CN103555326B - A kind of preparation method of oxygen-free Graphene fluorescence quantum - Google Patents
A kind of preparation method of oxygen-free Graphene fluorescence quantum Download PDFInfo
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Abstract
A preparation method for oxygen-free Graphene fluorescence quantum, relates to Graphene.Graphite Powder 99 is dispersed in tetrahydrofuran solution; ultrasonic disperse under nitrogen protection condition; metallic lithium and naphthalene is added successively in gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid; halo organic reagent or methyl alcohol is added in gained mixing solutions; after reaction; gained solid product is washed, after drying, obtains alkylation Graphene or hydrogenation Graphene.By obtained alkylation Graphene or hydrogenation graphene dispersion in organic solvent, after ultrasonic disperse, then transfer to reaction kettle for reaction, be cooled to room temperature, obtain oxygen-free Graphene fluorescence quantum.There is efficient, controlled feature.The graphene quantum dot prepared has conversion and lower conversion characteristic on good dispersiveness, fluorescence in water and common organic solvents, can be applicable to the fields such as sensor, biological labled material and energy and material.
Description
Technical field
The present invention relates to Graphene, especially relate to a kind of preparation method of oxygen-free Graphene fluorescence quantum.
Background technology
Owing to having large surface-area, high carrier mobility, good conduction and heat conductivility, Graphene was just obtained the extensive concern of people since preparing first from 2004, demonstrated application prospect widely in fields such as the energy, material, catalysis, biology, electronics.As a member brand-new in Graphene family, graphene quantum dot is except possessing the excellent properties of Graphene itself, also present unique performance because of quantum confined effect and side effect, as good chemical stability, biocompatibility, electroconductibility, stable fluorescence, lower bio-toxicity etc., all demonstrates more tempting application prospect at bio-imaging, photovoltaic device and sensor numerous areas.
In recent years, about the preparation method of zero dimension graphene quantum dot, there are reports, mainly can be divided into two kinds: one is from small molecules, adopt organic synthesis legal system for graphene quantum dot (Yan X et al, J.Am.Chem.Soc., 2010,132,5944-5945).These class methods are conducive to the pattern and the size that control graphene quantum dot, but the complex steps of synthesis, productive rate are low; Another kind method is from carbon fiber, graphite or graphene oxide, adopts the method for physics or chemistry cut or be cut into graphene quantum dot, as hydrothermal method (Pan D et al, Adv.Mater., 2010,22,734-738), electrochemical process (Li Y etal, Adv.Mater., 2011,23,776-780), carbon fiber stripping method (Peng J et al, Nano Lett., 2012,12,844-849) etc.This class methods energy one-step synthesis obtains graphene quantum dot, but the synthetic yield of product and purity are not high, to the pre-treatment (oxidizing reaction of graphite) of reaction raw materials or aftertreatment (post of crossing of product is separated or the dialysis purifying) length consuming time of reaction product, be unfavorable for the extensive Synthesis and applications of graphene quantum dot.Meanwhile, the graphene quantum dot adopting these methods to synthesize to obtain containing oxy radicals such as epoxy group(ing), carbonyl and carboxyls, should belong to graphene oxide quantum dot mostly strictly speaking, instead of graphene quantum dot truly.Therefore, the high-efficiency synthesis method developing a kind of oxygen-free graphene quantum dot is very necessary.
Summary of the invention
The object of the invention is to the deficiency for existing technology of preparing, a kind of preparation method of oxygen-free Graphene fluorescence quantum is provided.
One of preparation method of oxygen-free Graphene fluorescence quantum of the present invention, comprises the following steps:
1) preparation of alkylation Graphene: Graphite Powder 99 is dispersed in tetrahydrofuran solution, ultrasonic disperse under nitrogen protection condition, metallic lithium and naphthalene is added successively in gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, halo organic reagent is added in gained mixing solutions, after reaction, gained solid product is washed, after drying, obtains alkylation Graphene;
2) synthesis of graphene quantum dot (GQDs): by alkylation graphene dispersion obtained for step 1) in organic solvent, after ultrasonic disperse, then transfer to reaction kettle for reaction, be cooled to room temperature, obtain oxygen-free Graphene fluorescence quantum.
In step 1), the proportioning of described Graphite Powder 99 and tetrahydrofuran solution can be (10 ~ 100) mg: (50 ~ 150) mL, and wherein, Graphite Powder 99 is calculated in mass, and tetrahydrofuran solution is calculated by volume; The condition of described ultrasonic disperse can be the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 3 ~ 10min of ultrasonic disperse; The mol ratio of described metallic lithium and graphite (carbon atom) can be 30: 1, and the mol ratio of metallic lithium and naphthalene can >1; Described halo organic reagent can be selected from Dodecyl Bromide, 6-bromonexanoic acid, 6-bromonexanoic acid methyl esters, 11-bromoundecanoic acid; The time of described reaction can be 5 ~ 24h; Gained solid product can wash with ethanol, toluene, second alcohol and water by the method for described washing successively; The condition of described drying can be dry under 60 ~ 80 DEG C of vacuum conditions; When described halo organic reagent is Dodecyl Bromide, gained alkylation Graphene is Dodecyl Bromide modified graphene, when described halo organic reagent is 6-bromonexanoic acid, gained alkylation Graphene is 6-bromonexanoic acid modified graphene, when described halo organic reagent is 6-bromonexanoic acid methyl esters, gained alkylation Graphene is 6-bromonexanoic acid methyl esters modified graphene, when described halo organic reagent is 11-bromoundecanoic acid, gained alkylation Graphene is 11-bromoundecanoic acid modified graphene.
In step 2) in, described organic solvent can be selected from DMF (DMF), N-Methyl pyrrolidone (NMP), toluene, the one in dimethylbenzene etc.; The proportioning of described alkylation Graphene and organic solvent can be (3 ~ 50) mg: (20 ~ 50) mL, and wherein, alkylation Graphene is calculated in mass, and organic solvent is calculated by volume; The condition of described ultrasonic disperse can be the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 30 ~ 180min of ultrasonic disperse; Described reactor can adopt the autoclave of inner liner polytetrafluoroethylene; The temperature of described reaction can be 200 DEG C, and the time of reaction can be 5 ~ 20h.
The preparation method two of oxygen-free Graphene fluorescence quantum of the present invention, comprises the following steps:
1) preparation of hydrogenation Graphene: Graphite Powder 99 is dispersed in tetrahydrofuran solution; ultrasonic disperse under nitrogen protection condition; metallic lithium and naphthalene is added successively in gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid; methyl alcohol is added in gained mixing solutions; after reaction; gained solid product is washed, after drying, obtains hydrogenation Graphene.
2) synthesis of graphene quantum dot (GQDs): by hydrogenation graphene dispersion obtained for step 1) in organic solvent, after ultrasonic disperse, then transfer to reaction kettle for reaction, be cooled to room temperature, obtain oxygen-free Graphene fluorescence quantum.
In step 1), the proportioning of described Graphite Powder 99 and tetrahydrofuran solution can be (10 ~ 100) mg: (50 ~ 150) mL, and wherein, Graphite Powder 99 is calculated in mass, and tetrahydrofuran solution is calculated by volume; The condition of described ultrasonic disperse can be the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 3 ~ 10min of ultrasonic disperse; The mol ratio of described metallic lithium and graphite (carbon atom) can be 30: 1, and the mol ratio of metallic lithium and naphthalene can >1; The time of described reaction can be 5 ~ 24h; Gained solid product can wash with ethanol, toluene, second alcohol and water by the method for described washing successively; The condition of described drying can be dry under 60 ~ 80 DEG C of vacuum conditions.
In step 2) in, described organic solvent can be selected from DMF (DMF), N-Methyl pyrrolidone (NMP), toluene, the one in dimethylbenzene etc.; The proportioning of described hydrogenation Graphene and organic solvent can be (3 ~ 50) mg: (20 ~ 50) mL, and wherein, hydrogenation Graphene is calculated in mass, and organic solvent is calculated by volume; The condition of described ultrasonic disperse can be the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 30 ~ 180min of ultrasonic disperse; Described reactor can adopt the autoclave of inner liner polytetrafluoroethylene; The temperature of described reaction can be 200 DEG C, and the time of reaction can be 5 ~ 20h.
The graphene quantum dot preparation efficiency of gained of the present invention is high (>95%), without the need to just obtaining through dialysis or pillar layer separation the graphene quantum dot launching hyperfluorescenceZeng Yongminggaoyingguang, atomic force microscope (AFM) and transmission electron microscope (TEM) show, the graphene quantum dot prepared has good dispersiveness, particle size dispersion is about 2 ~ 7nm, and the height of graphene quantum dot is 0.5 ~ 1.5nm.Ultra-violet absorption spectrum and fluorescence spectrum show, the blue light of the graphene quantum dot that the present invention prepares energy emitting bright under 365nm ultra violet lamp and green glow, and show the fluorescent emission behavior with excitation light wave long correlation, there is good upper conversion characteristic.
The preparation method of a kind of Graphene fluorescence quantum provided by the invention has efficient, controlled feature.The graphene quantum dot prepared has conversion and lower conversion characteristic on good dispersiveness, fluorescence in water and common organic solvents, can be applicable to the fields such as sensor, biological labled material and energy and material.The graphene quantum dot that the present invention prepares is hardly containing oxygen-containing functional group (as epoxy group(ing), carboxyl, carbonyl etc.), significant to the deep fluorescence radiation mechanism understanding graphene quantum dot.
The invention provides a kind of efficient, controllable method for preparing of Graphene fluorescence quantum, the graphene quantum dot of gained is without the need to passing through dialysis or pillar layer separation, in water and common organic solvents, there is good dispersiveness, there is conversion and lower conversion characteristic on excellent fluorescence.The present invention is with alkylation Graphene or hydrogenation Graphene for raw material, and 200 DEG C of solvent thermal conditions, next step prepares the graphene quantum dot launching hyperfluorescenceZeng Yongminggaoyingguang.By changing the solvent of reaction, changing solvent-dispersible and the fluorescent emission peak position of graphene quantum dot further, obtaining the graphene quantum dot launching blue light and green glow.
Accompanying drawing explanation
Fig. 1 is the TEM figure of gained blue-fluorescence graphene quantum dot of the present invention.
Fig. 2 is the AFM figure of gained blue-fluorescence graphene quantum dot of the present invention.
Fig. 3 is the down-conversion fluorescent spectrogram of gained blue-fluorescence graphene quantum dot of the present invention under different wave length exciting light.In figure 3, X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity (a.u.); Curve a is 305nm, and curve b is 325nm, and curve c is 345nm, and curve d is 365nm, and curve e is 385nm, and curve f is 405nm, and curve g is 425nm.
Fig. 4 is the up-conversion fluorescence spectrogram of gained blue-fluorescence graphene quantum dot of the present invention under different wave length exciting light.In the diagram, X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity (a.u.); Curve a is 660nm, and curve b is 680nm, and curve c is 700nm, and curve d is 720nm, and curve e is 740nm, and curve f is 760nm, and curve g is 780nm, and curve h is 800nm.
Fig. 5 is C1s high resolution x-ray photoelectron spectroscopy (XPS) figure of gained blue-fluorescence graphene quantum dot of the present invention.In Figure 5, X-coordinate is for combining energy (eV), and ordinate zou is intensity (a.u.); Solid line is experimental data, and dotted line is fitting data.
Fig. 6 is the TEM figure of gained green fluorescence graphene quantum dot of the present invention.
Fig. 7 is the AFM figure of gained green fluorescence graphene quantum dot of the present invention.
Fig. 8 is the down-conversion fluorescent spectrogram of gained green fluorescence graphene quantum dot of the present invention under different wave length exciting light.In fig. 8, X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity (a.u.); Curve a is 345nm, and curve b is 365nm, and curve c is 385nm, and curve d is 405nm, and curve e is 425nm, and curve f is 445nm, and curve g is 465nm, and curve h is 485nm.
Fig. 9 is the up-conversion fluorescence spectrogram of gained green fluorescence graphene quantum dot of the present invention under different wave length exciting light.In fig .9, X-coordinate is wavelength (nm), and ordinate zou is fluorescence intensity (a.u.); Curve a is 740nm, and curve b is 760nm, and curve c is 780nm, and curve d is 800nm, and curve e is 820nm.
Embodiment
Embodiment 1
3mg1-bromododecane modified graphene is added in 45mL DMF, ultrasonic disperse 60min(90W, 100kHz), dispersion liquid is transferred in the autoclave of inner liner polytetrafluoroethylene, under 200 DEG C of conditions, react 20h, after reaction terminates, be cooled to room temperature.
As shown in Figure 1, being uniformly dispersed of graphene quantum dot, particle size dispersion is 2 ~ 6nm, and median size is 3.75nm.As shown in Figure 2, the height of graphene quantum dot is about 0.5 ~ 1nm.As shown in Figure 3, graphene quantum dot shows the fluorescent emission behavior with excitation light wave long correlation, under 365nm exciting light, have maximum emission peak near 440nm.As shown in Figure 4, graphene quantum dot has maximum emission peak under 780nm exciting light near 450nm.As shown in Figure 5, synthesize the graphene quantum dot obtained and contain oxygen-containing functional group hardly.
Embodiment 2
3mg1-bromododecane modified graphene is added in 45mL NMP, ultrasonic disperse 60min(90W, 100kHz), dispersion liquid is transferred in the autoclave of inner liner polytetrafluoroethylene, under 200 DEG C of conditions, react 20h, after reaction terminates, be cooled to room temperature.
As shown in Figure 6, being uniformly dispersed of graphene quantum dot, particle size dispersion is 2 ~ 7nm, and median size is 3.95nm.As shown in Figure 7, the height of graphene quantum dot is about 0.5 ~ 1.5nm., as shown in Figure 8, graphene quantum dot shows the fluorescent emission behavior with excitation light wave long correlation, under 405nm exciting light, have maximum emission peak near 490nm.As shown in Figure 9, graphene quantum dot has maximum emission peak under 780 ~ 800nm exciting light near 490nm.
Embodiment 3
3mg1-bromododecane modified graphene is added in 45mL toluene, ultrasonic disperse 60min(90W, 100kHz), dispersion liquid is transferred in the autoclave of inner liner polytetrafluoroethylene, 20h is reacted under 200 DEG C of conditions, be cooled to room temperature after reaction terminates, obtain the product being similar to embodiment 1.
Embodiment 4
3mg1-bromododecane modified graphene is added in 45mL dimethylbenzene, ultrasonic disperse 60min(90W, 100kHz), dispersion liquid is transferred in the autoclave of inner liner polytetrafluoroethylene, 20h is reacted under 200 DEG C of conditions, be cooled to room temperature after reaction terminates, obtain the product being similar to embodiment 1.
Embodiment 5
" Dodecyl Bromide modified graphene " in embodiment 1 changed into " 6-bromocaproic acid methyl esters modified graphene ", other conditions of preparation, with embodiment 1, obtain the product being similar to embodiment 1.
Embodiment 6
" Dodecyl Bromide modified graphene " in embodiment 1 changed into " 6-bromocaproic acid modified graphene ", other conditions of preparation, with embodiment 1, obtain the product being similar to embodiment 1.
Embodiment 7
" Dodecyl Bromide modified graphene " in embodiment 1 changed into " 11-bromine undeeanoic acid modified graphene ", other conditions of preparation, with embodiment 1, obtain the product being similar to embodiment 1.
Embodiment 8
" Dodecyl Bromide modified graphene " in embodiment 1 changed into " hydrogenation Graphene ", other conditions of preparation, with embodiment 1, obtain the product being similar to embodiment 1.
Embodiment 9
" Dodecyl Bromide modified graphene " in embodiment 2 changed into " 6-bromocaproic acid methyl esters modified graphene ", other conditions of preparation, with embodiment 2, obtain the product being similar to embodiment 2.
Embodiment 10
" Dodecyl Bromide modified graphene " in embodiment 2 changed into " 6-bromocaproic acid modified graphene ", other conditions of preparation, with embodiment 2, obtain the product being similar to embodiment 2.
Embodiment 11
" Dodecyl Bromide modified graphene " in embodiment 2 changed into " 11-bromine undeeanoic acid modified graphene ", other conditions of preparation, with embodiment 2, obtain the product being similar to embodiment 2.
Embodiment 12
" Dodecyl Bromide modified graphene " in embodiment 2 changed into " hydrogenation Graphene ", other conditions of preparation, with embodiment 2, obtain the product being similar to embodiment 2.
Claims (8)
1. a preparation method for oxygen-free Graphene fluorescence quantum, is characterized in that comprising the following steps:
1) preparation of alkylation Graphene: Graphite Powder 99 is dispersed in tetrahydrofuran solution, ultrasonic disperse under nitrogen protection condition, metallic lithium and naphthalene is added successively in gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, halo organic reagent is added in gained mixing solutions, after reaction, gained solid product is washed, after drying, obtains alkylation Graphene; The proportioning of described Graphite Powder 99 and tetrahydrofuran solution is (10 ~ 100) mg: (50 ~ 150) mL, and wherein, Graphite Powder 99 is calculated in mass, and tetrahydrofuran solution is calculated by volume; Described halo organic reagent is selected from Dodecyl Bromide, 6-bromonexanoic acid, 6-bromonexanoic acid methyl esters, 11-bromoundecanoic acid;
When described halo organic reagent is Dodecyl Bromide, gained alkylation Graphene is Dodecyl Bromide modified graphene, when described halo organic reagent is 6-bromonexanoic acid, gained alkylation Graphene is 6-bromonexanoic acid modified graphene, when described halo organic reagent is 6-bromonexanoic acid methyl esters, gained alkylation Graphene is 6-bromonexanoic acid methyl esters modified graphene, when described halo organic reagent is 11-bromoundecanoic acid, gained alkylation Graphene is 11-bromoundecanoic acid modified graphene;
2) synthesis of graphene quantum dot: by step 1) obtained alkylation graphene dispersion in organic solvent, after ultrasonic disperse, then transfer to reaction kettle for reaction, be cooled to room temperature, obtain oxygen-free Graphene fluorescence quantum; Described organic solvent is selected from DMF, N-Methyl pyrrolidone, toluene, the one in dimethylbenzene; The proportioning of described alkylation Graphene and organic solvent is (3 ~ 50) mg: (20 ~ 50) mL, wherein, alkylation Graphene is calculated in mass, and organic solvent is calculated by volume.
2. the preparation method of a kind of oxygen-free Graphene fluorescence quantum as claimed in claim 1, it is characterized in that in step 1) in, the condition of described ultrasonic disperse is the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 3 ~ 10min of ultrasonic disperse.
3. the preparation method of a kind of oxygen-free Graphene fluorescence quantum as claimed in claim 1, is characterized in that in step 1) in, the mol ratio of described metallic lithium and Graphite Powder 99 is 30: 1, the mol ratio >1 of metallic lithium and naphthalene; The time of described reaction is 5 ~ 24h; The method of described washing is washed with ethanol, toluene, second alcohol and water successively by gained solid product; The condition of described drying is dry under 60 ~ 80 DEG C of vacuum conditions.
4. the preparation method of a kind of oxygen-free Graphene fluorescence quantum as claimed in claim 1, it is characterized in that in step 2) in, the condition of described ultrasonic disperse is the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 30 ~ 180min of ultrasonic disperse; Described reactor adopts the autoclave of inner liner polytetrafluoroethylene; The temperature of described reaction is 200 DEG C, and the time of reaction is 5 ~ 20h.
5. a preparation method for oxygen-free Graphene fluorescence quantum, is characterized in that comprising the following steps:
1) preparation of hydrogenation Graphene: Graphite Powder 99 is dispersed in tetrahydrofuran solution, ultrasonic disperse under nitrogen protection condition, metallic lithium and naphthalene is added successively in gained Graphite Powder 99 tetrahydrofuran (THF) dispersion liquid, methyl alcohol is added in gained mixing solutions, after reaction, gained solid product is washed, after drying, obtains hydrogenation Graphene; The proportioning of described Graphite Powder 99 and tetrahydrofuran solution is (10 ~ 100) mg: (50 ~ 150) mL, and wherein, Graphite Powder 99 is calculated in mass, and tetrahydrofuran solution is calculated by volume;
2) synthesis of graphene quantum dot: by step 1) obtained hydrogenation graphene dispersion in organic solvent, after ultrasonic disperse, then transfer to reaction kettle for reaction, be cooled to room temperature, obtain oxygen-free Graphene fluorescence quantum; Described organic solvent is selected from DMF, N-Methyl pyrrolidone, toluene, the one in dimethylbenzene; The proportioning of described hydrogenation Graphene and organic solvent is (3 ~ 50) mg: (20 ~ 50) mL, wherein, hydrogenation Graphene is calculated in mass, and organic solvent is calculated by volume.
6. the preparation method of a kind of oxygen-free Graphene fluorescence quantum as claimed in claim 5, it is characterized in that in step 1) in, the condition of described ultrasonic disperse is the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 3 ~ 10min of ultrasonic disperse.
7. the preparation method of a kind of oxygen-free Graphene fluorescence quantum as claimed in claim 5, is characterized in that in step 1) in, the mol ratio of described metallic lithium and Graphite Powder 99 is 30: 1, the mol ratio >1 of metallic lithium and naphthalene; The time of described reaction is 5 ~ 24h; The method of described washing is washed with ethanol, toluene, second alcohol and water successively by gained solid product; The condition of described drying is dry under 60 ~ 80 DEG C of vacuum conditions.
8. the preparation method of a kind of oxygen-free Graphene fluorescence quantum as claimed in claim 5, it is characterized in that in step 2) in, the condition of described ultrasonic disperse is the power 90W of ultrasonic disperse, the frequency 100kHz of ultrasonic disperse, the time 30 ~ 180min of ultrasonic disperse; Described reactor adopts the autoclave of inner liner polytetrafluoroethylene; The temperature of described reaction is 200 DEG C, and the time of reaction is 5 ~ 20h.
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| CN103864046B (en) * | 2014-03-25 | 2016-06-01 | 中国科学院上海有机化学研究所 | A kind of method preparing hydrogenation Graphene |
| CN109135873A (en) * | 2017-06-28 | 2019-01-04 | 中国石油化工股份有限公司 | A kind of oil-soluble graphite ene compound and the preparation method and application thereof |
| CN110093157B (en) * | 2017-09-29 | 2022-06-03 | 相昌盛 | Method for extracting fluorescent nanostructure from carbon source through reduction reaction |
| CN107986268A (en) * | 2017-12-13 | 2018-05-04 | 天津宝兴威科技股份有限公司 | A kind of preparation method of alkyl functional graphite alkene quantum dot |
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