CN103553033B - The preparation method of grapheme material - Google Patents
The preparation method of grapheme material Download PDFInfo
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- CN103553033B CN103553033B CN201310555544.XA CN201310555544A CN103553033B CN 103553033 B CN103553033 B CN 103553033B CN 201310555544 A CN201310555544 A CN 201310555544A CN 103553033 B CN103553033 B CN 103553033B
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Abstract
The invention discloses a kind of preparation method of grapheme material, mainly comprise the oxidation intercalation of raw graphite, ultrasonic stripping obtains graphene oxide, reduction reaction generate Graphene, ultrasonic wave added be separated prepares graphene powder material four steps.Present method is simple to operate, and reaction conditions gentleness is easy to control, and made grapheme material specific surface area is large, homogeneous, is suitable as extraction sorbing material.
Description
Technical field
The present invention relates to materials synthesis and complex sample pre-treatment field, specifically, relate to the preparation method of grapheme material.
Background technology
Just the very big research interest of scientific circles' especially material science has been caused since grapheme material is obtained first from 2004.Grapheme material is a kind of Novel Carbon Nanomaterials with two-dimension plane structure, there is specific surface area large, satisfactory mechanical property, the features such as stable chemical nature, a large amount of conjugated pi electron is had on graphene sheet layer surface, stronger electrostatic adhesion can be produced, Graphene is a planar structure simultaneously, upper and lower surface both provides great loading capacity, so, grapheme material is counted as a kind of excellent sorbing material, in recent years, have and grapheme material is applied to the report in sample pre-treatments field (see Qian Liu as sorbent material, Jianbo Shi, Guibin Jiang,
trAC Trends in Analytical Chemistry, 2012,
37, 1).
At present, the synthetic method of grapheme material mainly contain mechanically peel method (K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigorieva, A.A.Firsov,
science, 2004,
306, 666), epitaxial growth method (C.Berger, Z.M.Song, X.B.Li, X.S.Wu, N.Brown, C.Naud, D.Mayou, T.B.Li, J.Hass, A.N.Marchenkov, E.H.Conrad, P.N.First, W.A.de Heer,
science2006,
312, 1191), chemical Vapor deposition process (K.S.Kim, Y.Zhao, H.Jang, S.Y.Lee, J.M.Kim, K.S.Kim, J.-H. Ahn, P.Kim, J.-Y.Choi, B.H.Hong,
nature, 2009,
457, 706), oxidation reduction process (S.J.Park, R.S.Ruoff,
nature Nanotechnology, 2009,
4, 217) etc.First three methods can prepare high-quality grapheme material, but cost is higher, and complicated operation, condition are wayward and productive rate is lower, and oxidation reduction process is widely applied because of its feature such as low cost, high yield.
Also there are some problems in practice in oxidation reduction process, the oxidation of graphite material is one of the method important step, in prior art, is generally first prepare dry graphite oxide powder, and then being distributed to ultrasonic stripping in the aqueous solution, this technique is loaded down with trivial details, consuming time and charge stripping efficiency is lower.Publication number is the molten liquid phase preparation process that the Chinese patent of CN101613098A reports a kind of Graphene, but its graphite oxidation complex process, process is comparatively loaded down with trivial details.In addition, as sorbing material, the specific surface area of graphene powder is the important factor affecting its absorption property, and grapheme material prepared in prior art exists self agglomeration problems and causes the product that cannot obtain bigger serface, and this is also the still unsolved difficult problem in one, this field.At present, sample pre-treatments field is very big to the demand of sorbing material, can prepare the Graphene sorbing material with bigger serface have very large practical application meaning with simple, economic method.
Summary of the invention
The object of this invention is to provide a kind of ultrasonic wave added preparation method of grapheme material, to prepare the graphene powder material with bigger serface.
The object of the present invention is achieved like this:
The preparation method of grapheme material comprises the following steps:
(1) the oxidation intercalation of graphite material:
Original graphite powder is distributed in strong acid under whipped state, then under condition of ice bath, strong oxidizer is added, 12 ~ 60 h are reacted at ambient temperature after removing ice bath, then under condition of ice bath, in system, add water and continue stirring 0.5 ~ 10 h, subsequently to adding hydrogen peroxide in system and mixture being poured out, wash with water to neutrality, obtain the solution phase of graphite oxide; Wherein the ratio of each material is original graphite powder: strong acid: strong oxidizer: water: g:30 ~ 100, mL:2 ~ 6, g:30 ~ 65, hydrogen peroxide=1 mL:1 ~ 10 mL;
(2) ultrasonic stripping obtains graphene oxide:
The graphite oxide solution of preparation be distributed to further mutually in water, under 100 ~ 1000 w intensity, ultrasonic stripping 0.5 ~ 10 h obtains the dispersion liquid of graphene oxide; Wherein the ratio of water and original graphite powder is 1.5 ~ 6 L:1 g;
(3) graphene oxide reduction generates Graphene:
In graphene oxide dispersion, add hydrazine hydrate, react 0.5 ~ 10 h under 60 ~ 100 DEG C of conditions and obtain graphene dispersing solution; When wherein using volumetric concentration to be the hydrazine hydrate of 80 %, the ratio of consumption and original graphite powder is 15 ~ 30 mL:1 g;
(4) ultrasonic wave added is separated and prepares graphene powder material:
Filtered the graphene dispersing solution that obtains, then transferred in methyl alcohol rapidly by Graphene solid, and be placed in ultrasonic wave washing and be no less than 1 min, washing times is no less than 1 time; Then change methyl alcohol into water, again wash; Washing time and number of times require same methyl alcohol; Finally, the Graphene solid obtained by suction filtration is added to the water, and the ratio of water and original graphite powder is 50 ~ 100 mL:1 g, and be fully dispersed into atherosclerotic in ultrasonic wave after, lyophilize, obtains graphene powder material.
In the ultrasonic wave added synthetic method of described grapheme material, strong acid used in step (1) is a kind of in the vitriol oil, concentrated nitric acid, perchloric acid or their combination.
In the ultrasonic wave added synthetic method of described grapheme material, in step (1), strong oxidizer used is a kind of in potassium permanganate, Potcrate, sodium chlorate, Potassium Persulphate, SODIUMNITRATE and potassium bichromate or their combination.
Require lower based on grapheme material to the degree of oxidation of requisite oxygen graphite, namely the feature peeled off and require can be met by the interlamellar spacing increased between monolayer carbon atom of oxidation to a certain degree, in the preparation method of grapheme material provided by the present invention, the graphite oxide reaction of synthesis intercalation is at room temperature carried out all the time, this not only makes reaction conditions gentle, be suitable for the technology controlling and process in large-scale industrial production, and, made graphite oxide not only can meet the preparation demand of grapheme material, also make it directly can complete stripping through supersound process, not only save time, also assures that good degree of scatter, thus make made graphene powder material have larger specific surface area.Further, in the separation, washing process of Graphene product, stop the gathering of material self to be lumpd using ultrasonic as supplementary means all the time, thus improve final product specific surface area further, and then ensure its good absorption property.The caking rendezvous problem of material when graphene preparation method provided by the invention effectively prevent preparation, its specific surface area improves 3 ~ 6 times than prior art, and its absorption property is also corresponding to be significantly improved.
Accompanying drawing explanation
In Fig. 1, Figure 1B, Fig. 1 D is the scanning electron microscope (SEM) photograph of the grapheme material that embodiment 1 prepares, Figure 1A, Fig. 1 C is the scanning electron microscope (SEM) photograph (wherein the magnification of Figure 1A and Figure 1B is 5000 times, and the magnification of Fig. 1 C and Fig. 1 D is 50000 times) of the grapheme material that comparative example 1 prepares in the conventional way.
Fig. 2 is in embodiment 4, the color atlas of sample after grapheme material process, and wherein A is the color atlas of actual sample, and B is the color atlas of mark-on sample.
Fig. 3 is in embodiment 5, the contrasting colour spectrogram of sample before and after grapheme material process, and wherein A is the color atlas before mark-on sample preparation, and B is the color atlas after mark-on sample preparation, and C is the color atlas after actual sample process.
Embodiment
Specific area measuring in embodiment: BET specific surface area assay method, TriStar II 3020 specific surface area measuring instrument.
Embodiment 1
Taking 1 g Graphite Powder 99 is distributed in 45 mL sulfuric acid (98%), 3 g potassium permanganate are added under ice bath and whipped state, 24 h are reacted under removing ice bath room temperature condition, in system, 60 mL water are added under condition of ice bath, in system, 3 mL hydrogen peroxide are added after continuing stirring 2 h, mixture poured out and washes with water to neutrality, obtaining the solution phase of graphite oxide.
Obtained graphite oxide solution is distributed to mutually further in 2 L water, 800 w are ultrasonic peels off 1 h, under 90 DEG C of water bath condition, add 20 mL hydrazine hydrate (v/v, 80 %) react 1 h, obtain graphene dispersing solution and by its suction filtration, then the Graphene solid obtained transferred to rapidly in 300 mL methyl alcohol, and be placed in ultrasonic wave washing 2 times, each 3 min; Then wash 5 times with water, each 2 min, finally, by the Graphene solid dispersal that obtains in 60 mL water, be fully dispersed into atherosclerotic in ultrasonic wave after, lyophilize, obtains graphene powder material, and specific area measuring is 812 m
2/ g.
Contrast said process, in the conventional way synthesizing graphite alkene material:
Taking 1 g Graphite Powder 99 is distributed in 45 mL sulfuric acid (98%), 3 g potassium permanganate are added under ice bath and whipped state, remove ice bath, temperature rises to 35 DEG C and keeps 4 h, adds 60 mL water subsequently under condition of ice bath in system, again temperature is risen to 98 DEG C and continue stirring 12 h, then in system, add 3 mL hydrogen peroxide, mixture is poured out and washes with water to neutrality, suction filtration, under the solid obtained being placed in 60 DEG C of conditions, dry 72 h, obtain oxidation graphite solid.
The oxidation graphite solid obtained is joined in 2 L water, ultrasonic 5 h of 800 w carry out disperseing, peeling off, under 90 DEG C of water bath condition, add 20 mL hydrazine hydrates (80 %) and react 1 h, obtaining graphene dispersing solution and by its suction filtration, then the Graphene solid obtained transferred to rapidly in 300 mL methyl alcohol, washing by stirring, suction filtration again after washing, repeats 2 times; Then with water repeated washing 5 times again, finally, the Graphene solid obtained by suction filtration carries out lyophilize, obtains graphene powder material, and specific area measuring is 202 m
2/ g.
Embodiment 2
Taking 1 g Graphite Powder 99 is distributed in 30 mL perchloric acid, 2 g Potassium Persulphates are added under ice bath and whipped state, 12 h are reacted under room temperature condition, then under condition of ice bath, in system, 30 mL water are added, in system, 1 mL hydrogen peroxide is added after continuing stirring 0.5 h, mixture poured out and washes with water to neutrality, obtaining the solution phase of graphite oxide.
Obtained graphite oxide solution is distributed to mutually further in 1.5 L water, 100 w are ultrasonic peels off 0.5 h, under 60 DEG C of water bath condition, add 15 mL hydrazine hydrates (80 %) and react 0.5 h, obtain graphene dispersing solution and by its suction filtration, then the Graphene solid obtained is transferred to rapidly in 200 mL methyl alcohol, and be placed in ultrasonic wave and wash 1 min; Then again wash with water, by the Graphene solid dispersal that obtains in 50 mL water, be fully dispersed into atherosclerotic in ultrasonic wave after, carry out lyophilize, obtain graphene powder material.
Embodiment 3
Taking 1 g Graphite Powder 99 is distributed in 65 mL nitric acid, 6 g SODIUMNITRATE are added under ice bath and whipped state, 60 h are reacted under removing ice bath room temperature condition, in system, 100 mL water are added under condition of ice bath, in system, 10 mL hydrogen peroxide are added after continuing stirring 10 h, mixture poured out and washes with water to neutrality, obtaining the solution phase of graphite oxide.
Obtained graphite oxide solution is distributed to mutually further in 6 L water, 1000 w are ultrasonic peels off 10 h, under 100 DEG C of oil bath conditions, add 30 mL hydrazine hydrates (80 %) and react 10 h, obtain graphene dispersing solution and by its suction filtration, then the Graphene solid obtained is transferred to rapidly in 1000 mL methyl alcohol, and be placed in ultrasonic wave washing 3 times, each 2 min; Then again wash with water, finally, the Graphene solid dispersal obtained by suction filtration, in 100 mL water, after being fully dispersed into atherosclerotic, carries out lyophilize, obtain graphene powder material in ultrasonic wave.
Grapheme material prepared by the embodiment 4 the present invention application in pharmaceutical extraction is separated
Graphene powder prepared by the embodiment of the present invention 1 is applied to the extracting and separating of sulfa drugs in ambient water:
Taking 20 mg graphene powders loads in 3 mL solid phase extraction columns, pillar two ends are filled with sieve plate respectively and prevent material from revealing, after pre-treatment being carried out to pillar with methyl alcohol and ultrapure water, get 20 mL environmental water samples (0.45 μm of filter membrane) and pass through pillar, with 1 mL 10% methanol-water washing pillar, 1 mL 5% ammonia-methyl alcohol carries out wash-out, collect elutriant, fluorescent derivatization laggard liquid chromatography-fluorimetric detector analysis, as shown in Figure 2, sample after the process of Graphene solid phase extraction column in spectrogram target peak noiseless, the rate of recovery >=95% as calculated, proof absorption property is good.
Embodiment 5 the present invention prepares the application of grapheme material in drug residue of food detects
Graphene powder prepared by the embodiment of the present invention 2 is applied to the detection of sulfa drug residue in milk:
Make and prepared microcolumn according to the method in embodiment 4, measure 2 mL milk samples (after process) by pillar, 1 mL 5% methanol-water washing pillar, 1 mL 5% ammonia-methyl alcohol carries out wash-out, collect elutriant also to dry up with nitrogen, redissolve laggard liquid-phase chromatographic analysis by moving phase.Color atlas as can be seen from Fig. 3 before and after sample preparation, to target compound absorption fully (as calculated the rate of recovery >=97%), sample after treatment decontamination effect improving is obvious for this Graphene sorbent material.
Embodiment 6 the present invention prepares the application of grapheme material in agricultural-food drug residue detects
Graphene powder prepared by the embodiment of the present invention 3 is applied to the detection that in tealeaves, kelthane is residual:
Make and prepared microcolumn according to the method in embodiment 4, measure 5 mL Tea Samples by pillar, 1 mL milli-Q water pillar, 2 mL eluent ethyl acetates, collect elutriant, nitrogen dries up, and 1 mL normal hexane redissolves laggard gas chromatographic analysis.The gained rate of recovery as calculated >=90%.
The contrast of grapheme material prepared by embodiment 7 the present invention and grapheme material prepared by traditional method is investigated:
When keeping other conditions constant, the grapheme material that grapheme material in embodiment 4,5,6 changes as preparing in the conventional way in embodiment 1 is operated, as calculated, the corresponding rate of recovery is respectively 78%, 42%, 50%, significantly lower than the gained rate of recovery in embodiment 4,5,6.
Above embodiment is only for illustration of the specific embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; in the ken that described exercising ordinary skill possesses; the any amendment done within the spirit and principles in the present invention, equivalent to substitute and improvement etc., it all should be encompassed within the technical scheme scope of request of the present invention protection.
Claims (3)
1. a preparation method for grapheme material, is characterized in that, the method comprises the steps:
The oxidation intercalation of graphite material:
Original graphite powder is distributed in strong acid under whipped state, then under condition of ice bath, strong oxidizer is added, 12 ~ 60 h are reacted at ambient temperature after removing ice bath, then under condition of ice bath, in system, add water and continue stirring 0.5 ~ 10 h, subsequently to adding hydrogen peroxide in system and mixture being poured out, wash with water to neutrality, obtain the solution phase of graphite oxide; Wherein the ratio of each material is original graphite powder: strong acid: strong oxidizer: water: g:30 ~ 100, mL:2 ~ 6, g:30 ~ 65, hydrogen peroxide=1 mL:1 ~ 10 mL;
Ultrasonic stripping obtains graphene oxide:
The graphite oxide solution of preparation be distributed to further mutually in water, under 100 ~ 1000W intensity, ultrasonic stripping 0.5 ~ 10 h obtains the dispersion liquid of graphene oxide; Wherein the ratio of water and original graphite powder is 1.5 ~ 6 L:1 g;
Graphene oxide reduction generates Graphene:
In graphene oxide dispersion, add hydrazine hydrate, react 0.5 ~ 10 h under 60 ~ 100 DEG C of conditions and obtain graphene dispersing solution; When wherein using volumetric concentration to be the hydrazine hydrate of 80 %, the ratio of consumption and original graphite powder is 15 ~ 30 mL:1 g;
Ultrasonic wave added is separated prepares graphene powder material:
Filtered the graphene dispersing solution that obtains, then transferred in methyl alcohol rapidly by Graphene solid, and be placed in ultrasonic wave washing and be no less than 1 min, washing times is no less than 1 time; Then change methyl alcohol into water, again wash; Washing time and number of times require same methyl alcohol; Finally, the Graphene solid obtained by suction filtration is added to the water, and the ratio of water and original graphite powder is 50 ~ 100 mL:1 g, and be fully dispersed into atherosclerotic in ultrasonic wave after, lyophilize, obtains graphene powder material.
2. the preparation method of grapheme material according to claim 1, is characterized in that: strong acid used in step (1) is a kind of in the vitriol oil, concentrated nitric acid, perchloric acid or their combination.
3. the preparation method of grapheme material according to claim 1, is characterized in that: in step (1), strong oxidizer used is a kind of in potassium permanganate, Potcrate, sodium chlorate, Potassium Persulphate, SODIUMNITRATE and potassium bichromate or their combination.
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| CN104030279A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Method for preparing graphene through acetylacetone reduction |
| CN104525118B (en) * | 2015-01-04 | 2017-10-03 | 兰州大学 | A kind of preparation method of high-efficient graphite alkene oil absorption material |
| CN105148880A (en) * | 2015-07-16 | 2015-12-16 | 东华大学 | Preparation method and application method for graphene microsphere solid-phase extractant |
| CN105047882A (en) * | 2015-09-09 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing lithium-sulfur battery positive pole material |
| CN106115669B (en) * | 2016-06-20 | 2019-02-12 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene oxide |
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| CN107910532B (en) * | 2017-11-20 | 2020-09-01 | 复旦大学 | Preparation method of graphene-coated nickel cobalt lithium manganate composite material |
| CN110171819A (en) * | 2019-06-11 | 2019-08-27 | 北京鼎臣石墨科技有限公司 | A method of efficiently preparing graphene |
| CN111646462B (en) * | 2020-04-21 | 2022-09-30 | 东北大学 | Method for preparing high-quality reduced graphene oxide by high-current pulsed electron beam |
| CN113582168A (en) * | 2020-04-30 | 2021-11-02 | 北京超思电子技术有限责任公司 | Graphene preparation method based on mixed inorganic acid solvent |
| CN113092537A (en) * | 2021-03-30 | 2021-07-09 | 海南聚能科技创新研究院有限公司 | Quadrupole type conductivity electrode capable of improving seawater conductivity measurement accuracy and preparation method and application thereof |
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