CN102145882B - Method for preparing water soluble graphene - Google Patents
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- CN102145882B CN102145882B CN 201110044749 CN201110044749A CN102145882B CN 102145882 B CN102145882 B CN 102145882B CN 201110044749 CN201110044749 CN 201110044749 CN 201110044749 A CN201110044749 A CN 201110044749A CN 102145882 B CN102145882 B CN 102145882B
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Abstract
The invention discloses a method for preparing water soluble graphene. The method for preparing the water soluble graphene comprises the following steps of: oxidizing graphite into graphite oxide; then adding coomassie brilliant blue; performing a reaction of the coomassie brilliant blue and the graphite oxide by ultrasound; adding a reducing agent; and performing a reaction to obtain the water soluble graphene. The solubility of the water soluble graphene can reach 1 to 1.5mg/mL, the electrical conductivity of the water soluble graphene can reach 1 to 2S m-1, and the water soluble graphene can be stably stored for 3 to 6 months without precipitates.
Description
Technical field
The invention belongs to Material Field, be specifically related to a kind of preparation method of water-soluble graphene---prepare water-soluble graphene based on the π between aromatic series soluble small molecular Xylene Brilliant Cyanine G and Graphene-pi-conjugated mechanism.
Background technology
Graphene (Graphene) by the monolayer carbon atomic building, is the Two-dimensional Inorganic carbon material with honeycomb structure, is the another great discovery after finding soccerballene and found CNT (carbon nano-tube) in 1991 in 1985.Be found fully to show so far it from 2004 in the infinite glamour aspect Material Field research and practical application, be the most active research object of present Materials science and Condensed Matter Physics field, show wide application prospect in fields such as electronics, information, the energy, material and biological medicines.(Novoselov KS, Geim AK, Morozov SV, et al.Electric field effect in atomically thin carbon films[J] .Science, 2004,306 (5696): 666-669; Cheng Huiming appoints literary talent .2008 scientific development report [M]. Beijing: Science Press, 2008; Geim AK, Novoselov KS.The rise of graphene[J] .Nature Materials, 2007,6 (3): 183-191.)
But, the Graphene of structural integrity is the two dimensional crystal that is combined by the benzene six-ring that does not contain any labile bond, chemical stability is high, the surface is inert condition, a little less than the interaction of other media (as solvent etc.), and stronger Van der Waals force is arranged between the sheet of Graphene and sheet, easily produce and assemble, make it be insoluble in water and organic solvent commonly used, this has caused great difficulty for further research and the functionalized application of Graphene.In order to give full play to its advantageous property, improve its forming process (as improving solvability, dispersiveness etc. in matrix), must carry out effective functionalization to Graphene.
Wherein, be the functional method the most widely of research at present to the covalent linkage functionalization of Graphene.The method prepares graphene oxide (Grapheneoxide) by the method for chemical oxidation, then utilize a large amount of carboxyls, hydroxyl and the epoxy bond isoreactivity group and the organism that contain on graphene oxide to react, prepare water-soluble graphene after sodium borohydride reduction, but due to Oxidative demage the structure of Graphene, the intrinsic propesties of this class functionalization graphene material significantly reduces (as electroconductibility).(Si?Y.C.，Samulski?E.T.Synthesis?of?water?soluble?graphene[J].Nano?Letters，2008，8(6)：1679-1682.；Patil?A.J.，Vickery?J.L.，Scott?T.B.，et?al.Aqueous?stabilization?and?self-assembly?of?graphene?sheets?into?layered?bio-nanocomposites?using?DNA[J].Advanced?Materials，2009，21(31)：3159-3164.)
Recently, preparing water-soluble graphene with π-π non covalent bond functionalization becomes the focus that everybody pays close attention to, and the method has improved the water-soluble of it on the basis of not destroying the complete performance structure of Graphene.There has been now bibliographical information to utilize π between polymkeric substance and Graphene-π non covalent bond, prepared water-soluble good Graphene.(X.Y.Qi，K.Y.Pu，X.Z.Zhou，H.Li，B.Liu，F.Boey，W.Huang，H.Zhang，Small?6(2010)663.；H.Yang，Q.Zhang，C.Shan，F.Li，D.Han，L.Niu，Langmuir?26(2010)6708.)
Summary of the invention
In order to solve the deficiencies in the prior art, the object of the present invention is to provide a kind of preparation method of water-soluble graphene---prepare water-soluble graphene based on the π between aromatic series soluble small molecular Xylene Brilliant Cyanine G and Graphene-pi-conjugated mechanism.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of water-soluble graphene, its preparation process comprises the following steps as shown in Figure 1: at first, graphite (water insoluble) is oxidized to graphite oxide (water-soluble), owing to containing a large amount of carboxyls, hydroxyl on graphite oxide, make the graphite oxide water soluble; Then add aromatic series soluble small molecular Xylene Brilliant Cyanine G, ultrasonic Xylene Brilliant Cyanine G and the effect of graphite oxide generation supramolecule, acquisition Xylene Brilliant Cyanine G π-pi-conjugated graphite oxide of making; Add at last reductive agent, graphite oxide is reduced into Graphene, obtain water-soluble graphene (being Xylene Brilliant Cyanine G π-pi-conjugated Graphene).
A kind of preparation method of water-soluble graphene specifically comprises the following steps:
(1) Graphite Powder 99 pre-treatment: add natural graphite powder in hydrochloric acid, soak under 20～40 ℃ after 24～48h centrifugally, the collecting precipitation thing washes throw out with water, then with drying precipitate, obtains the pre-treatment Graphite Powder 99;
(2) preparation graphite oxide: add the pre-treatment Graphite Powder 99 in the vitriol oil, cryosel is bathed and is cooled to 0 ℃, slowly adds KMnO under stirring
4, then being warming up to 30～35 ℃, reaction 2～3h adds entry, then adds hydrogen peroxide (can see that solution becomes glassy yellow), and centrifugal removal impurity obtains graphite oxide after 20～40 ℃ of dryings of supernatant liquor normal pressure;
(3) preparation water-soluble graphene: water intaking mixes with graphite oxide, ultrasonic lower reaction obtains the graphite oxide aqueous solution, add Xylene Brilliant Cyanine G, after ultrasonic lower reaction 30～60min, add hydrazine hydrate, after 80～90 ℃ of lower reflux 24～48h, filter, collect filter cake, washing leaching cake, filter cake is put into water, obtain water-soluble graphene after ultrasonic lower reaction 20～40min;
The mass concentration of the described hydrochloric acid of step (1) is 5%;
The described Graphite Powder 99 of step (1) with the ratio of the addition of hydrochloric acid is: the 1g Graphite Powder 99 adds 40～60mL hydrochloric acid;
The described precipitation drying of step (1) is at 105～115 ℃ of drying 24～48h;
The mass concentration of the described vitriol oil of step (2) is 98%;
The described vitriol oil of step (2) with the ratio of the addition of pre-treatment Graphite Powder 99 is: 1g pre-treatment Graphite Powder 99 adds 20～25mL vitriol oil;
The described KMnO of step (2)
4With the mass ratio of pre-treatment Graphite Powder 99 be 2.5～3: 1;
The described water of step (2) with the ratio of the addition of pre-treatment Graphite Powder 99 is: 1g pre-treatment Graphite Powder 99 adds 150～200mL water;
The consumption of the described hydrogen peroxide of step (2) is that 1g pre-treatment Graphite Powder 99 adds 2～3mL hydrogen peroxide;
The amount ratio of the described water of step (3) and graphite oxide is: the 1mg graphite oxide adds 1～2mL water;
The mass ratio of the described Xylene Brilliant Cyanine G of step (3) and graphite oxide is 1～3: 1;
The described hydrazine hydrate of step (3) is that to be mixed with mass concentration be that 50% hydrazine hydrate aqueous solution uses, and the consumption of described hydrazine hydrate is that the 1mg graphite oxide adds 4～6mL hydrazine hydrate aqueous solution;
The described filtration of step (3) is to filter with the polycarbonate film that the aperture is 0.22 μ m.
Described water is preferably distilled water.
The Zeta potential of the water-soluble graphene that obtains in the aqueous solution is-37.3 ± 4.2mV, according to the D4187-82 standard of U.S. ASTM (American Society for Testing and Materials) association, the water-soluble system of Zeta potential between ± 30 to ± 40mV has " sane stability " (moderate stability).(American?Society?for?Testing?and?Materials.Zeta?potential?of?Colloids?in?Water?and?Waste?Water.ASTM?Standard?D4187-82，(1985).)。
The structure of prepared water-soluble graphene x-ray photoelectron spectroscopy detection, result as shown in Figure 2, graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.9eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.3eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.2eV and 285.8eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.(Park，S.；Ruoff，R.S.Nat.Nanotechnol.2009，4，217.)
Simply adsorb or formed π-pi-conjugated between Xylene Brilliant Cyanine G and Graphene in order to further illustrate on water-soluble graphene, effective means is exactly to detect the Fluorescence-quenching of Xylene Brilliant Cyanine G under the state of the aqueous solution, is with the mode combination of π-pi-conjugated with explanation Graphene and Xylene Brilliant Cyanine G.
The quenching of fluorescence test-results of water-soluble graphene as shown in Figure 3.The concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then adds the Graphene of 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.(Qi，X.；Pu，K.Y.；Zhou，X.；Li，H.；Liu，B.；Boey，F.；Huang，W.；Zhang，H.Small.2010，6，663.)
By above-mentioned detection, the water-soluble mechanism of the water-soluble graphene that the present invention is prepared has been described: the aromatic nucleus of Xylene Brilliant Cyanine G is had an effect with the phenyl ring on Graphene by π-πconjugation, firmly is fixed on Graphene; The sulfonic acid group of Xylene Brilliant Cyanine G is water miscible, therefore Graphene has been had water-soluble.In addition, due to the electrostatic repulsion of sulfonic acid group on Xylene Brilliant Cyanine G, make again Xylene Brilliant Cyanine G π-pi-conjugated Graphene can not reunite in the aqueous solution, further improved its stability in the aqueous solution.
The present invention has following advantage and effect with respect to prior art:
(1) the inventive method can make water-fast Graphene become solvable; The prepared solubleness of water-soluble graphene in water of the present invention can reach 1～1.5mg/mL.
(2) the prepared water-soluble graphene of the present invention has good electroconductibility, and based on π-pi-conjugated mechanism, the structure of Graphene is able to maximum preservation.Specific conductivity after prepared water-soluble graphene drying compressing tablet can reach 1～2Sm
-1(sample preparation and testing method with reference to Kong B S, Yoo H W and Jung H T 2009 Langmuir 25 11008)
(3) the prepared water-soluble graphene of the present invention has satisfactory stability, can keep not occurring in 3～6 months precipitation under aqueous solution state.
Description of drawings
Fig. 1 is the preparation process schematic diagram of water-soluble graphene; Little oblique square frame wherein refers to graphite oxide, and little ellipse refers to Xylene Brilliant Cyanine G.
Fig. 2 is the x-ray photoelectron power spectrum of water-soluble graphene.
Fig. 3 is the quenching of fluorescence spectrum of different concns water-soluble graphene.
Fig. 4 is the x-ray photoelectron power spectrum of embodiment 1 water-soluble graphene.
Fig. 5 is the quenching of fluorescence spectrum of embodiment 1 different concns water-soluble graphene.
Fig. 6 is the x-ray photoelectron power spectrum of embodiment 2 water-soluble graphenes.
Fig. 7 is the quenching of fluorescence spectrum of embodiment 2 different concns water-soluble graphenes.
Fig. 8 is the x-ray photoelectron power spectrum of embodiment 3 water-soluble graphenes.
Fig. 9 is the quenching of fluorescence spectrum of embodiment 3 different concns water-soluble graphenes.
Figure 10 is the x-ray photoelectron power spectrum of embodiment 4 water-soluble graphenes.
Figure 11 is the quenching of fluorescence spectrum of embodiment 4 different concns water-soluble graphenes.
Figure 12 is the x-ray photoelectron power spectrum of embodiment 5 water-soluble graphenes.
Figure 13 is the quenching of fluorescence spectrum of embodiment 5 different concns water-soluble graphenes.
Figure 14 is the x-ray photoelectron power spectrum of embodiment 6 water-soluble graphenes.
Figure 15 is the quenching of fluorescence spectrum of embodiment 6 different concns water-soluble graphenes.
Figure 16 is the x-ray photoelectron power spectrum of embodiment 7 water-soluble graphenes.
Figure 17 is the quenching of fluorescence spectrum of embodiment 7 different concns water-soluble graphenes.
Figure 18 is the x-ray photoelectron power spectrum of embodiment 8 water-soluble graphenes.
Figure 19 is the quenching of fluorescence spectrum of embodiment 8 different concns water-soluble graphenes.
Figure 20 is the x-ray photoelectron power spectrum of embodiment 9 water-soluble graphenes.
Figure 21 is the quenching of fluorescence spectrum of embodiment 9 different concns water-soluble graphenes.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 400mL, then adds natural graphite powder 10g, soak under 20 ℃ after 24h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 48h in 105 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 200mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 60rpm, slowly adds 25g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 30 ℃ after adding, after reaction 2h, the reactant in flask slowly poured in the 4000mL beaker, add 1500mL distilled water, then add 20mL hydrogen peroxide (can see that solution becomes glassy yellow), the centrifugal removal impurity of 300rpm obtains graphite oxide after 40 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 100mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 100mg Xylene Brilliant Cyanine G, after the ultrasonic 30min of 60W, mentioned solution is poured in the 250mL flask, add 400mL hydrazine hydrate (aqueous solution of 50wt%), after 85 ℃ of lower reflux 48h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 30min of 60W.
Resulting water-soluble graphene solubleness is 1mg/mL, and specific conductivity is 2Sm
-1, Zeta potential is-33.1mV that stability reaches 3 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in Figure 4: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.9eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.3eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.2eV and 285.8eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in Figure 5: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 2
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 500mL, then adds natural graphite powder 10g, soak under 30 ℃ after 48h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 24h in 110 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 250mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 70rpm, slowly adds 30g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 35 ℃ after adding, after reaction 3h, the reactant in flask slowly poured in the 4000mL beaker, add 2000mL distilled water, then add 25mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 20 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 120mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 150mg Xylene Brilliant Cyanine G, after the ultrasonic 40min of 60W, mentioned solution is poured in the 250mL flask, add 500mL hydrazine hydrate (aqueous solution of 50wt%), after 90 ℃ of lower reflux 24h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 40min of 60W.
Resulting water-soluble graphene solubleness is 1.1mg/mL, and specific conductivity is 1.8Sm
-1, Zeta potential is-34.4mV that stability reaches 4 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in Figure 6: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.8eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.3eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.2eV and 285.7eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in Figure 7: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 3
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 600mL, then adds natural graphite powder 10g, soak under 40 ℃ after 24h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 48h in 115 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 200mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 80rpm, slowly adds 25g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 30 ℃ after adding, after reaction 2h, the reactant in flask slowly poured in the 4000mL beaker, add 1500mL distilled water, then add 30mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 30 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 140mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 200mg Xylene Brilliant Cyanine G, after the ultrasonic 50min of 60W, mentioned solution is poured in the 250mL flask, add 600mL hydrazine hydrate (aqueous solution of 50wt%), after 80 ℃ of lower reflux 36h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 20min of 60W.
Resulting water-soluble graphene solubleness is 1.2mg/mL, and specific conductivity is 1.6Sm
-1, Zeta potential is-35.9mV that stability reaches 4 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in Figure 8: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.9eV, the combination of C=O can be at 288.5eV, and the combination of O-C=O can be at 289.3eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.2eV and 285.9eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in Figure 9: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 4
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 400mL, then adds natural graphite powder 10g, soak under 20 ℃ after 48h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 24h in 105 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 250mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 90rpm, slowly adds 30g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 35 ℃ after adding, after reaction 2h, the reactant in flask slowly poured in the 4000mL beaker, add 2000mL distilled water, then add 20mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 40 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 160mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 250mg Xylene Brilliant Cyanine G, after the ultrasonic 60min of 60W, mentioned solution is poured in the 250mL flask, add 400mL hydrazine hydrate (aqueous solution of 50wt%), after 85 ℃ of lower reflux 48h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 30min of 60W.
Resulting water-soluble graphene solubleness is 1.4mg/mL, and specific conductivity is 1.4Sm
-1, Zeta potential is-40.1mV that stability reaches 5 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in figure 10: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.9eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.2eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.3eV and 285.8eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in figure 11: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 5
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 500mL, then adds natural graphite powder 10g, soak under 30 ℃ after 24h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 48h in 110 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 200mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 100rpm, slowly adds 25g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 30 ℃ after adding, after reaction 2h, the reactant in flask slowly poured in the 4000mL beaker, add 1500mL distilled water, then add 25mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 40 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 180mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 300mg Xylene Brilliant Cyanine G, after the ultrasonic 30min of 60W, mentioned solution is poured in the 250mL flask, add 500mL hydrazine hydrate (aqueous solution of 50wt%), after 85 ℃ of lower reflux 48h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 30min of 60W.
Resulting water-soluble graphene solubleness is 1.5mg/mL, and specific conductivity is 1Sm
-1, Zeta potential is-41.5mV that stability reaches 6 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in figure 12: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.8eV, the combination of C=O can be at 288.5eV, and the combination of O-C=O can be at 289.3eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.2eV and 285.8eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in figure 13: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 6
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 600mL, then adds natural graphite powder 10g, soak under 40 ℃ after 48h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 24h in 115 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 250mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 110rpm, slowly adds 30g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 35 ℃ after adding, after reaction 2h, the reactant in flask slowly poured in the 4000mL beaker, add 2000mL distilled water, then add 30mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 40 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 200mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 100mg Xylene Brilliant Cyanine G, after the ultrasonic 40min of 60W, mentioned solution is poured in the 250mL flask, add 600mL hydrazine hydrate (aqueous solution of 50wt%), after 85 ℃ of lower reflux 48h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 30min of 60W.
Resulting water-soluble graphene solubleness is 1.2mg/mL, and specific conductivity is 1.6Sm
-1, Zeta potential is-36.2mV that stability reaches 4 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in figure 14: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.9eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.2eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.3eV and 285.8eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in figure 15: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 7
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 400mL, then adds natural graphite powder 10g, soak under 20 ℃ after 24h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 48h in 105 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 200mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 120rpm, slowly adds 25g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 30 ℃ after adding, after reaction 2h, the reactant in flask slowly poured in the 4000mL beaker, add 2000mL distilled water, then add 20mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 40 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 100mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 150mg Xylene Brilliant Cyanine G, after the ultrasonic 50min of 60W, mentioned solution is poured in the 250mL flask, add 400mL hydrazine hydrate (aqueous solution of 50wt%), after 85 ℃ of lower reflux 48h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 30min of 60W.
Resulting water-soluble graphene solubleness is 1.3mg/mL, and specific conductivity is 1.5Sm
-1, Zeta potential is-38.1mV that stability reaches 4 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in figure 16: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.9eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.3eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.2eV and 285.7eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in figure 17: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 8
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 500mL, then adds natural graphite powder 10g, soak under 30 ℃ after 48h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 24h in 110 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 250mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 100rpm, slowly adds 30g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 35 ℃ after adding, after reaction 2.5h, reactant in flask is slowly poured in the 4000mL beaker, add 2000mL distilled water, then add 25mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 20 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 150mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 200mg Xylene Brilliant Cyanine G, after the ultrasonic 60min of 60W, mentioned solution is poured in the 250mL flask, add 500mL hydrazine hydrate (aqueous solution of 50wt%), after 80 ℃ of lower reflux 36h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 20min of 60W.
Resulting water-soluble graphene solubleness is 1.3mg/mL, and specific conductivity is 1.5Sm
-1, Zeta potential is-37.8mV that stability reaches 5 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in figure 18: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.8eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.3eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.3eV and 285.8eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in figure 19: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Embodiment 9
A kind of preparation method of water-soluble graphene as shown in Figure 1, comprises the steps:
In the 1000mL flask, adding mass concentration is 5% hydrochloric acid 600mL, then adds natural graphite powder 10g, soak under 40 ℃ after 24h centrifugal, and with distilled water wash filter cake 6 times, 100mL at every turn, then dry 48h in 115 ℃ of baking ovens, obtain the pre-treatment Graphite Powder 99.In the 1000mL flask, adding the 200mL mass concentration is 98% the vitriol oil, then adds pre-treatment Graphite Powder 99 10g, and cryosel is bathed and is cooled to 0 ℃, and stirring velocity is 120rpm, slowly adds 25g KMnO
4, keep the interior temperature of flask under 20 ℃.Be warmed up to 30 ℃ after adding, after reaction 3h, the reactant in flask slowly poured in the 4000mL beaker, add 2000mL distilled water, then add 30mL hydrogen peroxide (can see that solution becomes glassy yellow), 300 leave the heart removes impurity, obtains graphite oxide after 30 ℃ of dryings of supernatant liquor normal pressure.In the 250mL beaker, add 100mL distilled water and 100mg graphite oxide powder, obtain the graphite oxide aqueous solution after the ultrasonic 30min of 60W, then add the 250mg Xylene Brilliant Cyanine G, after the ultrasonic 50min of 60W, mentioned solution is poured in the 250mL flask, add 600mL hydrazine hydrate (aqueous solution of 50wt%), after 90 ℃ of lower reflux 24h, the polycarbonate film that is 0.22 μ m with the aperture filters, and uses distilled water wash filter cake 6 times, each 100mL, then collect filter cake, filter cake is put into 200mL distilled water, obtain water-soluble graphene after the ultrasonic 40min of 60W.
Resulting water-soluble graphene solubleness is 1.4mg/mL, and specific conductivity is 1.3Sm
-1, Zeta potential is-39.7mV that stability reaches 5 months and precipitation do not occur.
The x-ray photoelectron power spectrum of resulting water-soluble graphene is as shown in figure 20: graphite oxide has four typical carbon can be at 284.7eV in conjunction with the combination of energy: C=C, the combination of C-O can be at 286.9eV, the combination of C=O can be at 288.4eV, and the combination of O-C=O can be at 289.2eV.On the photoelectron spectrum of water-soluble graphene, the combination of carbon-carbon double bond can still exist, and other oxygenated functional group disappears substantially, illustrates that graphite oxide has been reduced into Graphene.And on the photoelectron spectrum of water-soluble graphene, occurred at 286.3eV and 285.8eV place new in conjunction with can, these in conjunction with can belong to C-N and C-S on Xylene Brilliant Cyanine G in conjunction with can, illustrate has the Xylene Brilliant Cyanine G existence on water-soluble graphene.
The quenching of fluorescence spectrum of resulting water-soluble graphene is as shown in figure 21: the concentration of Xylene Brilliant Cyanine G is set in 0.05mg/mL, then the Graphene that adds 0-0.05mg/mL, in the situation that excitation wavelength is 345nm, Xylene Brilliant Cyanine G has the strongest emissive porwer at the 394nm place.Along with adding of Graphene, Xylene Brilliant Cyanine G weakens gradually at the utilizing emitted light at 394nm place, illustrates in water-soluble graphene, and π-πconjugation has occured for Xylene Brilliant Cyanine G and Graphene.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (8)
1. the preparation method of a water-soluble graphene is characterized in that comprising the following steps: graphite oxidation is become graphite oxide, then graphite oxide is mixed with water and ultrasonic reaction obtains the graphite oxide aqueous solution; Then, add Xylene Brilliant Cyanine G, ultrasonic reaction, then add hydrazine hydrate, reaction obtains water-soluble graphene;
The mass ratio of described Xylene Brilliant Cyanine G and graphite oxide is 1～3: 1;
The consumption of described hydrazine hydrate is that the 1mg graphite oxide adds 4～6mL hydrazine hydrate aqueous solution; Add hydrazine hydrate reaction conditions afterwards to be: 80～90 ℃ of lower reflux 24～48h.
2. the preparation method of water-soluble graphene according to claim 1 is characterized in that comprising the following steps:
(1) add Graphite Powder 99 in hydrochloric acid, soak under 20～40 ℃ after 24～48h centrifugally, the collecting precipitation thing washes throw out with water, then with drying precipitate, obtains the pre-treatment Graphite Powder 99;
(2) add the pre-treatment Graphite Powder 99 in the vitriol oil, cryosel is bathed and is cooled to 0 ℃, adds KMnO under stirring
4, then being warming up to 30～35 ℃, reaction 2～3h adds entry, then adds hydrogen peroxide, and centrifugal removal impurity obtains graphite oxide after 20～40 ℃ of dryings of supernatant liquor;
(3) water intaking mixes with graphite oxide, ultrasonic lower reaction obtains the graphite oxide aqueous solution, add Xylene Brilliant Cyanine G, after ultrasonic lower reaction 30～60min, add hydrazine hydrate, after 80～90 ℃ of lower reflux 24～48h, filter, collect filter cake, washing leaching cake, filter cake is put into water, obtain water-soluble graphene after ultrasonic lower reaction 20～40min.
3. the preparation method of water-soluble graphene according to claim 2 is characterized in that:
The mass concentration of the described hydrochloric acid of step (1) is 5 ﹪;
The described Graphite Powder 99 of step (1) with the ratio of the addition of hydrochloric acid is: the 1g Graphite Powder 99 adds 40～60mL hydrochloric acid;
The described precipitation drying of step (1) is at 105～115 ℃ of drying 24～48h.
4. the preparation method of water-soluble graphene according to claim 2 is characterized in that:
The mass concentration of the described vitriol oil of step (2) is 98 ﹪;
The described vitriol oil of step (2) with the ratio of the addition of pre-treatment Graphite Powder 99 is: 1g pre-treatment Graphite Powder 99 adds 20～25mL vitriol oil.
5. the preparation method of water-soluble graphene according to claim 2 is characterized in that:
The described KMnO of step (2)
4With the mass ratio of pre-treatment Graphite Powder 99 be 2.5～3: 1;
The described water of step (2) with the ratio of the addition of pre-treatment Graphite Powder 99 is: 1g pre-treatment Graphite Powder 99 adds 150～200mL water;
The consumption of the described hydrogen peroxide of step (2) is: 1g pre-treatment Graphite Powder 99 adds 2～3mL hydrogen peroxide.
6. the preparation method of water-soluble graphene according to claim 2 is characterized in that:
The amount ratio of the described water of step (3) and graphite oxide is: the 1mg graphite oxide adds 1～2mL water;
The mass ratio of the described Xylene Brilliant Cyanine G of step (3) and graphite oxide is 1～3: 1.
7. the preparation method of water-soluble graphene according to claim 2 is characterized in that:
The described hydrazine hydrate of step (3) is that to be mixed with mass concentration be that 50% hydrazine hydrate aqueous solution uses, and the consumption of described hydrazine hydrate is that the 1mg graphite oxide adds 4～6mL hydrazine hydrate aqueous solution;
The described filtration of step (3) is to filter with the polycarbonate film that the aperture is 0.22 μ m.
8. the preparation method of water-soluble graphene according to claim 2, it is characterized in that: described water is distilled water.
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