CN103787319A - Large-scale preparation method of graphene quantum dots - Google Patents
Large-scale preparation method of graphene quantum dots Download PDFInfo
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Abstract
A large-scale preparation method of graphene quantum dots comprises the steps of adding graphene oxide into a first solvent to obtain a first dispersion liquid, and adding a reducing agent into the first dispersion liquid to obtain a mixed liquid; reacting the mixed solution in a microwave environment of 500-800 watts for 10-60 minutes, cooling, performing solid-liquid separation, and taking solid to obtain a crude product; mixing one of reducing polyhydroxy aldehyde and organic acid with the crude product, adding Lewis acid, uniformly mixing to obtain a mixture, and adding the mixture into a second solvent to obtain a second dispersion liquid; and reacting the second dispersion liquid in a microwave environment of 500-800 watts for 0.2-1 hour, then stripping for 2-3 hours in an ultrasonic environment of 120-300 watts, and separating and purifying to obtain the graphene quantum dots. The large-scale preparation is completed by a microwave-solvothermal method, the process is simple, the utilization rate of the graphene oxide is high, and the yield is high.
Description
Technical field
The present invention relates to nano material preparing technical field, particularly relate to a kind of large-scale producing method of graphene quantum dot.
Background technology
Since the Andre Geim of Univ Manchester UK in 2004 and Konstantin Novoselof successfully peel off first pyrolytic graphite and observe Graphene, the research temperature for new carbon in educational circles just never disappeared.The successful separation of Graphene means that theory is abolished for the prophesy of two dimensional crystal thermodynamic instability, has also just brought the possibility of many frontier researchs.
Perfectly Graphene has desirable two-dirnentional structure, it is made up of hexagonal lattice, each carbon atom is combined with other three carbon atoms in the direction of lattice plane by σ key, does not become the electronics of σ key as π-electron, has formed the π track system perpendicular to lattice plane.π-electron can move arbitrarily in the plane.But what is more important, due to the distinctive structure of Graphene, its energy band structure is the form of dirac cone, and on dirac point, the conduction band of Graphene and valence band overlap, therefore on its dirac point, the virtual mass in electronics and hole is all zero, corresponding electronics and the mobility in hole are all identical and be infinitely close to infinity, this means that its carrier can be both that hole can be also electronics, and its carrier transport factor is very big, therefore desirable Graphene should have fabulous electroconductibility, predicts that it can bear than the current density of high six orders of magnitude of copper.
Current research has had a series of breathtaking research work to deliver for the Graphene of large lamella, and be bound in the research of Graphene and the graphene oxide particle of Bohr radius for two-dimentional lamella scale size, also just like a raging fire carrying out.For such Graphene particle, owing to having retained certain oxygenated functional group or defect, and size decreases, therefore it can be with and be discontinuous, cause thus its carrier to be excited.After being excited, carrier forms exciton, and exciton has been limited in the band gap of three direction in spaces of this Graphene, single-layer graphene thickness is in 1nm left and right, lamella size is in Bohr radius left and right, the band gap corresponding due to such Graphene is larger, this laser emission wavelength that causes exciton de excitation to send out formation rear is wider, has fabulous laser characteristics.And this class Graphene particle, the characteristic that has the semiconductor-quantum-point in similar inorganic materials to have, therefore be referred to as graphene quantum dot, the radius of graphene quantum dot is within Bohr radius, it is nontoxic, wavelength of fluorescence is narrow, and laser wave length and width can play fabulous application on light emitting diode (LED) and bio-imaging and photovoltaic device and sensor.
In research for graphene quantum dot, the main preparation method who adopts has four kinds at present.These four kinds of methods are respectively secondary oxidation methods that Graphene is reoxidized, from the method for organic synthesis method, electron beam or the ion beam milling of organic molecule and the method for carbon material being carried out to microcosmic cutting.In the middle of this, secondary oxidation method need to first be prepared the grapheme material of high-quality, just can carry out follow-up oxidation step, and cost is higher, is also unfavorable for industrialization; The related complex process of organic synthesis method and loaded down with trivial details, is unfavorable for industrial production; The method of electronics or ion beam milling exists output little, the problem that cannot produce in enormous quantities; Also there is step complexity and the lower defect of productive rate in the method for carbon material being carried out to microcosmic cutting.Therefore, proposing a kind of technique simple, and can prepare on a large scale the method for graphene quantum dot, for promoting quantum dot progress of research, is imperative.
Summary of the invention
Based on this, be necessary to provide the large-scale producing method of the graphene quantum dot that a kind of technique is simple, productive rate is higher, to prepare on a large scale graphene quantum dot.
A large-scale producing method for graphene quantum dot, comprises the steps:
Graphene oxide is added in the first solvent, and dispersed first dispersion liquid that obtains, adds reductive agent in described the first dispersion liquid the dispersed mixed solution that obtains;
Described mixed solution is reacted 10 minutes～60 minutes in the microwave environment of 500 watts～800 watts, carry out solid-liquid separation after cooling, get solid, obtain crude product;
One in reductibility poly-hydroxy aldehyde and organic acid is mixed with described crude product, add Lewis acid, mix and obtain mixture, described mixture is added in the second solvent, dispersed second dispersion liquid that obtains; And
Described the second dispersion liquid is reacted 0.2 hour～1 hour in 500 watts～800 watts microwave environments, then under the ultrasound environments of 120 watts～300 watts, peel off 2 hours～3 hours, after separation and purification, obtain described graphene quantum dot.
Therein in an embodiment, before described mixed solution being reacted in the microwave environment of 500 watts～800 watts to the step of 10 minutes～60 minutes, comprise the step of ultrasonic agitation, the step of described ultrasonic agitation is specially: described mixed solution is stirred 0.5 hour～4 hours under the ultrasound environments of 120 watts～300 watts.
Therein in an embodiment, before described the second dispersion liquid being reacted in 500 watts～800 watts microwave environments to the step of 0.2 hour～1 hour, also comprise the step of ultrasonic dispersion, the step of described ultrasonic dispersion is specially: described the second dispersion liquid is disperseed 0.5 hour～2 hours in the ultrasound environments of 120 watts～300 watts.
Therein in an embodiment, described the first solvent and the second solvent are all selected from least one in the aqueous solution, glycerol, three diglycol ethylenes and the N-Methyl pyrrolidone of water, glycol dimethyl ether, polyvinyl alcohol.
In an embodiment, in described the first dispersion liquid, the concentration of described graphene oxide is 2 mg/ml～10 mg/ml therein.
In an embodiment, described reductive agent is selected from least one in citric acid, gluconic acid, formic acid, xitix, oxalic acid, Trisodium Citrate, Sunmorl N 60S, sodium formiate, sodium ascorbate and sodium oxalate therein.
In an embodiment, the mass ratio of described graphene oxide and described reductive agent is 1:3～10 therein.
Therein in an embodiment, the described operation that described mixed solution is reacted 10 minutes～60 minutes in the microwave environment of 500 watts～800 watts is specially: described mixed solution is reacted 5 minutes～30 minutes in the microwave environment of 500 watts～800 watts, taking-up is added after described the first solvent, continues in the microwave environment of 500 watts～800 watts and reacts 5 minutes～30 minutes; The volume of the first solvent of wherein, adding be described the first solvent original volume 10%～15%.
In an embodiment, a kind of mass ratio in described crude product and described reductibility poly-hydroxy aldehyde and organic acid is 1:5～10 therein.
In an embodiment, described reductibility poly-hydroxy aldehyde is glucose or hexanedial therein.
In an embodiment, described Lewis acid is selected from least one in iron(ic) chloride, aluminum chloride, zinc chloride, boron trifluoride, magnesium chloride, cupric chloride and lithium chloride therein.
In an embodiment, described organic acid is selected from least one in citric acid, gluconic acid, formic acid, xitix and oxalic acid therein.
In an embodiment, in described the second dispersion liquid, the concentration of described mixture is 0.1 grams per milliliter～1 grams per milliliter therein.
Therein in an embodiment, described lewis acidic quality account for described mixture quality 1%～3%.
Therein in an embodiment, the step that obtains described graphene quantum dot after described separation and purification is specially: by be set forth in and under the ultrasound environments of 120 watts～300 watts, peel off the 2 hours～reaction product that obtains for 3 hours and carry out column chromatography for separation, then vacuum is revolved and is steamed except desolventizing, obtains described graphene quantum dot; Wherein, the stationary phase of described column chromatography is silica gel or polyacrylamide, and first-phase developping agent is methylene dichloride and the methyl alcohol mixed solution that mix 1:1～3 by volume, and second-phase developping agent is deionized water.
The large-scale producing method of above-mentioned graphene quantum dot has completed a large amount of preparations of graphene quantum dot by the method for microwave-solvent thermal, technique is simple, effectively reduce cost, and reacting weight is large, the preparation of the graphene quantum dot of gram level or even kilogram levels can be once completed, Graphene can be prepared on a large scale., after repeatedly peeling off, the graphene oxide of raw material can be utilized completely meanwhile, obtain high productive rate.
Accompanying drawing explanation
Fig. 1 is the schema of the large-scale producing method of the graphene quantum dot of an embodiment;
Fig. 2 is the fluorescence spectrum figure of the graphene quantum dot for preparing of embodiment 1;
Fig. 3 is the fluorescence spectrum figure of the black alkene quantum dot for preparing of embodiment 2;
Fig. 4 is the fluorescence spectrum figure of the black alkene quantum dot for preparing of embodiment 3;
Fig. 5 is the fluorescence spectrum figure of the black alkene quantum dot for preparing of embodiment 4.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the large-scale producing method of the graphene quantum dot of an embodiment, comprises the steps S110～step S140.
Step S110: graphene oxide is added in the first solvent, and dispersed first dispersion liquid that obtains, adds reductive agent in the first dispersion liquid, the dispersed mixed solution that obtains.
Graphene oxide is preferably the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers.
The first solvent is selected from least one in the aqueous solution, glycerol, three diglycol ethylenes and the N-Methyl pyrrolidone of water, glycol dimethyl ether, polyvinyl alcohol.The boiling point of these several solvents is higher, and high boiling solvent can provide the sufficiently high envrionment temperature that makes graphene oxide deoxidation and reduction, and above-mentioned high boiling solvent and graphene oxide have no adverse reaction.
Preferably, the aqueous solution that the first solvent is polyvinyl alcohol.More preferably, the mass percent of the aqueous solution of polyvinyl alcohol is 10%.
Preferably, in the first dispersion liquid, concentration thing 2 mg/ml～10 mg/ml of graphene oxide.
Reductive agent is selected from least one in citric acid, gluconic acid, formic acid, xitix, oxalic acid, Trisodium Citrate, Sunmorl N 60S, sodium formiate, sodium ascorbate and sodium oxalate.Preferably, reductive agent is oxalic acid.
Preferably, the mass ratio of graphene oxide and reductive agent is 1:3～10.Select this mass ratio, with by graphene oxide partial reduction, make the oxygen level of the graphene oxide after partial reduction less, but still retain partial oxygen, graphene oxide is because the dirac that the introducing of oxygen has destroyed Graphene is bored, make being with of Graphene discontinuous, just the possible semiconductor structure of tool, is conducive to the higher graphene quantum dot of follow-up formation quality.
Reductive agent is added to the mixture that obtains reductive agent and the first dispersion liquid in the first dispersion liquid, the mixture of reductive agent and the first dispersion liquid is carried out to ultrasonic dispersion, make graphene oxide and reductive agent dispersed, obtain mixed solution.
Step S120: mixed solution is reacted 10 minutes～60 minutes in the microwave environment of 500 watts～800 watts, carry out solid-liquid separation after cooling, get filter cake, obtain crude product.
Preferably, before mixed solution is reacted in microwave environment, also comprise the step of ultrasonic agitation.The step of ultrasonic agitation is specially: mixed solution is stirred 0.5 hour～4 hours under 120 watts～300 watts ultrasound environments.
The object of ultrasonic agitation is the graphene oxide of peeling off after the reduction that may reunite, and promotes the destruction of the graphene oxide after reduction, thereby makes the formation of quantum dot.Under 120 watts～300 watts ultrasound environments, stir 0.5 hour～4 hours, to guarantee to peel off completely the graphene oxide after the reduction of reunion, and the graphene oxide after reduction is destroyed, to guarantee the generation of graphene quantum dot.
Mixed solution after ultrasonic agitation is placed in to microwave environment and reacts, graphene oxide is carried out to the cracking of microwave-solvothermal.Under microwave-solvent thermal condition, reduce, effectively by graphene oxide reductive cleavage, thereby the size of attenuating graphene sheet layer is convenient to the control of next step graphene quantum dot size.
Preferably, the operation that mixed solution is reacted 10 minutes～60 minutes in the microwave environment of 500 watts～800 watts is specially: mixed solution is put into airtight reaction vessel, in the microwave environment of 500 watts～800 watts, react 5 minutes～30 minutes, taking-up is added after the first solvent, continues in the microwave environment of 500 watts～800 watts and reacts 5 minutes～30 minutes.The volume of the first solvent of wherein, adding be the first solvent original volume 10%～15%.
In airtight reaction vessel, in the microwave environment of 500 watts～800 watts, react after 5 minutes～30 minutes, part the first solvent can be in the reaction process of microwave-solvent thermal directly decomposes sedimentation carbon on reactant, so need to add the first solvent and maintain vapour pressure and be beneficial to the carrying out of reaction.Therefore, mixed solution is carried out to microwave-solvent thermal reaction in two steps, and after the first step has been reacted, carry out again second step reaction after adding the first solvent.
After reaction finishes, solid-liquid separation, gets solid, obtains crude product.The operation of solid-liquid separation is specially: question response liquid cooling but, in reaction solution, add deionized water, obtain reactant dispersion liquid, by the ultrasonic dispersion 5 minutes～30 minutes in the ultrasound environments of 120 watts～300 watts of reactant dispersion liquid, then carry out suction filtration, obtain filtrate and filter cake, get filter cake, obtain crude product.Retain filtrate further separates to subsequent step S140.
Be 1:10～20 to the deionized water adding in reaction solution and the initial volume ratio of the first solvent.
Filtrate is the solution of the graphene quantum dot that size is less.Filter cake, crude product is larger-size graphene quantum dot.In order further to control the size of graphene quantum dot, carry out subsequent step S130 and step S140, to obtain the graphene quantum dot of desired size.
Step S130: the one in reductibility poly-hydroxy aldehyde and organic acid is mixed with crude product, add Lewis acid, mix and obtain mixture, mixture is added in the second solvent, dispersed second dispersion liquid that obtains.
Reductibility poly-hydroxy aldehyde is preferably the carbohydrate of six-ring, more preferably glucose or hexanedial.Glucose and hexanedial, on the one hand as reductive agent, also supplement carbocyclic ring on the other hand on graphene quantum dot as carbon source.
Select this carbohydrate with six-ring of glucose or hexanedial, the structure of its six-membered ring structure and Graphene matches, can in graphene-structured, not introduce Stone-Wales topological defect, guarantee that the graphene quantum dot finally preparing has higher quality.
Organic acid is selected from least one in citric acid, gluconic acid, formic acid, xitix and oxalic acid.
The second solvent is selected from least one in the aqueous solution, glycerol, three diglycol ethylenes and the N-Methyl pyrrolidone of water, glycol dimethyl ether, polyvinyl alcohol.
Lewis acid is selected from least one in iron(ic) chloride, aluminum chloride, zinc chloride, boron trifluoride, magnesium chloride, cupric chloride and lithium chloride.
While wishing to increase quantum dot size, reductibility poly-hydroxy aldehyde is mixed with crude product, add Lewis acid, mix and obtain mixture, mixture is added in the second solvent to dispersed second dispersion liquid that obtains.
Preferably, the mass ratio of crude product and reductibility poly-hydroxy aldehyde is 1:5～10.Preferably, lewis acidic quality be reductibility poly-hydroxy aldehyde, crude product and lewis acidic mixture quality 1%～3%.
While wishing to reduce quantum dot size, organic acid is mixed with crude product, add Lewis acid, mix and obtain mixture, mixture is added in the second solvent to dispersed second dispersion liquid that obtains.
Preferably, crude product and organic acid mass ratio are 1:5～10.Preferably, lewis acidic quality be organic acid, crude product and lewis acidic mixture quality 1%～3%.
One in reductibility poly-hydroxy aldehyde and organic acid is mixed with crude product, add Lewis acid, mix and obtain mixture, mixture is added in the second solvent, dispersed second dispersion liquid that obtains under ultrasound environments.
Preferably, in the second dispersion liquid, a kind of, the crude product in reductibility poly-hydroxy aldehyde and organic acid and the concentration of lewis acidic mixture are 0.1g/mL～1g/mL.
Step S140: the second dispersion liquid is reacted 0.2 hour～1 hour in 500 watts～800 watts microwave environments, then peel off under the ultrasound environments of 120 watts～300 watts 2 hours～3 hours, obtain graphene quantum dot after separation and purification.
Preferably, before the second dispersion liquid is reacted in microwave environment, also comprise the step of ultrasonic dispersion.The step of ultrasonic dispersion is specially: the second dispersion liquid is disperseed 0.5 hour～2 hours in the ultrasound environments of 120 watts～300 watts, so that one, crude product and Lewis acid in reductibility poly-hydroxy aldehyde and the organic acid in the second dispersion liquid are dispersed, be conducive to reaction.
The second dispersion liquid after ultrasonic dispersion is reacted 0.2 hour～1 hour in 500 watts～800 watts microwave environments, then under the ultrasound environments of 120 watts～300 watts, disperse and peel off 2 hours～3 hours, after separation and purification, obtaining the graphene quantum dot of desired size.
Preferably, the second dispersion liquid is reacted after 0.2 hour～1 hour in 500 watts～800 watts microwave environments, for the ease of follow-up dispersion with peel off, after the reaction solution that first adds deionized water that microwave reaction is obtained dilutes, under the ultrasound environments of 120 watts～300 watts, disperse again and peel off 2 hours～3 hours, obtaining the aqueous solution of graphene quantum dot.
The volume ratio of the second solvent of deionized water and the second dispersion liquid is preferably 1:10～20.
Step S130 and step S140 prepare graphene quantum dot take reductibility poly-hydroxy aldehyde as the hydrothermal method of carbon source, and recycling Graphene particle, as the nucleation source of quantum dot, has increased the size of graphene quantum dot, the red shift of its corresponding fluorescence spectrum effectively.Thus, can obtain the yellow red graphene quantum dot that arrives.
Or; step S130 and step S140 prepare graphene oxide quantum dot take solvent thermal and the large ultrasonic method as carbon-coating cracking of frequency of the second solvent under organic acid environment; recycling Graphene particle is as the nucleation source of quantum dot; with the second solvent protection method quantum dot; thereby effectively reduce the size of graphene quantum dot, the blue shift of its corresponding fluorescence spectrum.Thus, can obtain green and blue graphene quantum dot.
The operation of separation and purification is specially: the aqueous solution of graphene quantum dot is carried out to column chromatography, obtain successively the aqueous solution of the graphene quantum dot that size is different, respectively the aqueous solution of the graphene quantum dots different size obtaining is carried out to vacuum and revolve and boil off solvent, obtain respectively the graphene quantum dot powder being dried, size is different.
Preferably, for convenient steaming desolventizes, the graphite quantum dot solution in water first by methylene dichloride and methyl alcohol by volume for the mixed solvent of 1:1～3:1 extracts, then revolve and boil off solvent, the little graphene quantum dot powder of acquisition size.
Preferably, the stationary phase of column chromatography is silica gel or polyacrylamide.First-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:1～3 by volume, and second-phase developping agent is deionized water.
Mode with column chromatography rather than dialysis is carried out separation and purification, can effectively improve productive rate, simultaneously fast reaction speed.Equally, because chromatography column can be observed the movement of graphene quantum dot on post by UV-light, thereby can effectively obtain graphene quantum dot particle.
Preferably, the filtrate that step S120 prepares, the solution of graphene quantum dot also adopts the method for above-mentioned column chromatography for separation to separate, and carries out vacuum and boil off solvent, obtains dry graphene quantum dot powder, improves productive rate.
The large-scale producing method of above-mentioned graphene quantum dot has completed a large amount of preparations of graphene quantum dot by the method for microwave-solvent thermal, technique is simple, effectively reduce cost, and reacting weight is large, the preparation of the graphene quantum dot of gram level or even kilogram levels can be once completed, Graphene can be prepared on a large scale., through repeatedly peeling off and repeatedly reducing after size, the graphene oxide of raw material can be utilized completely meanwhile, obtain high productive rate.
The large-scale producing method of above-mentioned graphene quantum dot as the hydrothermal method of carbon source or adopt solvent-thermal method under organic acid environment to control the size of graphene quantum dot, can be controlled the size of graphene quantum dot with reductibility poly-hydroxy aldehyde preferably.Controlled good, be conducive to carry out continuous batch production.
Further set forth by specific embodiment below.
Embodiment 1
Prepare graphene quantum dot
1, provide the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers, mono-layer graphite oxide alkene is scattered in glycol dimethyl ether, the first dispersion liquid that the dispersed concentration that obtains mono-layer graphite oxide alkene is 2mg/mL, oxalic acid is added in the first dispersion liquid to the dispersed mixed solution that obtains; Wherein, the mass ratio of mono-layer graphite oxide alkene and oxalic acid is 1:3;
2, the ultrasonic dispersion under the ultrasound environments of 120W of this mixed solution is put into airtight reaction vessel after 4 hours, in the microwave environment of 500W, react 30min; Taking-up adds glycol dimethyl ether, the volume of the glycol dimethyl ether adding be the initial glycol dimethyl ether in the first dispersion liquid volume 15%; Continue in the microwave environment of 500W and react 10min, after reaction finishes, question response liquid cooling but, in reaction solution, add deionized water (in deionized water and the first dispersion liquid, the volume ratio of initial glycol dimethyl ether is 1:10), obtain reactant dispersion liquid, by the ultrasonic dispersion 30 minutes in the ultrasound environments of 120W of reactant dispersion liquid, then carry out suction filtration, get filtrate, obtain the solution of graphene quantum dot, for subsequent use; Get filter cake, obtain crude product;
3, citric acid is mixed with crude product, and add iron(ic) chloride, mix and obtain mixture, wherein, the mass ratio of crude product and citric acid is 1:5, the quality of iron(ic) chloride account for the mixture of crude product, citric acid, iron(ic) chloride quality 3%; This mixture is added in N-Methyl pyrrolidone, be uniformly dispersed and obtain the second dispersion liquid that the concentration of mixture is 0.5g/mL;
4, the second dispersion liquid is disperseed under the ultrasound environments of 120W after 2 hours, put into airtight reaction vessel, in 500W microwave environment, react 1 hour, add the reaction solution that deionized water obtains microwave reaction to dilute rear (volume ratio of the N-Methyl pyrrolidone in deionized water and the second dispersion liquid is 1:15), then under the ultrasound environments of 300W, disperse and peel off 2 hours, obtain the aqueous solution of graphene quantum dot, the solution that the aqueous solution of graphene quantum dot and above-mentioned steps 2 is obtained to Graphene carries out column chromatography, wherein, the stationary phase of column chromatography is silica gel, first-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:3 by volume, second-phase developping agent is deionized water, carry out column chromatography and obtain successively the solution of the graphene quantum dot that size is different, the solution that is the graphene quantum dot of the mixed solution that mixes for 1:3 by volume of methylene dichloride and methyl alcohol by solvent carries out vacuum backspin and boils off solvent, obtains dry graphene quantum dot powder, the solution of the graphene quantum dot that is deionized water by solvent, then is revolved and boils off solvent by volume for the mixed solvent of 1:1 extracts by methylene dichloride and methyl alcohol, obtains dry graphene quantum dot powder.
Fig. 2 is the fluorescence spectrum figure of the present embodiment 1 preparation-obtained graphene quantum dot.The fluorescent emission wavelength of the graphene quantum dot obtaining of being prepared by the present embodiment 1 as seen from Figure 2, is in 435nm left and right.
Embodiment 2
Prepare graphene quantum dot
1, provide the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers, it is in three diglycol ethylenes of 1:1 and the mixed solvent of N-Methyl pyrrolidone that mono-layer graphite oxide alkene is scattered in to volume ratio, the first dispersion liquid that the dispersed concentration that obtains mono-layer graphite oxide alkene is 6mg/mL, sodium oxalate is added in the first dispersion liquid to the dispersed mixed solution that obtains; Wherein, the mass ratio of mono-layer graphite oxide alkene and sodium oxalate is 1:8;
2, the ultrasonic dispersion under the ultrasound environments of 150W of this mixed solution is put into airtight reaction vessel after 1 hour, in the microwave environment of 700W, react 20min; It is three diglycol ethylenes of 1:1 and the mixed solvent of N-Methyl pyrrolidone that taking-up adds volume ratio, the volume of three diglycol ethylenes that the volume ratio adding is 1:1 and the mixed solvent of N-Methyl pyrrolidone be the mixed solvent of three diglycol ethylenes that are 1:1 of the initial volume ratio in the first dispersion liquid and N-Methyl pyrrolidone volume 12%; Continue in the microwave environment of 700W and react 20min, after reaction finishes, question response liquid cooling but, in reaction solution, add deionized water (volume ratio of three diglycol ethylenes that in deionized water and the first dispersion liquid, initial volume ratio is 1:1 and the mixed solvent of N-Methyl pyrrolidone is 1:20), obtain reactant dispersion liquid, by the ultrasonic dispersion 15 minutes in the ultrasound environments of 300W of reactant dispersion liquid, then carry out suction filtration, get filtrate, obtain the solution of graphene quantum dot, for subsequent use; Get filter cake, obtain crude product;
3, formic acid, xitix are mixed with crude product, and add magnesium chloride and cupric chloride, mix and obtain mixture, wherein, the mass ratio of crude product, formic acid and xitix is 1:4:4, the mass ratio of magnesium chloride and cupric chloride is 1:1, the quality sum of magnesium chloride and cupric chloride account for the mixture of crude product, formic acid, xitix, magnesium chloride and cupric chloride quality 2.5%; It is in three diglycol ethylenes of 1:1 and the mixed solvent of N-Methyl pyrrolidone that this mixture is added to volume ratio, is uniformly dispersed and obtains the second dispersion liquid that the concentration of mixture is 0.6g/mL;
4, the second dispersion liquid is disperseed under the ultrasound environments of 180W after 1.5 hours, put into airtight reaction vessel, in 550W microwave environment, react 0.5 hour, add the reaction solution that deionized water obtains microwave reaction to dilute rear (volume ratio of the glycol dimethyl ether in deionized water and the second dispersion liquid is 1:15), then under the ultrasound environments of 180W, disperse and peel off 3 hours, obtain the aqueous solution of graphene quantum dot, the solution that the aqueous solution of graphene quantum dot and above-mentioned steps 2 is obtained to Graphene carries out column chromatography, wherein, the stationary phase of column chromatography is silica gel, first-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:2 by volume, second-phase developping agent is deionized water, carry out column chromatography and obtain successively the solution of the graphene quantum dot that size is different, the solution that is the graphene quantum dot of the mixed solution that mixes for 1:2 by volume of methylene dichloride and methyl alcohol by solvent carries out vacuum backspin and boils off solvent, obtains dry graphene quantum dot powder, the solution of the graphene quantum dot that is deionized water by solvent, then is revolved and boils off solvent by volume for the mixed solvent of 2:1 extracts by methylene dichloride and methyl alcohol, obtains dry graphene quantum dot powder.
Fig. 3 is the fluorescence spectrum figure of the present embodiment 2 preparation-obtained graphene quantum dots.The fluorescent emission wavelength of the graphene quantum dot obtaining of being prepared by the present embodiment 2 as seen from Figure 3, is in 380nm left and right.
Embodiment 3
Prepare graphene quantum dot
1, provide the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers, mono-layer graphite oxide alkene is scattered in water, the first dispersion liquid that the dispersed concentration that obtains mono-layer graphite oxide alkene is 3mg/mL, adds xitix in the first dispersion liquid, the dispersed mixed solution that obtains; Wherein, the mass ratio of mono-layer graphite oxide alkene and xitix is 1:4;
2, the ultrasonic dispersion under the ultrasound environments of 200W of this mixed solution is put into airtight reaction vessel after 3 hours, in the microwave environment of 650W, react 8min; Taking-up adds water, the volume of the water adding be the initial water in the first dispersion liquid volume 10%; Continue in the microwave environment of 650W and react 8min, after reaction finishes, question response liquid cooling but, in reaction solution, add deionized water (in deionized water and the first dispersion liquid, the volume ratio of initial water is 1:10), obtain reactant dispersion liquid, by the ultrasonic dispersion 18 minutes in the ultrasound environments of 150W of reactant dispersion liquid, then carry out suction filtration, get filtrate, obtain the solution of graphene quantum dot, for subsequent use; Get filter cake, obtain crude product;
3, xitix is mixed with crude product, and add boron trifluoride, mix and obtain mixture, wherein, the mass ratio of crude product and xitix is 1:9, the quality of boron trifluoride account for the mixture of xitix, crude product and boron trifluoride quality 1.5%; This mixture is added to the water, is uniformly dispersed and obtains the second dispersion liquid that the concentration of mixture is 0.2g/mL;
4, the second dispersion liquid is disperseed under the ultrasound environments of 250W after 1 hour, put into airtight reaction vessel, in 650W microwave environment, react 0.5 hour, add the reaction solution that deionized water obtains microwave reaction to dilute rear (volume ratio of the glycol dimethyl ether in deionized water and the second dispersion liquid is 1:10), then under the ultrasound environments of 270W, disperse and peel off 3 hours, obtain the aqueous solution of graphene quantum dot, the solution that the aqueous solution of graphene quantum dot and above-mentioned steps 2 is obtained to Graphene carries out column chromatography, wherein, the stationary phase of column chromatography is silica gel, first-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:2 by volume, second-phase developping agent is deionized water, carry out column chromatography and obtain successively the solution of the graphene quantum dot that size is different, the solution that is the graphene quantum dot of the mixed solution that mixes for 1:2 by volume of methylene dichloride and methyl alcohol by solvent carries out vacuum backspin and boils off solvent, obtains dry graphene quantum dot powder, the solution of the graphene quantum dot that is deionized water by solvent, then is revolved and boils off solvent by volume for the mixed solvent of 2:1 extracts by methylene dichloride and methyl alcohol, obtains dry graphene quantum dot powder.
Fig. 4 is the fluorescence spectrum figure of the present embodiment 3 preparation-obtained graphene quantum dots.The fluorescent emission wavelength of the graphene quantum dot obtaining of being prepared by this law as seen from Figure 4, is in 390nm left and right.
Embodiment 4
Prepare graphene quantum dot
1, provide the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers, mono-layer graphite oxide alkene is scattered in glycerol, the first dispersion liquid that the dispersed concentration that obtains mono-layer graphite oxide alkene is 5mg/mL, Sunmorl N 60S is added in the first dispersion liquid to the dispersed mixed solution that obtains; Wherein, the mass ratio of mono-layer graphite oxide alkene and Sunmorl N 60S is 1:6;
2, the ultrasonic dispersion under the ultrasound environments of 200W of this mixed solution is put into airtight reaction vessel after 2 hours, in the microwave environment of 600W, react 10min; Taking-up adds glycerol, the volume of the glycerol adding be the initial glycerol in the first dispersion liquid volume 10%; Continue in the microwave environment of 600W and react 10min, after reaction finishes, question response liquid cooling but, in reaction solution, add deionized water (in deionized water and the first dispersion liquid, the volume ratio of initial glycerol is 1:15), obtain reactant dispersion liquid, by the ultrasonic dispersion 20 minutes in the ultrasound environments of 180W of reactant dispersion liquid, then carry out suction filtration, get filtrate, obtain the solution of graphene quantum dot, for subsequent use; Get filter cake, obtain crude product;
3, citric acid is mixed with crude product, and add zinc chloride, mix and obtain mixture, wherein, the mass ratio of crude product and citric acid is 1:7, the quality of zinc chloride be the mixture of citric acid, crude product and zinc chloride quality 2%; This mixture is added in glycerol, be uniformly dispersed and obtain the second dispersion liquid that the concentration of mixture is 0.5g/mL;
4, the second dispersion liquid is disperseed under the ultrasound environments of 250W after 1 hour, put into airtight reaction vessel, in 700W microwave environment, react 0.5 hour, add the reaction solution that deionized water obtains microwave reaction to dilute rear (volume ratio of the glycol dimethyl ether in deionized water and the second dispersion liquid is 1:15), then under the ultrasound environments of 180W, disperse and peel off 3 hours, obtain the aqueous solution of graphene quantum dot, the solution that the aqueous solution of graphene quantum dot and above-mentioned steps 2 is obtained to Graphene carries out column chromatography, wherein, the stationary phase of column chromatography is silica gel, first-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:2 by volume, second-phase developping agent is deionized water, carry out column chromatography and obtain successively the solution of the graphene quantum dot that size is different, the solution that is the graphene quantum dot of the mixed solution that mixes for 1:2 by volume of methylene dichloride and methyl alcohol by solvent carries out vacuum backspin and boils off solvent, obtains dry graphene quantum dot powder, the solution of the graphene quantum dot that is deionized water by solvent, then is revolved and boils off solvent by volume for the mixed solvent of 2:1 extracts by methylene dichloride and methyl alcohol, obtains dry graphene quantum dot powder.
Fig. 5 is the fluorescence spectrum figure of the present embodiment 4 preparation-obtained graphene quantum dots.The fluorescent emission wavelength of the graphene quantum dot obtaining of being prepared by this law as seen from Figure 5, is in 410nm left and right.
Embodiment 5
Prepare graphene quantum dot
1, provide the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers, mono-layer graphite oxide alkene is scattered in glycol dimethyl ether, the first dispersion liquid that the dispersed concentration that obtains mono-layer graphite oxide alkene is 2mg/mL, oxalic acid is added in the first dispersion liquid to the dispersed mixed solution that obtains; Wherein, the mass ratio of mono-layer graphite oxide alkene and oxalic acid is 1:3;
2, the ultrasonic dispersion under the ultrasound environments of 120W of this mixed solution is put into airtight reaction vessel after 4 hours, in the microwave environment of 500W, react 30min; Taking-up adds glycol dimethyl ether, the volume of the glycol dimethyl ether adding be the initial glycol dimethyl ether in the first dispersion liquid volume 15%; Continue in the microwave environment of 500W and react 10min, after reaction finishes, question response liquid cooling but, in reaction solution, add deionized water (in deionized water and the first dispersion liquid, the volume ratio of initial glycol dimethyl ether is 1:10), obtain reactant dispersion liquid, by the ultrasonic dispersion 5 minutes in the ultrasound environments of 280W of reactant dispersion liquid, then carry out suction filtration, get filtrate, obtain the solution of graphene quantum dot, for subsequent use; Get filter cake, obtain crude product;
3, glucose is mixed with crude product, and add iron(ic) chloride, mix and obtain mixture, wherein, the mass ratio of crude product and glucose is 1:5, the quality of iron(ic) chloride account for the mixture of glucose, crude product and iron(ic) chloride quality 1%; This mixture is added in glycol dimethyl ether, be uniformly dispersed and obtain the second dispersion liquid that the concentration of mixture is 0.1g/mL;
4, the second dispersion liquid is disperseed under the ultrasound environments of 120W after 2 hours, put into airtight reaction vessel, in 500W microwave environment, react 1 hour, add the reaction solution that deionized water obtains microwave reaction to dilute rear (volume ratio of the glycol dimethyl ether in deionized water and the second dispersion liquid is 1:20), then under the ultrasound environments of 300W, disperse and peel off 2 hours, obtain the aqueous solution of graphene quantum dot, the solution that the aqueous solution of graphene quantum dot and above-mentioned steps 2 is obtained to Graphene carries out column chromatography, wherein, the stationary phase of column chromatography is silica gel, first-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:3 by volume, second-phase developping agent is deionized water, carry out column chromatography and obtain successively the solution of the graphene quantum dot that size is different, the solution that is the graphene quantum dot of the mixed solution that mixes for 1:3 by volume of methylene dichloride and methyl alcohol by solvent carries out vacuum backspin and boils off solvent, obtains dry graphene quantum dot powder, the solution of the graphene quantum dot that is deionized water by solvent, then is revolved and boils off solvent by volume for the mixed solvent of 1:1 extracts by methylene dichloride and methyl alcohol, obtains dry graphene quantum dot powder.
Embodiment 6
Prepare graphene quantum dot
1, provide the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers, it is in 10% the aqueous solution of polyvinyl alcohol that mono-layer graphite oxide alkene is scattered in to mass concentration, the first dispersion liquid that the dispersed concentration that obtains mono-layer graphite oxide alkene is 10mg/mL, the citric acid that is 1:1 by mass ratio and Trisodium Citrate add in the first dispersion liquid, the dispersed mixed solution that obtains; Wherein, the ratio of the quality sum of the quality of mono-layer graphite oxide alkene and citric acid and Trisodium Citrate is 1:10;
2, the ultrasonic dispersion under the ultrasound environments of 300W of this mixed solution is put into airtight reaction vessel after 0.4 hour, in the microwave environment of 800W, react 5min; It is the aqueous solution of 10% polyvinyl alcohol that taking-up adds mass concentration, the volume of the aqueous solution of the polyvinyl alcohol that the mass concentration adding is 10% be the aqueous solution of the polyvinyl alcohol that is 10% of the initial mass concentration in the first dispersion liquid volume 10%; Continue in the microwave environment of 800W and react 5min, after reaction finishes, question response liquid cooling but, in reaction solution, add deionized water (volume ratio of the aqueous solution of the polyvinyl alcohol that in deionized water and the first dispersion liquid, initial mass concentration is 10% is 1:12), obtain reactant dispersion liquid, by the ultrasonic dispersion 30 minutes in the ultrasound environments of 200W of reactant dispersion liquid, then carry out suction filtration, get filtrate, obtain the solution of graphene quantum dot, for subsequent use; Get filter cake, obtain crude product;
3, glucose is mixed with crude product, and add aluminum chloride, mix and obtain mixture, wherein, the mass ratio of crude product and glucose is 1:10, the quality of aluminum chloride account for the mixture of glucose, crude product and aluminum chloride quality 3%; It is in 10% the aqueous solution of polyvinyl alcohol that this mixture is added to mass concentration, is uniformly dispersed and obtains the second dispersion liquid that the concentration of mixture is 1g/mL;
4, the second dispersion liquid is disperseed under the ultrasound environments of 300W after 0.5 hour, put into airtight reaction vessel, in 800W microwave environment, react 0.2 hour, add the reaction solution that deionized water obtains microwave reaction to dilute rear (volume ratio of the glycol dimethyl ether in deionized water and the second dispersion liquid is 1:15), then under the ultrasound environments of 120W, disperse and peel off 3 hours, obtain the aqueous solution of graphene quantum dot, the solution that the aqueous solution of graphene quantum dot and above-mentioned steps 2 is obtained to Graphene carries out column chromatography, wherein, the stationary phase of column chromatography is silica gel, first-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:1 by volume, second-phase developping agent is deionized water, carry out column chromatography and obtain successively the solution of the graphene quantum dot that size is different, the solution that is the graphene quantum dot of the mixed solution that mixes for 1:1 by volume of methylene dichloride and methyl alcohol by solvent carries out vacuum backspin and boils off solvent, obtains dry graphene quantum dot powder, the solution of the graphene quantum dot that is deionized water by solvent, then is revolved and boils off solvent by volume for the mixed solvent of 1:1 extracts by methylene dichloride and methyl alcohol, obtains dry graphene quantum dot powder.
Embodiment 7
Prepare graphene quantum dot
1, provide the mono-layer graphite oxide alkene of being prepared by the chemical method that improves Hummers, mono-layer graphite oxide alkene is scattered in three diglycol ethylenes, the first dispersion liquid that the dispersed concentration that obtains mono-layer graphite oxide alkene is 4mg/mL, sodium oxalate is added in the first dispersion liquid to the dispersed mixed solution that obtains; Wherein, the mass ratio of mono-layer graphite oxide alkene and sodium oxalate is 1:7;
2, the ultrasonic dispersion under the ultrasound environments of 250W of this mixed solution is put into airtight reaction vessel after 2.5 hours, in the microwave environment of 550W, react 25min; Taking-up adds three diglycol ethylenes, the volume of three diglycol ethylenes that add be the three initial diglycol ethylenes in the first dispersion liquid volume 13%; Continue in the microwave environment of 550W and react 25min, after reaction finishes, question response liquid cooling but, in reaction solution, add deionized water (in deionized water and the first dispersion liquid, the volume ratio of three initial diglycol ethylenes is 1:18), obtain reactant dispersion liquid, by the ultrasonic dispersion 10 minutes in the ultrasound environments of 220W of reactant dispersion liquid, then carry out suction filtration, get filtrate, obtain the solution of graphene quantum dot, for subsequent use; Get filter cake, obtain crude product;
3, hexanedial is mixed with crude product, and add lithium chloride, mix and obtain mixture, wherein, the mass ratio of crude product and hexanedial is 1:6, the quality of lithium chloride be the mixture of hexanedial, crude product and lithium chloride quality 2.5%; This mixture is added in three diglycol ethylenes, be uniformly dispersed and obtain the second dispersion liquid that the concentration of mixture is 0.3g/mL;
4, the second dispersion liquid is disperseed under the ultrasound environments of 150W after 1.8 hours, put into airtight reaction vessel, in 750W microwave environment, react 0.4 hour, add the reaction solution that deionized water obtains microwave reaction to dilute rear (volume ratio of the glycol dimethyl ether in deionized water and the second dispersion liquid is 1:15), then under the ultrasound environments of 250W, disperse and peel off 2.5 hours, obtain the aqueous solution of graphene quantum dot, the solution that the aqueous solution of graphene quantum dot and above-mentioned steps 2 is obtained to Graphene carries out column chromatography, wherein, the stationary phase of column chromatography is silica gel, first-phase developping agent is the mixed solution that methylene dichloride and methyl alcohol mix for 1:2 by volume, second-phase developping agent is deionized water, carry out column chromatography and obtain successively the solution of the graphene quantum dot that size is different, the solution that is the graphene quantum dot of the mixed solution that mixes for 1:2 by volume of methylene dichloride and methyl alcohol by solvent carries out vacuum backspin and boils off solvent, obtains dry graphene quantum dot powder, the solution of the graphene quantum dot that is deionized water by solvent, then is revolved and boils off solvent by volume for the mixed solvent of 2:1 extracts by methylene dichloride and methyl alcohol, obtains dry graphene quantum dot powder.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (15)
1. a large-scale producing method for graphene quantum dot, is characterized in that, comprises the steps:
Graphene oxide is added in the first solvent, and dispersed first dispersion liquid that obtains, adds reductive agent in described the first dispersion liquid the dispersed mixed solution that obtains;
Described mixed solution is reacted 10 minutes～60 minutes in the microwave environment of 500 watts～800 watts, carry out solid-liquid separation after cooling, get solid, obtain crude product;
One in reductibility poly-hydroxy aldehyde and organic acid is mixed with described crude product, add Lewis acid, mix and obtain mixture, described mixture is added in the second solvent, dispersed second dispersion liquid that obtains; And
Described the second dispersion liquid is reacted 0.2 hour～1 hour in 500 watts～800 watts microwave environments, then under the ultrasound environments of 120 watts～300 watts, peel off 2 hours～3 hours, after separation and purification, obtain described graphene quantum dot.
2. the large-scale producing method of graphene quantum dot according to claim 1, it is characterized in that, before described mixed solution being reacted in the microwave environment of 500 watts～800 watts to the step of 10 minutes～60 minutes, comprise the step of ultrasonic agitation, the step of described ultrasonic agitation is specially: described mixed solution is stirred 0.5 hour～4 hours under the ultrasound environments of 120 watts～300 watts.
3. the large-scale producing method of graphene quantum dot according to claim 1, it is characterized in that, before described the second dispersion liquid being reacted in 500 watts～800 watts microwave environments to the step of 0.2 hour～1 hour, also comprise the step of ultrasonic dispersion, the step of described ultrasonic dispersion is specially: described the second dispersion liquid is disperseed 0.5 hour～2 hours in the ultrasound environments of 120 watts～300 watts.
4. the large-scale producing method of graphene quantum dot according to claim 1, it is characterized in that, described the first solvent and the second solvent are all selected from least one in the aqueous solution, glycerol, three diglycol ethylenes and the N-Methyl pyrrolidone of water, glycol dimethyl ether, polyvinyl alcohol.
5. the large-scale producing method of graphene quantum dot according to claim 1, is characterized in that, in described the first dispersion liquid, the concentration of described graphene oxide is 2 mg/ml～10 mg/ml.
6. the large-scale producing method of graphene quantum dot according to claim 1, it is characterized in that, described reductive agent is selected from least one in citric acid, gluconic acid, formic acid, xitix, oxalic acid, Trisodium Citrate, Sunmorl N 60S, sodium formiate, sodium ascorbate and sodium oxalate.
7. the large-scale producing method of graphene quantum dot according to claim 1, is characterized in that, the mass ratio of described graphene oxide and described reductive agent is 1:3～10.
8. the large-scale producing method of graphene quantum dot according to claim 1, it is characterized in that, the described operation that described mixed solution is reacted 10 minutes～60 minutes in the microwave environment of 500 watts～800 watts is specially: described mixed solution is reacted 5 minutes～30 minutes in the microwave environment of 500 watts～800 watts, taking-up is added after described the first solvent, continues in the microwave environment of 500 watts～800 watts and reacts 5 minutes～30 minutes; The volume of the first solvent of wherein, adding be described the first solvent original volume 10%～15%.
9. the large-scale producing method of graphene quantum dot according to claim 1, is characterized in that, a kind of mass ratio in described crude product and described reductibility poly-hydroxy aldehyde and organic acid is 1:5～10.
10. according to the large-scale producing method of the graphene quantum dot described in claim 1 or 9, it is characterized in that, described reductibility poly-hydroxy aldehyde is glucose or hexanedial.
The large-scale producing method of 11. graphene quantum dots according to claim 1, is characterized in that, described Lewis acid is selected from least one in iron(ic) chloride, aluminum chloride, zinc chloride, boron trifluoride, magnesium chloride, cupric chloride and lithium chloride.
The large-scale producing method of 12. graphene quantum dots according to claim 1, is characterized in that, described organic acid is selected from least one in citric acid, gluconic acid, formic acid, xitix and oxalic acid.
The large-scale producing method of 13. graphene quantum dots according to claim 1, is characterized in that, in described the second dispersion liquid, the concentration of described mixture is 0.1 grams per milliliter～1 grams per milliliter.
The large-scale producing method of 14. graphene quantum dots according to claim 1, is characterized in that, described lewis acidic quality account for described mixture quality 1%～3%.
The large-scale producing method of 15. graphene quantum dots according to claim 1, it is characterized in that, the step that obtains described graphene quantum dot after described separation and purification is specially: by be set forth in and under the ultrasound environments of 120 watts～300 watts, peel off the 2 hours～reaction product that obtains for 3 hours and carry out column chromatography for separation, then vacuum is revolved and is steamed except desolventizing, obtains described graphene quantum dot; Wherein, the stationary phase of described column chromatography is silica gel or polyacrylamide, and first-phase developping agent is methylene dichloride and the methyl alcohol mixed solution that mix 1:1～3 by volume, and second-phase developping agent is deionized water.
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| CN103787319B (en) | 2015-10-14 |
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