CN104401987A - Preparation method of porous graphene flexible foam - Google Patents
Preparation method of porous graphene flexible foam Download PDFInfo
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- CN104401987A CN104401987A CN201410705370.5A CN201410705370A CN104401987A CN 104401987 A CN104401987 A CN 104401987A CN 201410705370 A CN201410705370 A CN 201410705370A CN 104401987 A CN104401987 A CN 104401987A
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Abstract
The invention relates to a preparation method of porous graphene flexible foam, which comprises the following steps: adding graphite oxide prepared by an improved Hummers method into distilled water to obtain a graphite oxide dispersion liquid, conducting ultrasonic dispersion to obtain a graphene oxide solution, and conducting vacuum filtration to obtain a graphene oxide film; reducing the graphene oxide film with a hydroiodic acid solution, and conducting washing and drying to obtain a graphene film; exposing the graphene film to infrared laser to obtain the porous graphene flexible foam. The preparation method provided by the invention is simple, and the prepared porous graphene flexible foam has a continuous three-dimensional porous structure, lower density and excellent mechanical properties.
Description
Technical field
The invention belongs to the preparation field of grapheme foam, particularly a kind of preparation method of porous graphene elastic foam.
Background technology
Since English physicist in 2004 successfully prepares Graphene, its special two-dirnentional structure and excellent performance have attracted the concern of numerous scientific research personnel.Research shows, Graphene is with SP by carbon atom
2the novel material of the individual layer sheet structure of the regular hexagon cycle honeycomb dot matrix Structure composing of hydridization composition, the Graphene thickness of the two-dimension single layer of a carbon atom thickness is only had to be about 0.35nm, the characteristics such as Graphene has high transparency and thermal conductivity, hard, specific conductivity is high of individual layer.The Graphene of two dimension can form three-dimensional graphite, the carbon nanotube of one dimension, the soccerballene etc. of zero dimension by stacking, winding, warpage etc.The excellent properties of Graphene is widely used at nanometer electronic device, transistor, sensing and aeronautical material.
Grapheme foam has high specific surface area and low-density porous nanometer material.Grapheme foam has a large amount of pore passage structures and higher porosity, has excellent absorption property.Grapheme foam material has its character singularity, and the application of porous graphene foam is studied widely.There is the grapheme foam of conductivity as framework material, the polymethyl methacrylate materials with self-healing properties is filled in vesicular structure, Graphene artificial skin (the Hou C with self-reparing capability can be prepared, et al.Scientific reports, 2013,3.).By carrying out special treatment process to the graphene film prepared, graphene film is made to have certain thermoelectricity capability, can be used for preparing the vital sign (Hou C, et al.Adv.Mater.DOI:10.1002/adma.201401367) that wearable device carrys out the monitoring record mankind.In addition, relevant utilize the pore space structure of grapheme foam and large specific surface area and good conductivity, prepare Graphene ultracapacitor (Deng W, et al.AppliedSurface Science, 2014,305:433-438.) etc.
At present, the preparation of grapheme foam adopts steam reduction method usually, steam is obtained by hydrazine hydrate can be heated at closed reactor, steam enters in graphene film lamella, many empty grapheme foam (Niu Z can be obtained, et al.Adv.Mater., 2012,24:4144 – 4150.).But these methods obtain the condition harshness that grapheme foam needs, and preparation flow is complicated, and cost is high.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of porous graphene elastic foam, and the method is simple to operate, and preparation method is quick; Prepared porous graphene elastic foam has excellent mechanical property, repeatedly can compress and can well keep its Young's modulus, and the graphene film after hydroiodic acid HI reduction has oleophilic drainage performance, can be used for except the oily matter in anhydrating.
The preparation method of a kind of porous graphene elastic foam of the present invention, comprising:
(1) graphite oxide prepared by the Hummers method improved: be oxidized 500 object Graphite Powder 99s with potassium permanganate and the vitriol oil, the filter cake that suction filtration obtains is placed in 60 DEG C of oven drying 24h, and grinding obtains graphite oxide powder.Graphite oxide prepared by the Hummers method of improvement is added in distilled water, obtains graphite oxide dispersion, ultrasonic disperse, obtain graphene oxide solution, vacuum filtration, obtain graphene oxide film;
(2) by above-mentioned graphene oxide film hydroiodic acid HI solution reduction, washing, dry, obtain graphene film;
(3) above-mentioned graphene film infrared laser is irradiated, obtain porous graphene elastic foam.
In described step (1), the concentration of graphite oxide dispersion is 1-10mg/mL.
In described step (1), the ultrasonic disperse time is 1-5h.
In described step (1), vacuum filtration is specially: graphene oxide solution adds in core filter funnel, uses cellulose mixture filter membrane vacuum filtration 48-72h.
The aperture of described cellulose mixture filter membrane is 0.22 μm.
In described step (2), the concentration expressed in percentage by volume of hydroiodic acid HI solution is 40-60%; Recovery time is 1-4h.
In described step (2), washing is deionized water wash 2-5 time; Drying is natural drying at room temperature.
The power density of described step (3) mid-infrared laser is 8 ~ 16w/cm
2, irradiation time is 5-60s.
The porous graphene elastic foam of the present invention by regulating graphite oxide concentration and volume to prepare different thickness, the time of adjustment hydroiodic acid HI reduction and concentration and control the pattern of porous graphene elastic foam pore space structure with the time of laser radiation.
Graphite oxide dispersion is obtained graphene oxide solution through ultrasonic stripping by the inventive method, and by graphene oxide solution vacuum filtration, in the process that moisture detaches, between graphene oxide, self-assembly forms graphene oxide film.Then obtain graphene film with hydroiodic acid HI reduction, then obtain porous graphene elastic foam by laser reduction.
Preparation method of the present invention is simple, and the porous graphene elastic foam obtained has the three-dimensional cavernous structure of continuous print, mechanical property that density is lower, excellent.In addition, this porous graphene elastic foam has the performance of lipophilicity substance.Therefore, obtained porous graphene elastic foam has very large application prospect in absorption, oily water separation etc.
beneficial effect
(1) working method of the present invention is simple, preparation process fast and easy;
(2) the porous graphene elastic foam prepared by the present invention has excellent mechanical property, repeatedly can compress and can well keep its Young's modulus, graphene film after hydroiodic acid HI reduction has oleophilic drainage performance, can be used for except the oily matter in anhydrating;
(3) the porous graphene elastic foam prepared by the present invention has larger specific surface area, inner void similar rhombus, there are stable elasticity, flexibility and electroconductibility, can having broad application prospects in the electronic component and absorb polluted matter etc. of deformation.
Accompanying drawing explanation
Fig. 1 embodiment 1 prepares the XRD figure spectrum of porous graphene elastic foam;
Fig. 2 embodiment 1 prepares the Raman spectrogram of porous graphene elastic foam;
Fig. 3 embodiment 1 prepares nitrogen adsorption desorption figure and the specific surface area of porous graphene elastic foam;
Fig. 4 embodiment 1 prepare porous graphene elastic foam strain-time m-stress curve;
Fig. 5 embodiment 2 prepares the SEM figure of porous graphene elastic foam;
Fig. 6 embodiment 3 prepares the SEM figure of porous graphene elastic foam.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
At room temperature, take the graphite oxide 160mg prepared by the Hummers method improved, be placed in the beaker of 100mL, then deionized water 40mL is made into the dispersion liquid that concentration is 4mg/mL, then beaker is put into ultrasonic pond to process 2h graphite oxide is peeled off as graphene oxide, obtain homodisperse graphene oxide solution 40mL; Vacuum filtration is carried out with the core filtration unit of 250mL, under room temperature, it is 0.22 μm of cellulose mixture filter membrane that the core of sand core funnel adds one deck aperture, fixes device and connects vacuum pump, scattered graphene oxide solution poured into, vacuum filtration 48h obtains graphene oxide film; The above-mentioned graphene oxide film that is attached together and cellulose mixture filter membrane are taken off and puts into the culture dish that diameter is 90mm, add the hydroiodic acid HI reductase 12 h that volume fraction is 50%, by washed with de-ionized water 3-5 time, namely at room temperature seasoning obtains graphene film; Be 8W/cm by power density
2infrared laser irradiate graphene film 10s, elastic graphite alkene foam can be obtained.Fig. 1 is the XRD figure spectrum of elastic graphite alkene foam prepared by the present embodiment, can find out: peak value 2 θ=10.8 ° of graphene film, correspond to (002) face, and peak value 2 θ=24.5 ° of grapheme foam, the carbon atom spacing obtaining grapheme foam is about 0.46nm.Fig. 2 is the Raman spectrogram of grapheme foam prepared by the present embodiment, can find out: in figure, significantly bimodal (D peak and G peak) all changes before and after hydroiodic acid HI reduction and laser radiation, the ratio I of peak value
d/ I
gbe increased to 1.43 after reduction by 1.08 before reducing, then become 1.45 after laser radiation, show that hydroiodic acid HI reduction makes graphenic surface structure change, reduction degree is very large, and laser radiation has reductive action while obtaining vesicular structure.Fig. 3 be the grapheme foam prepared of the present embodiment to the adsorption/desorption curve of nitrogen, obtain the specific surface area S of grapheme foam
bET=68.9m
3g
-1.Fig. 4 to be thickness prepared by this example be elastic graphite alkene foam of 1.26mm strain-time m-stress curve, can find out from figure, original volume can be returned to during the every second compression 60% of elasticity aerogel, and repeatedly this phenomenon rear can keep, can find out, during every second compression, the maximum stress of elastogel keeps stable value, shows that this elastogel can keep the stable of its mechanical property after repeatedly deformation.
Embodiment 2
At room temperature, take the graphite oxide 120mg prepared by the Hummers method improved, be placed in the beaker of 100mL, then deionized water 40mL is made into the dispersion liquid that concentration is 3mg/mL, then beaker is put into ultrasonic pond to process 1h graphite oxide is peeled off as graphene oxide, obtain homodisperse graphene oxide solution 40mL; Vacuum filtration is carried out with the core filtration unit of 250mL, under room temperature, it is 0.22 μm of cellulose mixture filter membrane that the core of sand core funnel adds one deck aperture, fixes device and connects vacuum pump, scattered graphene oxide solution poured into, vacuum filtration 48h obtains graphene oxide film; The above-mentioned graphene oxide film that is attached together and cellulose mixture filter membrane are lifted down and puts into the culture dish that diameter is 90mm, add the hydroiodic acid HI reductase 12 h that volume fraction is 50%, by washed with de-ionized water 3-5 time, namely at room temperature seasoning obtains graphene film; Be 8W/cm by power density
2infrared laser irradiate graphene film 10s, elastic graphite alkene foam can be obtained.The elastogel obtained is tested, finds that its thickness is thin relative to the sample in example 1, surveys its Raman spectrum, according to I
d/ I
gratio can be observed the sample of reducing degree substantially and in example 1 and be consistent.
Embodiment 3
At room temperature, take the graphite oxide 160mg prepared by the Hummers method improved, be placed in the beaker of 100mL, then deionized water 40mL is made into the dispersion liquid that concentration is 4mg/mL, then beaker is put into ultrasonic pond to process 2h graphite oxide is peeled off as graphene oxide, obtain homodisperse graphene oxide solution 40mL; Vacuum filtration is carried out with the core filtration unit of 250mL, under room temperature, it is 0.22 μm of cellulose mixture filter membrane that the core of sand core funnel adds one deck aperture, fixes device and connects vacuum pump, scattered graphene oxide solution poured into, vacuum filtration 48h obtains graphene oxide film; The above-mentioned graphene oxide film that is attached together and cellulose mixture filter membrane are lifted down and puts into the culture dish that diameter is 90mm, add the hydroiodic acid HI reductase 12 h that volume fraction is 50%, by washed with de-ionized water 3-5 time, namely at room temperature seasoning obtains graphene film; Be 16W/cm by power density
2infrared laser irradiate graphene film 10s, elastic graphite alkene foam can be obtained.The power density of the laser used when preparing sample by example 3 is the twice of example 1, and the dimensional thickness obtaining sample increases to some extent; Survey its Raman spectrum, can from I
d/ I
gfind out, the sample reducing degree in example 3 in the reducing degree of sample and example 1 is basically identical.
Claims (8)
1. a preparation method for porous graphene elastic foam, comprising:
(1) graphite oxide prepared by the Hummers method of improvement is added in distilled water, obtain graphite oxide dispersion, ultrasonic disperse, obtain graphene oxide solution, vacuum filtration, obtain graphene oxide film;
(2) by above-mentioned graphene oxide film hydroiodic acid HI solution reduction, washing, dry, obtain graphene film;
(3) above-mentioned graphene film infrared laser is irradiated, obtain porous graphene elastic foam.
2. the preparation method of a kind of porous graphene elastic foam according to claim 1, is characterized in that: in described step (1), the concentration of graphite oxide dispersion is 1-10mg/mL.
3. the preparation method of a kind of porous graphene elastic foam according to claim 1, is characterized in that: in described step (1), the ultrasonic disperse time is 1-5h.
4. the preparation method of a kind of porous graphene elastic foam according to claim 1, it is characterized in that: in described step (1), vacuum filtration is specially: graphene oxide solution adds in core filter funnel, use cellulose mixture filter membrane vacuum filtration 48-72h.
5. the preparation method of a kind of porous graphene elastic foam according to claim 4, is characterized in that: the aperture of described cellulose mixture filter membrane is 0.22 μm.
6. the preparation method of a kind of porous graphene elastic foam according to claim 1, is characterized in that: in described step (2), the concentration expressed in percentage by volume of hydroiodic acid HI solution is 40-60%; Recovery time is 1-4h.
7. the preparation method of a kind of porous graphene elastic foam according to claim 1, is characterized in that: in described step (2), washing is deionized water wash 2-5 time; Drying is natural drying at room temperature.
8. the preparation method of a kind of porous graphene elastic foam according to claim 1, is characterized in that: the power density of described step (3) mid-infrared laser is 8 ~ 16w/cm
2, irradiation time is 5-60s.
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| CN106672944A (en) * | 2016-12-15 | 2017-05-17 | 东华大学 | Graphene foam film, and preparation and application thereof |
| CN106773143A (en) * | 2016-12-06 | 2017-05-31 | 东华大学 | A kind of near infrared light mutagens shape Graphene/NIPAAm laminated films and its preparation and application |
| CN106732738A (en) * | 2017-02-15 | 2017-05-31 | 东华大学 | A kind of Graphene/g C3N4Three-dimensional network laminated film and its preparation and application |
| CN108002366A (en) * | 2017-11-10 | 2018-05-08 | 清华大学 | Graphene solar energy water cleaning foam and its preparation method and application |
| CN108467026A (en) * | 2018-01-16 | 2018-08-31 | 中国科学院上海应用物理研究所 | Porous graphene material and its preparation method and application |
| WO2019071943A1 (en) * | 2017-10-13 | 2019-04-18 | 浙江大学 | Independent self-supporting graphene film and preparation method therefor |
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| CN106773143A (en) * | 2016-12-06 | 2017-05-31 | 东华大学 | A kind of near infrared light mutagens shape Graphene/NIPAAm laminated films and its preparation and application |
| CN106672944A (en) * | 2016-12-15 | 2017-05-17 | 东华大学 | Graphene foam film, and preparation and application thereof |
| CN106732738A (en) * | 2017-02-15 | 2017-05-31 | 东华大学 | A kind of Graphene/g C3N4Three-dimensional network laminated film and its preparation and application |
| CN106732738B (en) * | 2017-02-15 | 2019-08-06 | 东华大学 | A kind of graphene/g-C3N4Three-dimensional network laminated film and its preparation and application |
| WO2019071943A1 (en) * | 2017-10-13 | 2019-04-18 | 浙江大学 | Independent self-supporting graphene film and preparation method therefor |
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| CN108002366A (en) * | 2017-11-10 | 2018-05-08 | 清华大学 | Graphene solar energy water cleaning foam and its preparation method and application |
| CN108002366B (en) * | 2017-11-10 | 2020-10-27 | 清华大学 | Graphene solar water cleaning foam and preparation method and application thereof |
| CN108467026A (en) * | 2018-01-16 | 2018-08-31 | 中国科学院上海应用物理研究所 | Porous graphene material and its preparation method and application |
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