CN103553033A - Method for preparing graphene material - Google Patents
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Abstract
The invention discloses a method for preparing a graphene material. The method mainly comprises the following four steps of oxidizing and intercalating raw material graphite, ultrasonically stripping to obtain graphene oxide, carrying out a reduction reaction to generate graphene, and performing ultrasonic auxiliary separation to prepare a graphene powder material. The method is simple to operate, the reaction conditions are mild and easily controlled, and the prepared graphene material is large in specific surface area, uniform in texture and suitable for serving as an extraction and adsorption material.
Description
Technical field
The present invention relates to material and synthesize and complex sample pre-treatment field, specifically, relate to the preparation method of grapheme material.
Background technology
Grapheme material has just caused the especially very big research interest of material science of scientific circles since 2004 make first.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, on graphene sheet layer surface, there is a large amount of conjugated pi electron, can produce stronger electrostatic adhesion, Graphene is a planar structure simultaneously, upper and lower surface all provides great loading capacity, so, grapheme material is counted as a kind of good sorbing material, in recent years, the existing report that is applied to sample pre-treatments field using grapheme material as sorbent material (is shown in Qian Liu, 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 be prepared high-quality grapheme material, but cost is higher, and complicated operation, condition is wayward and productive rate is lower, and oxidation reduction process is widely applied because of features such as its low cost, high yields.
Also there are in practice some problems in oxidation reduction process, the oxidation of graphite material is one of the method important step, in prior art, is generally first to prepare dry graphite oxide powder, and then being distributed to ultrasonic peeling off in the aqueous solution, this technique is loaded down with trivial details, consuming time and charge stripping efficiency is lower.Publication number is the solution phase preparation method that the Chinese patent of CN101613098A has been reported 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 an important factor that affects its absorption property, and in prior art, prepared grapheme material exists self agglomeration problems and causes obtaining the product of bigger serface, and this is also a still unsolved difficult problem of 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 with simple, economic method and have very large practical application meaning.
Summary of the invention
The ultrasonic assistant preparation method that the object of this invention is to provide a kind 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 99 is distributed in strong acid under whipped state, then under condition of ice bath, add strong oxidizer, after removing ice bath, react at ambient temperature 12～60 h, then under condition of ice bath, in system, add water and continue to stir 0.5～10 h, with adding hydrogen peroxide in backward 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 99: strong acid: strong oxidizer: water: g:30～100, mL:2～6, g:30～65, hydrogen peroxide=1 mL:1～10 mL;
(2) ultrasonic peeling off obtains graphene oxide:
The graphite oxide solution of preparation is further distributed in water mutually, ultrasonicly under 100～1000 w intensity peels off the dispersion liquid that 0.5～10 h obtains graphene oxide; Wherein the ratio of water and original Graphite Powder 99 is 1.5～6 L:1 g;
(3) graphene oxide reduction generates Graphene:
In graphene oxide dispersion liquid, add hydrazine hydrate, under 60～100 ℃ of conditions, react 0.5～10 h and make graphene dispersing solution; While wherein using volumetric concentration to be the hydrazine hydrate of 80 %, the ratio of consumption and original Graphite Powder 99 is 15～30 mL:1 g;
(4) ultrasonic auxiliary separating is from preparing graphene powder material:
The graphene dispersing solution that obtains is filtered, then Graphene solid is transferred in methyl alcohol rapidly, 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 washing; Washing time and number of times require same methyl alcohol; Finally, the Graphene solid that suction filtration is obtained is added to the water, and the ratio of water and original Graphite Powder 99 is 50～100 mL:1 g, is fully dispersed into after atherosclerotic in ultrasonic wave, and lyophilize, obtains graphene powder material.
In the ultrasonic assisted synthesizing method of described grapheme material, in step (1), strong acid used is a kind of in the vitriol oil, concentrated nitric acid, perchloric acid or their combination.
In the ultrasonic assisted synthesizing 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.
Based on grapheme material, to the degree of oxidation of required graphite oxide, require lower, by the interlamellar spacing between oxidation increase monolayer carbon atom to a certain degree, can meet the feature of peeling off requirement, in the preparation method of grapheme material provided by the present invention, the graphite oxide reaction of synthetic 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 through supersound process, can complete and peel off, not only save time, also guaranteed good degree of scatter, thereby make made graphene powder material there is larger specific surface area.Further, in the separation of Graphene product, washing process, using all the time the ultrasonic gathering caking that stops material self as supplementary means, thereby further improve final product specific surface area, and then guarantee the absorption property that it is good.The caking rendezvous problem of material when graphene preparation method provided by the invention has effectively been avoided preparation, its specific surface area improves 3～6 times than prior art, and its absorption property is corresponding significantly improving also.
Accompanying drawing explanation
In Fig. 1, Figure 1B, Fig. 1 D are the scanning electron microscope (SEM) photograph of the grapheme material for preparing of embodiment 1, Figure 1A, Fig. 1 C be take 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 grapheme material prepared by traditional method for comparative example 1.
Fig. 2 is in embodiment 4, the color atlas of sample after grapheme material is processed, and the color atlas that wherein A is actual sample, 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 is processed, 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 is processed.
Embodiment
Specific area measuring in embodiment: BET specific area measuring method, TriStar II 3020 specific surface area measuring instruments.
Embodiment 1
Taking 1 g Graphite Powder 99 is distributed in 45 mL sulfuric acid (98%), under ice bath and whipped state, add 3 g potassium permanganate, remove and under ice bath room temperature condition, react 24 h, under condition of ice bath, in system, add 60 mL water, continue to stir in the backward system of 2 h and add 3 mL hydrogen peroxide, mixture is poured out and washed with water to neutrality, obtain the solution phase of graphite oxide.
The graphite oxide solution making is further distributed in 2 L water mutually, ultrasonic 1 h that peels off of 800 w, under 90 ℃ 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 obtaining transferred to rapidly in 300 mL methyl alcohol, and be placed in ultrasonic wave and wash 2 times, each 3 min; Then wash with water 5 times, each 2 min, last, the Graphene solid obtaining is distributed in 60 mL water, in ultrasonic wave, be fully dispersed into after atherosclerotic, lyophilize, obtains graphene powder material, and specific area measuring is 812 m
2/ g.
Contrast said process, with traditional method synthesizing graphite alkene material:
Taking 1 g Graphite Powder 99 is distributed in 45 mL sulfuric acid (98%), under ice bath and whipped state, add 3 g potassium permanganate, remove ice bath, temperature rises to 35 ℃ and keep 4 h, adds 60 mL water subsequently under condition of ice bath in system, again temperature is risen to 98 ℃ and continue to stir 12 h, then in system, add 3 mL hydrogen peroxide, mixture is poured out and washed with water to neutrality, suction filtration, the solid obtaining is placed in to dry 72 h under 60 ℃ of conditions, obtains oxidation graphite solid.
The oxidation graphite solid obtaining is joined in 2 L water, ultrasonic 5 h of 800 w disperse, peel off, under 90 ℃ of water bath condition, add 20 mL hydrazine hydrates (80 %) to react 1 h, obtain graphene dispersing solution and by its suction filtration, then the Graphene solid obtaining transferred to rapidly in 300 mL methyl alcohol, by stirring, washing, suction filtration again after washing, repeats 2 times; Then water repeated washing 5 times again, last, the Graphene solid that suction filtration is obtained carries out lyophilize, obtains graphene powder material, and specific area measuring is 202 m
2/ g.
Taking 1 g Graphite Powder 99 is distributed in 30 mL perchloric acid, under ice bath and whipped state, add 2 g Potassium Persulphates, under room temperature condition, react 12 h, then under condition of ice bath, in system, add 30 mL water, continue to stir in the backward system of 0.5 h and add 1 mL hydrogen peroxide, mixture is poured out and washed with water to neutrality, obtain the solution phase of graphite oxide.
The graphite oxide solution making is further distributed in 1.5 L water mutually, ultrasonic 0.5 h that peels off of 100 w, under 60 ℃ of water bath condition, add 15 mL hydrazine hydrates (80 %) to react 0.5 h, obtain graphene dispersing solution and by its suction filtration, then the Graphene solid obtaining is transferred to rapidly in 200 mL methyl alcohol, and be placed in ultrasonic wave and wash 1 min; Then water washs again, and the Graphene solid obtaining is distributed in 50 mL water, is fully dispersed into after atherosclerotic in ultrasonic wave, carries out lyophilize, obtains graphene powder material.
Taking 1 g Graphite Powder 99 is distributed in 65 mL nitric acid, under ice bath and whipped state, add 6 g SODIUMNITRATE, remove and under ice bath room temperature condition, react 60 h, under condition of ice bath, in system, add 100 mL water, continue to stir in the backward system of 10 h and add 10 mL hydrogen peroxide, mixture is poured out and washed with water to neutrality, obtain the solution phase of graphite oxide.
The graphite oxide solution making is further distributed in 6 L water mutually, ultrasonic 10 h that peel off of 1000 w, under 100 ℃ of oil bath conditions, add 30 mL hydrazine hydrates (80 %) to react 10 h, obtain graphene dispersing solution and by its suction filtration, then the Graphene solid obtaining is transferred to rapidly in 1000 mL methyl alcohol, and be placed in ultrasonic wave and wash 3 times, each 2 min; Then water washs again, and last, the Graphene solid that suction filtration is obtained is distributed in 100 mL water, is fully dispersed into after atherosclerotic in ultrasonic wave, carries out lyophilize, obtains graphene powder material.
Grapheme material prepared by the embodiment 4 the present invention application in pharmaceutical extraction separation
The graphene powder of the embodiment of the present invention 1 preparation 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 respectively sieve plate and prevent material leakage, with methyl alcohol and ultrapure water, pillar is carried out after pre-treatment, get 20 mL environmental water samples (0.45 μ m 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, fluorescence derives the analysis of laggard liquid chromatography-fluorimetric detector, as shown in Figure 2, sample after Graphene solid phase extraction column is processed in spectrogram target peak noiseless, the rate of recovery >=95% as calculated, proof absorption property is good.
Embodiment 5 the present invention prepare the application of grapheme material in drug residue of food detects
The graphene powder of the embodiment of the present invention 2 preparations is applied to the detection of sulfa drug residue in milk:
According to the method in embodiment 4, make and pre-treatment pillar, measure 2 mL milk samples (after processing) by pillar, 1 mL 5% methanol-water washing pillar, 1 mL 5% ammonia-methyl alcohol carries out wash-out, collect elutriant and also with nitrogen, dry up, by moving phase, redissolve laggard liquid-phase chromatographic analysis.From Fig. 3, the color atlas of sample preparation front and back can be found out, this Graphene sorbent material is to target compound absorption abundant (rate of recovery >=97% as calculated), and sample after treatment decontamination effect improving is obvious.
The graphene powder of the embodiment of the present invention 3 preparations is applied to the residual detection of kelthane in tealeaves:
According to method in embodiment 4, make and pre-treatment pillar, measure 5 mL Tea Samples by pillar, 1 mL ultrapure water washing pillar, 2 mL eluent ethyl acetates, collect elutriant, and 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 grapheme material prepared by embodiment 7 the present invention and traditional method is investigated:
In the situation that keeping other conditions constant, the grapheme material that grapheme material in embodiment 4,5,6 is changed as preparing with traditional method in embodiment 1 operates, 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 illustrating the specific embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; in the ken possessing at described field those of ordinary skill; it any modification of doing within the spirit and principles in the present invention, is equal to and substitutes and improvement etc., within all should be encompassed in the technical scheme scope that the present invention asks for 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 99 is distributed in strong acid under whipped state, then under condition of ice bath, add strong oxidizer, after removing ice bath, react at ambient temperature 12～60 h, then under condition of ice bath, in system, add water and continue to stir 0.5～10 h, with adding hydrogen peroxide in backward 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 99: strong acid: strong oxidizer: water: g:30～100, mL:2～6, g:30～65, hydrogen peroxide=1 mL:1～10 mL;
Ultrasonic peeling off obtains graphene oxide:
The graphite oxide solution of preparation is further distributed in water mutually, ultrasonicly under 100～1000 w intensity peels off the dispersion liquid that 0.5～10 h obtains graphene oxide; Wherein the ratio of water and original Graphite Powder 99 is 1.5～6 L:1 g;
Graphene oxide reduction generates Graphene:
In graphene oxide dispersion liquid, add hydrazine hydrate, under 60～100 ℃ of conditions, react 0.5～10 h and make graphene dispersing solution; While wherein using volumetric concentration to be the hydrazine hydrate of 80 %, the ratio of consumption and original Graphite Powder 99 is 15～30 mL:1 g;
Ultrasonic auxiliary separating is from preparing graphene powder material:
The graphene dispersing solution that obtains is filtered, then Graphene solid is transferred in methyl alcohol rapidly, 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 washing; Washing time and number of times require same methyl alcohol; Finally, the Graphene solid that suction filtration is obtained is added to the water, and the ratio of water and original Graphite Powder 99 is 50～100 mL:1 g, is fully dispersed into after atherosclerotic in ultrasonic wave, and lyophilize, obtains graphene powder material.
2. the preparation method of grapheme material according to claim 1, is characterized in that: in step (1), strong acid used 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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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030279A (en) * | 2014-06-16 | 2014-09-10 | 上海交通大学 | Method for preparing graphene through acetylacetone reduction |
| CN104525118A (en) * | 2015-01-04 | 2015-04-22 | 兰州大学 | Efficient graphene oil absorption material preparing method |
| CN105047882A (en) * | 2015-09-09 | 2015-11-11 | 哈尔滨工业大学 | Method for preparing lithium-sulfur battery positive pole material |
| CN105148880A (en) * | 2015-07-16 | 2015-12-16 | 东华大学 | Preparation method and application method for graphene microsphere solid-phase extractant |
| CN106115669A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene oxide |
| CN106238060A (en) * | 2016-09-29 | 2016-12-21 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene/nickel composite |
| CN106802295A (en) * | 2017-03-16 | 2017-06-06 | 合肥学院 | A kind of chemical preparation process of the graphene quantum dot fluorescence probe to trace TNT detections |
| CN107910532A (en) * | 2017-11-20 | 2018-04-13 | 复旦大学 | A kind of preparation method of graphene coated nickle 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 |
| CN111646462A (en) * | 2020-04-21 | 2020-09-11 | 东北大学 | Method for preparing high-quality reduced graphene oxide by high-current pulsed electron beam |
| 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 |
| 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 |
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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 |
| CN104525118A (en) * | 2015-01-04 | 2015-04-22 | 兰州大学 | Efficient graphene oil absorption material preparing method |
| 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 |
| CN106115669A (en) * | 2016-06-20 | 2016-11-16 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene oxide |
| CN106238060B (en) * | 2016-09-29 | 2019-04-26 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene/nickel composite material |
| CN106238060A (en) * | 2016-09-29 | 2016-12-21 | 山东欧铂新材料有限公司 | A kind of preparation method of graphene/nickel composite |
| CN106802295A (en) * | 2017-03-16 | 2017-06-06 | 合肥学院 | A kind of chemical preparation process of the graphene quantum dot fluorescence probe to trace TNT detections |
| CN107910532A (en) * | 2017-11-20 | 2018-04-13 | 复旦大学 | A kind of preparation method of graphene coated nickle cobalt lithium manganate composite material |
| 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 |
| CN111646462A (en) * | 2020-04-21 | 2020-09-11 | 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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