purpose replaced；Disclosed all features or all methods or during step, in addition to mutually exclusive feature and/or step, all can be combined in any way.
Claims (9)
1. the preparation method of a cellular three-dimensional grapheme, it is characterised in that comprise the following steps:
(1) phthalocyanine compound is stirred in deionized water with graphene oxide mix, obtain graphene oxide/phthalocyanine composite precursor；
(2) use solid phase cracking process to be sintered under inert gas shielding by graphene oxide/phthalocyanine composite precursor, obtain cellular three-dimensional grapheme.
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 1, it is characterized in that, step (1) method particularly includes: phthalocyanine compound is placed in ultrasonic disperse in deionized water and obtains phthalocyanine compound dispersion liquid, phthalocyanine compound dispersion liquid is mixed with graphene oxide water solution, mechanical agitation 12 ~ 36 under room temperature
Centrifugation after h, obtains blue tan precipitate, cleans to neutral with deionized water, i.e. obtain graphene oxide/phthalocyanine composite precursor, be 40 ~ 60 in temperatureoC vacuum drying oven is dried 24 ~ 48h, obtains final brown graphene oxide/phthalocyanine composite precursor.
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 1, it is characterised in that in step (2), noble gas is the one in argon, nitrogen, argon+hydrogen or nitrogen+hydrogen, and throughput is 10 ~ 50 cm3·min-1。
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 1, it is characterised in that in step (2), the method for sintering is: the method for sintering is to heat successively through 300 according to certain programming rateoC、350 oC、400 oC、500 oC、800 oC, is incubated Temperature fall after 1h, 1h, 1h, 4h, 8h respectively.
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 1, it is characterised in that in step (1), phthalocyanine compound is one or more in metal-free phthalocyanine, Nickel Phthalocyanine, Phthalocyanine Zinc, Cobalt Phthalocyanine, CuPc or FePC.
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 1, it is characterised in that in step (1), graphene oxide is 1 0.5 ~ 2 with the part by weight of phthalocyanine compound.
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 1, it is characterized in that, in step (1), graphene oxide uses the Hummers method improved, and prepares graphene oxide with crystalline graphite powder, concentrated sulphuric acid, strong phosphoric acid, potassium permanganate, deionized water, hydrogen peroxide, dilute hydrochloric acid for raw material.
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 7, it is characterized in that, the preparation method of graphene oxide is: with crystalline graphite powder, concentrated sulphuric acid, strong phosphoric acid, potassium permanganate, deionized water, hydrogen peroxide, dilute hydrochloric acid as raw material, carries out weighing according to a certain ratio；Under the conditions of room-temperature water bath, in the three-necked bottle with condensing tube, add concentrated sulphuric acid and strong phosphoric acid nitration mixture, after mechanical agitation is back to room temperature to nitration mixture temperature；Adding crystalline graphite powder within half an hour in three times, room temperature mechanical stirs 1 ~ 3 hour；It is slowly added to potassium permanganate by several times, controls potassium permanganate addition speed and make system temperature be not higher than 40oC；Treating that potassium permanganate charging is complete, obtain blackish green solution, liter high-temperature, to 40 ~ 60 DEG C, stirs 8 ~ 24h, obtains crystalline graphite powder oxidation stripper；Crystalline graphite powder is aoxidized and is slowly poured in the deionized water of ice cube under stripper mechanical agitation, obtain sepia mixing liquid, continue stirring until system is back to room temperature；Then pipetting hydrogen peroxide with pipet, dropping to mix liquid color is glassy yellow by brown stain.
The preparation method of a kind of cellular three-dimensional grapheme the most according to claim 8, it is characterised in that crystalline graphite powder: concentrated sulphuric acid: strong phosphoric acid: the ratio of potassium permanganate is 1g 90 ~ 150 mL 10 ~ 18 mL 3 ~ 10g, and hydrogen peroxide concentration is 18 ~ 35%.
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Cited By (5)
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| 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 |
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| CN110078054A (en) * | 2019-05-10 | 2019-08-02 | 淮海工学院 | A kind of preparation method and applications of graphene-carbon nano tube three-dimensional composite |
| 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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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110078054A (en) * | 2019-05-10 | 2019-08-02 | 淮海工学院 | A kind of preparation method and applications of graphene-carbon nano tube three-dimensional composite |
| 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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