CN103086371A - Method for preparing hydrophobic graphene sponge - Google Patents
Method for preparing hydrophobic graphene sponge Download PDFInfo
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- CN103086371A CN103086371A CN2013100276248A CN201310027624A CN103086371A CN 103086371 A CN103086371 A CN 103086371A CN 2013100276248 A CN2013100276248 A CN 2013100276248A CN 201310027624 A CN201310027624 A CN 201310027624A CN 103086371 A CN103086371 A CN 103086371A
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Abstract
The invention discloses a method for preparing a hydrophobic graphene sponge. The method comprises the following steps: firstly performing freeze-drying on a dispersion solution of graphene oxide, then performing high-temperature treatment on a dried sample and finally performing carbon particle modification on the obtained sample to get the graphene sponge with super hydrophobicity and super lipophilicity. Compared with the sponge which is reported before, the sponge is quite low, and the adsorption capability can be improved by about 8 times. Therefore, the method has huge application value in the aspects of environmental protection and energy.
Description
Technical field
The present invention relates to a kind of method that improves the graphene sponge adsorptive power.
Background technology
Due to the leakage of crude oil and the pollution of industrial organic solvent, the water pollution problems in the whole world just becoming more and more serious (M.Toyoda, M.Inagaki, Spill Sci.Technol.Bull.2007,8,467; H.M.Choi, R.M.Cloud, Environ.Sci.Technol.1992,26,772), in order to address this problem, scientists has been developed various sorbent materials, and particularly we organize graphene sponge (H.C.Bi, the X.Xie for preparing not long ago, K.B.Yin, et al.Adv.Funct.Mater.2012,22,4421), has advantages of other traditional sorbent material separately, their shortcoming (D.Bastani, A.A.Safekordi, A.Alihosseini.et al.Sep.Purif.Technol.2006 have separately been overcome again simultaneously, 52,295; M.M.Radetic, D.M.Jocic, P.M.Jovanccic.et al.Environ.Sci.Technol.2003,37,1008), have huge value on the releasing water pollution problems.But in order to realize the commercial applications of this sponge, further improve its adsorptive power and become necessary selection, like this, just can adsorb more oil and organic solvent with sorbent material still less, thereby can significantly reduce costs.
Summary of the invention
Technical problem: the invention provides a kind of method for preparing the hydrophobic nature graphene sponge that sponge that makes has low-down density and excellent adsorption selectivity.
Technical scheme: the present invention prepares the method for hydrophobic nature graphene sponge, comprises the following steps:
at first graphite oxide is added in water solvent, ultra-sonic dispersion forms 3mg/ml to the graphene oxide dispersion liquid of 10mg/ml, at-10 ℃ to-176 ℃ temperature, described graphene oxide dispersion liquid is carried out lyophilize, then the product after lyophilize being carried out high temperature reduction processes, product after soon lyophilize is placed in the protection of the environment of nitrogen or argon gas, naturally cooling at least 5 minutes after annealing under 500 ℃ to 1000 ℃ of high temperature, at last the high temperature reduction products therefrom being carried out carbon granule modifies, the product that obtains after soon high temperature reduction processing, be placed in the flame calcination fully two to three seconds, obtain having the graphene sponge of ultraphobic water-based super-oleophilic.
In the present invention, the flame during carbon granule is modified is originated and is the burning of following arbitrary material: candle, alcohol, gasoline, diesel oil and various alkane derivative.
In the present invention, cryodesiccated concrete steps are: the graphene oxide dispersion liquid is placed in container, then container is placed in the environment of-10 ℃ to-176 ℃ and carries out freezingly, then freezing sample being put into freeze drier maybe can provide the container of low pressure to carry out drying treatment.
One aspect of the present invention utilizes the direct lyophilize of graphene oxide to increase temperature the sponge that reduction has obtained extremely-low density; On the other hand, utilize the burning of candle flame to carry out finishing to this sponge, thereby obtain practical graphene sponge super-hydrophobic but super oleophylic.Lyophilize and carbon granule are modified indispensable for the adsorption applications of graphene sponge, because be hydrophilic by the sponge that obtains after lyophilize and high temperature reduction, that is to say that this sponge does not have adsorption selectivity, therefore the crude oil leakage for the sea does not have extraordinary adsorptive power (because also suction simultaneously), can not realize the purpose that scrubbing separates with liquid liquid.In addition, the temperature of high temperature reduction is to be also necessary more than 500 ℃ because the temperature of general flame is 500 ℃ of left and right, if the temperature of reduction lower than this temperature, so follow-up flame treating probably can be destroyed the structure of graphene sponge.
Beneficial effect: the present invention can obtain low-density graphene sponge (0.9mg/cm by to the direct lyophilize of the dispersion liquid of graphite oxide
3), with respect to traditional preparation method such as hydrothermal method, sponge (tens mg/cm of the gained such as reductive agent reduction
3), density is low a lot.In addition, modify by the sponge after annealing is carried out carbon granule, given the characteristic of its hydrophobic oleophylic, thereby made this sponge can be used for adsorbed oil and organic solvent.Directly absorb water after the complete sponge annealing of lyophilize, therefore never the people uses it for the selective adsorption aspect, in order to reach good adsorption selectivity, must carry out to the sponge after annealing the carbon granule modification.Lower density has given this sponge huge adsorptive power.
The present invention modifies in conjunction with lyophilize and carbon granule, has realized the preparation of ultralight sponge, and the modification of carbon granule has been given this sponge and had characteristic hydrophobic but oleophylic, thereby made it have good adsorption selectivity.Ultralow density makes this sponge have potential using value in environment protection in conjunction with outstanding adsorption selectivity.
Description of drawings
Fig. 1 is the scanning electron microscope picture of the graphene sponge before the carbon granule unmodified.
Fig. 2 is the scanning electron microscope picture of the graphene sponge after carbon granule is modified.
Fig. 3 is the transmission electron microscope displaing micro picture of accompanying carbon granule on graphene film in sponge.
Fig. 4 is that graphene sponge after improving is to the contrast of oil and organic solvent adsorptive power and former prepared graphene sponge adsorptive power.
Embodiment
Below by embodiment, the present invention is done further and illustrate.
Embodiment 1:
The first step is got the graphene oxide dispersion liquid of 3mg/ml and pours in aluminium pot, then with aluminium pot as in liquid nitrogen (176 ℃), after dispersion liquid build-ups ice, it is put in freeze drier, carried out vacuum drying treatment 24 hours.
Second step, with dried sample, in tube furnace, logical nitrogen protection, naturally cooling after annealing at least 5 minutes under 1000 ℃ of high temperature.Fig. 1 is its scanning electron microscope picture, can significantly see the structure of porous.These vesicular structures have been given the extremely-low density of sponge just.
The 3rd step, second step is obtained early stage sponge as for burning in the candle flame, can obtain the super-hydrophobic graphene sponge of extremely-low density.Fig. 2 is its scanning electron microscope picture, can see that clearly the fine hair shape structure that is comprised of carbon granule is attached on graphene film, and this structure has given this sponge hydrophobic characteristic just.Fig. 3 is the transmission electron microscope picture of carbon granule, and as can be seen from the figure, these carbon granules are of a size of 30-50nm.
In the 4th step, the graphene sponge of gained has been carried out the adsorption rate test.The testing method of graphene sponge adsorption rate is: the graphene sponge of preparation is cut into fritter, and take every quality, being designated as W does, then every graphene sponge is put into solvent upon adsorption, graphene sponge fully adsorbs liquid to be measured, take at last the weight of every graphene sponge, be designated as W wet, the adsorption rate of graphene sponge is calculated by following formula:
Fig. 4 be graphene sponge to the adsorption rate of various oil and organic solvent, also adsorption rate and the adsorption rate of made graphene sponge are before contrasted in figure in addition, can find out, adsorption rate has improved more than 8 times.
Embodiment 2:
The preparation method is substantially with embodiment 1, and difference is: adopt-10 ℃ to carry out freezingly, the picture before and after prepared sponge flame treating is similar to respectively Fig. 1 and Fig. 2.
Embodiment 3:
The preparation method is substantially with embodiment 1, and difference is: adopt-50 ℃ to carry out freezingly, the concentration of graphene oxide dispersion liquid is 7mg/ml, and the picture before and after prepared sponge flame treating is similar to respectively Fig. 1 and Fig. 2.
Embodiment 4:
The preparation method is substantially with embodiment 1, and difference is: flame used is the ethanol burned flame, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 5
The preparation method is substantially with embodiment 3, and difference is: flame used is the flame of gasoline combustion, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
The preparation method is substantially with embodiment 3, and difference is: flame used is the flame of diesel combustion, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 7
The preparation method is substantially with embodiment 5, and difference is: flame used is the flame of methyl hydride combustion, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 8
The preparation method is substantially with embodiment 3, and difference is: flame used is the octane burned flame, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 9
The preparation method is substantially with embodiment 7, and difference is: flame used is the heptane burned flame, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 10
The preparation method is substantially with embodiment 7, and difference is: flame used is the decane burned flame, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 11
The preparation method is substantially with embodiment 8, and difference is: flame used is the dodecane burned flame, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 12
The preparation method is substantially with embodiment 1, and difference is: the concentration of graphene oxide dispersion liquid is 10mg/ml, and the high temperature reduction temperature is 500 ℃, and flame used is the dodecane burned flame, and the graphene sponge of gained is similar to Fig. 2, and carbon granule is similar to Fig. 3.
Embodiment 13
The preparation method is substantially with embodiment 12, and difference is: the high temperature reduction temperature is 750 ℃, and the graphene sponge of gained is similar to Fig. 1,2, and carbon granule is similar to Fig. 3.
Claims (3)
1. a method for preparing the hydrophobic nature graphene sponge, is characterized in that, the method comprises the following steps:
at first graphite oxide is added in water solvent, ultra-sonic dispersion forms 3mg/ml to the graphene oxide dispersion liquid of 10mg/ml, at-10 ℃ to-176 ℃ temperature, described graphene oxide dispersion liquid is carried out lyophilize, then the product after lyophilize being carried out high temperature reduction processes, product after soon lyophilize is placed in the protection of the environment of nitrogen or argon gas, annealing naturally cooling after at least 5 minutes under 500 ℃ to 1000 ℃ of high temperature, at last the high temperature reduction products therefrom being carried out carbon granule modifies, the product that obtains after soon high temperature reduction processing, be placed in the flame calcination fully two to three seconds, obtain having the graphene sponge of ultraphobic water-based super-oleophilic.
2. the method for preparing the hydrophobic nature graphene sponge according to claim 1, is characterized in that, during described carbon granule was modified, flame was originated and is the burning of following arbitrary material: candle, alcohol, gasoline, diesel oil and various alkane derivative.
3. the method for preparing the hydrophobic nature graphene sponge according to claim 1, it is characterized in that, described cryodesiccated concrete steps are: the graphene oxide dispersion liquid is placed in container, then container is placed in the environment of-10 ℃ to-176 ℃ and carries out freezingly, then freezing sample being put into freeze drier maybe can provide the container of low pressure to carry out drying treatment.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103466607A (en) * | 2013-09-09 | 2013-12-25 | 东南大学 | Graphene-metallic oxide nano-particle three-dimensional porous composite material |
| CN103482615A (en) * | 2013-09-09 | 2014-01-01 | 东南大学 | Preparation method of foamed graphene-ZnO composite material |
| CN104291329A (en) * | 2014-09-28 | 2015-01-21 | 北京理工大学 | Graphene sponge and preparation method thereof |
| CN104445153A (en) * | 2013-09-13 | 2015-03-25 | 中国科学院兰州化学物理研究所 | Method for macroscopic quantity preparation of carbon nano coil from graphene |
| CN104555979A (en) * | 2014-12-04 | 2015-04-29 | 中北大学 | Preparation method of novel fluoride-free and silicon-free super-hydrophobic carbon material |
| CN105110320A (en) * | 2015-06-26 | 2015-12-02 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of graphene porous material used for flue gas adsorption |
| CN105694915A (en) * | 2015-11-25 | 2016-06-22 | 北京旭碳新材料科技有限公司 | Composition for flame-retardant composite material and graphene flame-retardant foam and preparation method and application of foam |
| CN105694092A (en) * | 2016-02-01 | 2016-06-22 | 东南大学 | Preparation method of super-hydrophobic graphene sponge |
| CN106219524A (en) * | 2016-07-15 | 2016-12-14 | 东华大学 | A kind of low temperature prepares the method for shelly texture elastic graphite alkene foam |
| CN108102610A (en) * | 2017-12-21 | 2018-06-01 | 湖北大学 | A kind of based superhydrophobic thin films and preparation method thereof |
| CN109179822A (en) * | 2018-10-30 | 2019-01-11 | 薛燕 | A kind of water body processing apparatus convenient for purifying sterilizing |
| CN110156014A (en) * | 2019-05-28 | 2019-08-23 | 南昌大学 | It is a kind of based on alkylated reaction prepare hydrophobic strong acid Carbon Materials method and its hydrophobic strong acid Carbon Materials |
| CN111422856A (en) * | 2020-04-03 | 2020-07-17 | 常州富烯科技股份有限公司 | Method for flame reduction of graphene oxide film and preparation method of graphene film |
| CN113663366A (en) * | 2021-08-20 | 2021-11-19 | 鼎泰瑞通(北京)科技有限公司 | Preparation method of condensate structure body for marine oil spill microbial treatment |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103482615A (en) * | 2013-09-09 | 2014-01-01 | 东南大学 | Preparation method of foamed graphene-ZnO composite material |
| CN103482615B (en) * | 2013-09-09 | 2015-11-25 | 东南大学 | A kind of preparation method of spumescence Graphene-ZnO matrix material |
| CN103466607A (en) * | 2013-09-09 | 2013-12-25 | 东南大学 | Graphene-metallic oxide nano-particle three-dimensional porous composite material |
| CN104445153A (en) * | 2013-09-13 | 2015-03-25 | 中国科学院兰州化学物理研究所 | Method for macroscopic quantity preparation of carbon nano coil from graphene |
| CN104445153B (en) * | 2013-09-13 | 2016-09-21 | 中国科学院兰州化学物理研究所 | A kind of method being prepared charcoal nanometer roll by Graphene magnanimity |
| CN104291329B (en) * | 2014-09-28 | 2017-01-11 | 北京理工大学 | Graphene sponge and preparation method thereof |
| CN104291329A (en) * | 2014-09-28 | 2015-01-21 | 北京理工大学 | Graphene sponge and preparation method thereof |
| CN104555979A (en) * | 2014-12-04 | 2015-04-29 | 中北大学 | Preparation method of novel fluoride-free and silicon-free super-hydrophobic carbon material |
| CN105110320A (en) * | 2015-06-26 | 2015-12-02 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of graphene porous material used for flue gas adsorption |
| CN105694915A (en) * | 2015-11-25 | 2016-06-22 | 北京旭碳新材料科技有限公司 | Composition for flame-retardant composite material and graphene flame-retardant foam and preparation method and application of foam |
| CN105694092A (en) * | 2016-02-01 | 2016-06-22 | 东南大学 | Preparation method of super-hydrophobic graphene sponge |
| CN106219524A (en) * | 2016-07-15 | 2016-12-14 | 东华大学 | A kind of low temperature prepares the method for shelly texture elastic graphite alkene foam |
| CN108102610A (en) * | 2017-12-21 | 2018-06-01 | 湖北大学 | A kind of based superhydrophobic thin films and preparation method thereof |
| CN108102610B (en) * | 2017-12-21 | 2020-07-14 | 湖北大学 | Super-hydrophobic film and preparation method thereof |
| CN109179822A (en) * | 2018-10-30 | 2019-01-11 | 薛燕 | A kind of water body processing apparatus convenient for purifying sterilizing |
| CN110156014A (en) * | 2019-05-28 | 2019-08-23 | 南昌大学 | It is a kind of based on alkylated reaction prepare hydrophobic strong acid Carbon Materials method and its hydrophobic strong acid Carbon Materials |
| CN111422856A (en) * | 2020-04-03 | 2020-07-17 | 常州富烯科技股份有限公司 | Method for flame reduction of graphene oxide film and preparation method of graphene film |
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Application publication date: 20130508 |