CN103738941A - Graphene quantum dot preparation method - Google Patents
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Abstract
The present invention discloses a graphene quantum dot preparation method, belongs to the technical field of nanometer material preparation, and particularly relates to a graphene quantum dot preparation method. The technical scheme comprises that: a carbon material being subjected to deep oxidation is cut into graphene oxide nano-sheets, C=C bonds and C-C bonds of the graphene oxide are broken to prepare green fluorescence graphene oxide quantum dots, and a reduction or high temperature annealing method is further adopted to prepare the blue fluorescence graphene quantum dots. According to the present invention, the operations are simple, the raw materials are easy to obtain, and the prepared graphene quantum dots have characteristics of excellent monodispersity, good water solubility and strong fluorescence, and have potential application prospects in the fields of supercapacitors, lithium batteries, biological imaging, solar cells, field-effect transistors, OLEDs and the like.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of graphene quantum dot.
Background technology
Graphene has a wide range of applications in field of nanometer technology because it has unique physical properties, has also caused the extensive concern of academia.But, Graphene is the semi-conductor of zero band gap, do not have pure zirconia Graphene or the Graphene of band gap not to observe fluorescence property, this just limits its application at electronics and optoelectronic areas, but the limitation of size of Graphene below 100 nanometers, this class graphene nanometer sheet is called as graphene quantum dot, and it has quantum confined effect and side effect, makes graphene quantum dot produce band gap.If the size of Graphene quantum further can be reduced to below 10 nanometers, its quantum confined effect and limit effect will significantly strengthen, and can make this undersized Graphene (being graphene quantum dot) be endowed new physical properties.
At present, the technology of opening Graphene band gap mainly contains two kinds, and the first is introduced size and quantum confined effect, forms graphene nanobelt quantum dot alive; It two is exactly chemical doping.The Dai Hongjie of Stanford Univ USA teach problem group is being made many breakthrough progress aspect the preparation of graphene nanobelt and applied research, the technology of exploitation has realized the graphene nanobelt of certain width, the field-effect of preparing based on graphene nanobelt, transistor has up to 10
7the on-off ratio of the order of magnitude, these researchs have illustrated that Graphene can be with the importance of cutting out.
But the method for preparing graphene quantum dot mainly contains two classes, the first is smashed system by Graphene by top-down mode, main method has ultrasonic oxidation, hydro-thermal, ultraviolet etching method, uses carbon nano-particle by Hummers method stripping method, also has investigator to use the methods such as electron beam lithography, focused-ion-beam lithography to prepare graphene quantum dot; It two is to be self-assembled into graphene quantum dot by mode from bottom to top.But these methods of preparing graphene quantum dot exist the shortcomings such as technique is loaded down with trivial details, cost is expensive, productive rate is lower, be not suitable for batch production and application.
Summary of the invention
The object of the invention is to solve the deficiencies in the prior art and shortcoming, a kind of method of directly being prepared graphene quantum dot by carbon material is provided.It is raw material that this method adopts cheap carbon material, by simple controlled heating in water bath, stir and prepare graphene oxide quantum dot, then by reductive agent, reduce or high temperature annealing mode makes graphene oxide quantum dot have the characteristics such as strong fluorescent effect and good aqueous solubility, and explained the mechanism (see figure 1) of correlated response, graphene oxide quantum dot provided by the invention has very large application prospect at aspects such as photoelectric material and device preparation, super capacitor and biological fluorescent labellings.
Technical scheme provided by the invention comprises the following steps: 1. the preparation of green fluorescence graphene oxide quantum dot; 2. the preparation of blue-fluorescence graphene quantum dot.
1. the preparation of green fluorescence graphene oxide quantum dot
In beaker, add carbon material, add the vitriol oil with respect to carbon material consumption 80-1600 wt%, then in condition of ice bath, slowly add the potassium permanganate of relative vitriol oil consumption 10-80 wt%, solution is transferred under the cold condition of 20-50 ℃ and reacted 0.5-3 hour, then shift the hot stage reaction of 80-150 ℃ 0.5-4 hour.Question response completely after, to adding with respect to the hydrogen peroxide of potassium permanganate consumption 10-80 wt% in solution, remove excessive potassium permanganate, obtain lurid clear solution.Then add excessive NaOH that pH is adjusted to 7-8, add again a small amount of rare HCl solution to make its pH for neutral, with deionized water by centrifugal yellow mercury oxide, washing, then, obtain yellow solution with the filtering with microporous membrane of 0.22-0.4 micron, by solution, at cut-off molecular weight, be to dialyse in the dialysis tubing of 3000-14500 Da, dialysis graphene oxide solution is later obtained to green fluorescence graphene oxide quantum dot (GOQDs) through lyophilize.
2. the preparation of blue-fluorescence graphene quantum dot
(1) by reduction mode, prepare blue-fluorescence graphene quantum dot
In beaker, add the green fluorescence graphene oxide quantum dot making in a certain amount of step 1, add the reductive agent with respect to green oxidation graphene quantum dot consumption (GOQDs) 60-200 wt %, reductase 12-24 h at normal temperatures, adding deionized water, to be diluted to pH value of solution be 5-7, its solution is placed in the dialysis tubing that cut-off molecular weight is 3000-14500 Da and is dialysed, obtain blue-fluorescence graphene quantum dot (GQDs).
(2) by high temperature annealing mode, prepare blue-fluorescence graphene quantum dot
Taking a certain amount of green fluorescence graphene oxide quantum dot (GOQDs) is placed in porcelain boat, porcelain boat is placed in tube furnace and passes into rare gas element (nitrogen or argon gas, helium etc.), with the speed of 10 ℃/min, be warmed up to 200-600 ℃ of maintenance cooling naturally after 5-60 minute.Obtained blue-fluorescence graphene quantum dot (GQDs), be again dispersed in water, had water-solublely preferably, under ultraviolet lamp, by different excitation wavelengths, can see blue light-emitting, thereby obtain blue fluorescence graphene quantum dot.
Described carbon material is any one or multiple mixture in graphite oxide, graphene oxide, Graphene, graphene nanobelt, graphene nano particle, nano-graphite, single wall or multi-walled carbon nano-tubes, carbon fiber.
Described millipore filtration be in tetrafluoroethylene filtering membrane, polycarbonate filtering membrane, nitrocellulose filtering membrane, polyvinylidene difluoride (PVDF) filtering membrane, cellulose acetate filtering membrane, regenerated cellulose filtering membrane, polymeric amide filtering membrane any one.
Described reductive agent can be in hydrazine hydrate, sodium borohydride, hydroiodic acid HI, phenylhydrazine any one.
Use aforesaid method can prepare the double-deck green fluorescence graphene quantum dot of list (GOQDs) that mean sizes is 1-12nm, after reduction, can prepare mean sizes is the single, double layer blue-fluorescence graphene quantum dot (GQDs) of 2-10 nm.
Beneficial effect of the present invention is:
The preparation method of graphene oxide quantum dot provided by the invention, its synthesis technique is simple, the purity of the graphene quantum dot of preparation and productive rate all compared with high, monodispersity good, particle diameter is little, good water solubility and have strong fluorescence property.At aspects such as lithium cell, micro super capacitor, biological fluorescent labelling, ultracapacitor, field-effect transistor, solar cell, OLEDs, there is important prospect.
Accompanying drawing explanation
Fig. 1 is for preparing the schematic diagram of graphene oxide quantum dot (GOQDs) and graphene quantum dot (GQDs).
Fig. 2 is transmission electron microscope, the size distribution figure of embodiment 1 Green fluorescence graphene quantum dot (GOQDs) and blue-fluorescence graphene quantum dot (GQDs).The TEM figure that wherein (a) is GO, (b) be the TEM figure of GOQDs, (c) be the lattice fringe figure of GOQDs, (d) be the size distribution figure of GOQDs, (e, f, g) be the TEM figure of GQDs under different amplification, (h) be the particle size distribution figure of GQDs.
Fig. 3 is atomic force microscope figure, the altitude distribution figure of graphene oxide quantum dot in embodiment 1 (GOQDs) and graphene quantum dot (GQDs).Wherein A is GOQDs atomic force microscope and altitude distribution figure, and B is GQDs atomic force microscope and altitude distribution figure, the scanning tunnel microscope figure that C is GOQDs, the scanning tunnel microscope figure that D is GQDs.
Fig. 4 is infrared, Raman spectrum and the XPS figure of graphene oxide quantum dot in embodiment 1 (GOQDs) and graphene quantum dot (GQDs).Wherein (a) is the infrared spectrogram of GOQDs, GQDs, is (b) Raman spectrogram of GO, GOQDs and GQDs, is (c) level scheme of GO, GOQDs and GQDs, (d-f) is expressed as the XPS figure of GO, GOQDs, GQDs.
Fig. 5 is UV/Vis and the fluorescence spectrum figure of graphene oxide quantum dot in embodiment 1 (GOQDs) and graphene quantum dot (GQDs).Wherein, (A) for the UV/Vis figure of graphene oxide quantum dot (GOQDs) be the fluorescence spectrum figure under 354nm excites at wavelength, (B) for the fluorescence spectrum figure under different wave length excites of graphene oxide quantum dot (GOQDs), (C) be the fluorescence spectrum figure of graphene quantum dot (GQDs) under different wave length excites.
the concrete mode of implementing
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in detail, but the explanation of described embodiment is only a part of embodiment of the present invention, wherein major part is not limited in this.
embodiment 1
1. the preparation of green fluorescence graphene oxide quantum dot
In beaker, add 1 g graphite oxide, slowly add the 50 ml vitriol oils and 5.0g potassium permanganate, first under ice bath, stir one hour, then transfer under the medium temperature condition of 40 ℃ and react 2 hours, shift again the hot stage reaction half hour at 90 ℃, stopped reaction, and add the water diluting reaction of 120 mL.Then add the hydrogen peroxide of 13 mL to react excessive potassium permanganate, obtain lurid clear solution.Adding excessive NaOH to make pH is 8 again, then adds a small amount of rare HCl solution to make its pH for neutral.Obtain yellow solution with the polycarbonate membrane filtration of 0.22 micron, its solution is dialysed 3 days in the dialysis tubing of 3000-8000 Da, obtain green glow graphene oxide quantum dot.Wherein graphene oxide quantum dot is of a size of 3-7 nm(and sees Fig. 2 b-c), thickness is approximately 1-4 nm(and sees Fig. 3 b), and the atomic force microscope figure of graphene oxide quantum dot (GOQDs) and scanning tunnel microscope figure are as shown in Fig. 3 a-c.By infrared, Raman and XPS analysis the structure properties of graphene quantum dot (seeing Fig. 4 a-d).In addition the fluorescence spectrum figure of graphene quantum dot is as shown in Fig. 5 a, b.The productive rate of the graphene oxide quantum dot of preparation is up to 25.4%.
2. the preparation of blue-fluorescence graphene quantum dot
The green glow fluorescence graphene oxide quantum dot that takes 0.1g adds the deionized water of 40 mL in the flask of 100 mL, then, after ultrasonic dispersion half an hour, adds the NH of 0.8 mL
2nH
2h
2o solution, stirs 12 hours at normal temperatures.After reaction finishes, adding the dilute hydrochloric acid of 0.1 mol/L to make the pH of solution is 6, solution is put into 3000-8000 Da dialysis tubing and dialyse 5 days, and evaporate to dryness water obtains blue-fluorescence graphene quantum dot.In Fig. 2 e-h, can observe graphene quantum dot and be of a size of 2-7 nm, the height that draws graphene quantum dot in Fig. 3 d is 1-4 nm, and the atomic force microscope of graphene quantum dot (GQDs) and scanning tunnel microscope figure are as shown in Fig. 3 b and d.By infrared, Raman spectrum, XPS analysis the structure properties of graphene quantum dot (seeing Fig. 4 a-d), fluorescence spectrum figure is as shown in Fig. 5 c, the productive rate of the graphene oxide quantum dot of preparation is up to 23.6 %.
embodiment 2
1. the preparation of green fluorescence graphene oxide quantum dot
According to the method in embodiment 1, graphite oxide is replaced with to Graphene, prepare green fluorescence graphene oxide quantum dot.
2. blue-fluorescence graphene quantum dot preparation
The green oxidation graphene quantum dot that takes 0.4g adds the water of 80 mL in the flask of 200 mL, then, after ultrasonic dispersion half an hour, adds the hydrazine hydrate solution of 1.2 mL, stirring reaction 10 hours at normal temperatures.After reaction finishes, adding the dilute hydrochloric acid of 0.1 mol/L to make the pH of solution is 6, solution is put into 3000-8000 Da dialysis tubing and dialyse 7 days, obtains blue-fluorescence graphene quantum dot.The size of the blue-fluorescence graphene quantum dot obtaining after reduction is approximately 2-6 nm, and its thickness is approximately 1-5 nm, and its productive rate is 22.7 %.
embodiment 3
1. the preparation of green fluorescence graphene oxide quantum dot
According to the method in embodiment 1, graphite oxide is replaced with to graphene nanobelt, the consumption of graphene nanobelt is 0.68g, the consumption of sulfuric acid is 73mL, the consumption of potassium permanganate is 5.6 g, uses microporous teflon membran filtering solution, prepares green fluorescence graphene oxide quantum dot.
2. blue-fluorescence graphene quantum dot preparation
The green oxidation graphene quantum dot that takes 0.1g adds the water of 40 mL in the flask of 100 mL, then, after ultrasonic dispersion half an hour, adds the NaBH of 2 g
4, stirring reaction 8 hours at normal temperatures.After reaction finishes, adding the dilute hydrochloric acid of 0.1 mol/L to make the PH of solution is 7, solution is put into 3000-8000 Da dialysis tubing and dialyse 7 days, obtains blue-fluorescence graphene quantum dot.It is of a size of 3-6 nm, and productive rate is 28.4 %.
embodiment 4
1. the preparation of green fluorescence graphene oxide quantum dot
According to the method in embodiment 1, graphite oxide is replaced with to Graphene, prepare green fluorescence graphene oxide quantum dot.
2. blue-fluorescence graphene quantum dot preparation
The green oxidation graphene quantum dot that takes 0.3g adds the water of 70 mL in the flask of 200 mL, during then ultrasonic dispersion 2 after, add the phenylhydrazine solution of 6 mL, stirring reaction 10 hours at normal temperatures.After reaction finishes, adding the dilute hydrochloric acid of 0.1 mol/L to make the PH of solution is 6, solution is put into 3000-8000 Da dialysis tubing and dialyse 7 days, obtains blue-fluorescence graphene quantum dot.The size of the blue-fluorescence graphene quantum dot obtaining after reduction is approximately 2-6 nm, and its thickness is approximately 1-5 nm.
1. the preparation of green fluorescence graphene oxide quantum dot as described in Example 1.
2. blue-fluorescence graphene quantum dot preparation
Taking 0.2 g green fluorescence graphene oxide quantum dot is placed in small beaker, then with tinfoil, build, plug aperture, be placed on and in tube furnace, pass into nitrogen (or the rare gas element such as argon gas, helium), with 10 ℃/min of temperature rise rate, be warming up to 400 ℃ of maintenances cooling naturally after 10 minutes, obtain, graphene quantum dot, it is dispersed in water again, have water-solublely preferably, under ultraviolet lamp, by different excitation wavelengths, can see blue light-emitting, thereby obtain blue fluorescence graphene quantum dot, it is of a size of 2-5 nm, and thickness is 1-3 nm.
embodiment 6
1. the preparation of green fluorescence graphene oxide quantum dot as described in Example 1.
2. blue-fluorescence graphene quantum dot preparation
By the method in embodiment 1, make graphene oxide quantum dot, be placed in porcelain boat, porcelain boat is placed on and in tube furnace, passes into nitrogen rare gas elementes such as (or) argon gas, helium, take temperature rise rate as 10 ℃/min, be warming up to 500 ℃ and keep naturally lowering the temperature after 30 minutes.Obtained blue-fluorescence graphene quantum dot (GQDs), be again dispersed in water, obtained the fluorescence graphene quantum dot of water-soluble good blueness, it is of a size of 2-8 nm, and thickness is 1-5 nm.
Claims (10)
1. a preparation method for graphene quantum dot, is characterized in that, comprises the following steps:
(1) get a certain amount of carbon material and under condition of ice bath, be dispersed in a certain amount of H
2sO
4in, add a certain amount of KMnO
4and under differing temps stirring reaction for some time, reaction finish after, in solution, add a small amount of hydrogen peroxide to react excessive KMnO
4, obtain shallow yellow transparent solution (GO);
(2) in the shallow yellow transparent solution of preparing in step (1), add the solution of NaOH that pH is adjusted to 7-8, add again a small amount of rare HCl solution to make its pH for neutral, then, obtain transparent pale yellow solution with filtering with microporous membrane, its solution is dialysed in the dialysis tubing of certain cut-off molecular weight, water evaporate to dryness, obtain green fluorescence graphene oxide quantum dot (GOQDs);
(3) the green fluorescence graphene oxide quantum dot that utilizes step (2) to prepare, reduces or high temperature annealing mode is prepared blue-fluorescence graphene quantum dot (GQDs) by reductive agent.
2. the preparation method of graphene quantum dot according to claim 1, is characterized in that: the carbon material described in step (1) is any one or multiple mixture in graphite oxide, graphene oxide, Graphene, graphene nanobelt, graphene nano particle, nano-graphite, single wall or multi-walled carbon nano-tubes, carbon fiber.
3. the preparation method of graphene quantum dot according to claim 1, is characterized in that: the consumption of the vitriol oil described in step (1) is the 80-1600 wt% of carbon material consumption, and potassium permanganate consumption is the 10-80 wt% of vitriol oil consumption.
4. the preparation method of graphene quantum dot according to claim 1, it is characterized in that: the temperature of reaction described in step (1) is 30-150 ℃, the stirring reaction time is 1-7 hour, wherein reaction is divided into two stages and carries out, first at 20-50 ℃ low thermophase stirring reaction 0.5-3 hour, then at 80-150 ℃ of hot stage stirring reaction 0.5-4 hour.
5. the preparation method of graphene quantum dot according to claim 1, is characterized in that: the consumption of the hydrogen peroxide described in step (1) is the 10-80 wt% of potassium permanganate consumption.
6. the preparation method of graphene quantum dot according to claim 1, is characterized in that: the millipore filtration described in step (2) is any one in tetrafluoroethylene filtering membrane, polycarbonate filtering membrane, nitrocellulose filtering membrane, polyvinylidene difluoride (PVDF) filtering membrane, cellulose acetate filtering membrane, regenerated cellulose filtering membrane, polymeric amide filtering membrane.
7. the preparation method of graphene quantum dot according to claim 1, it is characterized in that: the step of preparing blue-fluorescence graphene quantum dot (GQDs) by reductive agent reduction mode described in step (3) is: in the green glow graphene oxide quantum dot of preparing to step (2), add a certain amount of reductive agent to reduce for some time at normal temperatures, add deionized water and be diluted to pH for neutral, its solution is dialysed in the dialysis tubing of certain cut-off molecular weight, water evaporate to dryness, obtained blue-fluorescence graphene quantum dot (GQDs).
8. according to the preparation method of the graphene quantum dot described in claim 1 or 7, it is characterized in that: described reductive agent comprises any one or the multiple mixture in hydrazine hydrate, sodium borohydride, hydroiodic acid HI, phenylhydrazine, reductive agent consumption is the 60-200 wt % of relative GOQDs consumption, stirring reaction 2-24 hour at normal temperatures.
9. the preparation method of graphene quantum dot according to claim 1, it is characterized in that: high temperature annealing mode described in step (3) is prepared the step of blue-fluorescence graphene quantum dot (GQDs) and is: the green fluorescence graphene quantum dot (GOQDs) that step (2) is obtained is placed in inert gas environment, in temperature, be under 200-600 ℃ of condition, high temperature annealing 5-60 min obtains blue-fluorescence graphene quantum dot (GQDs).
10. the preparation method of graphene quantum dot according to claim 1, it is characterized in that: the mean sizes of the green fluorescence graphene quantum dot (GOQDs) of preparation is single double-layer graphite alkene quantum dot of 1-12 nm, the blue light graphene quantum dot (GQDs) obtaining after reductive agent reduction or high temperature annealing is that mean sizes is 2-10 nm.
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