CN103922329A - Method for extracting graphene quantum dots from coal - Google Patents
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- CN103922329A CN103922329A CN201410160436.7A CN201410160436A CN103922329A CN 103922329 A CN103922329 A CN 103922329A CN 201410160436 A CN201410160436 A CN 201410160436A CN 103922329 A CN103922329 A CN 103922329A
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Abstract
The invention provides a method for extracting graphene quantum dots from coal. By using coal which is low in price and easy to obtain as a carbon source, through a simple chemical oxidation process and subsequent simple filtration and evaporation, a large quantity of water-soluble graphene quantum dots are obtained. The obtained graphene quantum dots are 1-100 nanometers in plane size and 0.3-10 nanometer in thickness, have a large quantity of carboxyls on the surface, and show better luminescent property and electrogenerated chemiluminescence activity. The method is efficient, rapid, simple and cheap, and is remarkable in economic and social benefits.
Description
Technical field
The invention belongs to field of material preparation, be specifically related to extract in a kind of coal the method for graphene quantum dot.
Background technology
Luminous nano granule has important using value at opto-electronic device, biomarker and biomedicine field.Semiconductor-quantum-point is as CdS, CdSe, CdTe, CdSe/ZnSe, PbS, although Si etc. have advantages of the luminescent quantum productive rate that size is controlled, the scope of emission wavelength is narrower and higher, because its water-soluble bad, poor chemical stability and major part have compared with shortcomings such as strong toxicity, its application is very restricted, particularly at biomedicine field.
Compare with above-mentioned common semiconductor-quantum-point, graphene quantum dot (graphene quantum dots, GQDs) has a lot of advantages, such as good chemical stability and biocompatibility and hypotoxicity etc., thereby obtains increasing attention.Yet as a kind of emerging nano material, there is few preparation method about GQDs.Preparation method mainly can be divided into " bottom-up " and " top-down " two classes at present." bottom-up " method mainly refers to by thermal treatment (comprising hydro-thermal, direct heating etc.) some special organism (as aromatics of citric acid, glucose, starch or some larger molecular weight etc.) is converted into the water miscible nanometer sheet with graphene-structured feature, and " top-down " method mainly refers to by means such as chemical oxidation, electrochemical oxidation, hydro-thermal or solvent thermal some large-sized carbon material (as carbon nanotube, carbon fiber, graphite, graphene oxide, carbon black etc.) is cut into undersized graphene nanometer sheet.Yet from the angle of scale operation GQDs, consider, these methods all exist many significantly weak points.For example instrument is expensive, and process is complicated, and productive rate is low, is difficult to purify etc., and particularly source material used is all relatively costly, is not suitable for scale operation.Therefore searching for a kind of method simple, effective, cheap, that be suitable for the synthetic GQDs of scale operation is a very challenging job.
Summary of the invention
The object of the present invention is to provide a kind of extract graphene quantum dot in coal method, the method is simple to operate, with low cost, and productive rate is high.
For achieving the above object, the present invention adopts following technical scheme:
A kind of extract graphene quantum dot in coal method comprises the following steps:
A, coal dust is added and in hydrochloric acid soln, carries out stirring and refluxing;
B, stop refluxing, filter, with deionized water repetitive scrubbing coal dust, dry;
C, by dried coal dust and salpeter solution stirring and refluxing;
D, stop refluxing, cooling, to filter, dried filtrate, obtains graphene quantum dot powder.
Coal described in step a comprises hard coal, bituminous coal, subbituminous coal, peat.
The concentration of the hydrochloric acid soln described in step a is 1 ~ 12 mol/L.
Coal dust described in step a and the usage ratio of hydrochloric acid soln are to add 0.5～50g coal dust in every 100mL hydrochloric acid soln.
Reflux temperature described in step a is 20～200 ℃, and return time is 10～30h.
The concentration of the salpeter solution described in step c is 1 ~ 16 mol/L.
Coal dust described in step c and the usage ratio of salpeter solution are to add 0.5～50g coal dust in every 100mL salpeter solution.
Reflux temperature described in step c is 20～200 ℃, and return time is 10～30h.
Filtrate drying temperature described in steps d is 20～200 ℃.
Described graphene quantum dot is that planar dimension is 1 ~ 100 nanometer, and thickness is the single or multiple lift graphene nanometer sheet of 0.3 ~ 10 nanometer.
Remarkable advantage of the present invention is: the present invention adopts coal cheap and easy to get as raw material, extracts water-soluble GQDs by chemical oxidation from activated carbon.Coal is a kind of natural ore fuel, is distributed in all over the world in a large number and widely.In coal, contain a large amount of graphitic composition, and these graphitic composition mainly exist with the form of chips of nanoscale.By refluxing with oxidizing acid, can make the fractal surfaces of these graphite-structures be oxidized to carboxyl, and be finally discharged in solution.This preparation method is except raw material is cheap and easy to get, its preparation process is also simple especially, without special laboratory apparatus, product yield is very high and easily purify, gained GQDs thickness homogeneous (being individual layer substantially) and planar dimension be relative homogeneous also, so the method is particularly suitable for scale operation GQDs.The GQDs good water solubility, fluorescence and the electrogenerated chemiluminescence(ECL) that by chemical oxidization method, from coal, extract are functional.
Accompanying drawing explanation
Fig. 1 is field transmission Electronic Speculum figure (left side) and the atomic force microscope figure (right side) of GQDs.
Fig. 2 is the Raman spectrum (a) of GQDs, the x-ray photoelectron power spectrum (c) of X-ray powder diffraction figure (b), C1s, infrared absorption spectrum (d).
Fig. 3 is the ultra-violet absorption spectrum of GQDs and the emmission spectrum under different excitation wavelength condition.Illustration is the optics picture of the GQD aqueous solution under visible ray and 365nm ultraviolet.
Fig. 4 is GQDs and K
2s
2o
8between coreaction electrogenerated chemiluminescence(ECL) response (dotted line is the electrogenerated chemiluminescence(ECL) response of GQDs body; Solid line is the K of GQDS and 1mM
2s
2o
8coreaction electrogenerated chemiluminescence(ECL) response).The shape electrogenerated chemiluminescence(ECL) of burying in oblivion that illustration (a) is GQDs responds; (b) be GQDs and K
2s
2o
8the electrogenerated chemiluminescence(ECL) spectrum of co-reactant electrogenerated chemiluminescence(ECL) system.
Embodiment
For a better understanding of the present invention, by example, further illustrate, but the present invention is not limited only to this.
Embodiment 1
1.00 grams of dry bituminous coal powder are joined in the 5 mol/L hydrochloric acid of 100 mL, 24 h reflux under the condition of 130 ℃.After naturally cooling to room temperature, with filter paper filtering, remove hydrochloric acid and coal dust transferred in the 5 mol/L nitric acid of 100 mL, 24 h further reflux under the condition of 130 ℃.After solution naturally cools to room temperature, with filter paper filtering, take out filtrate, and control heater temperature be 150 ℃ gained filtrate evaporate to dryness, obtain reddish-brown powder (approximately 0.53 gram), can estimate that the productive rate of GQDs is about 53%.
The GQDs that transmission electron microscope and atomic force microscope (see figure 1) show to test gained is mainly that yardstick is about the nanometer sheet that 10 nanometers, thickness are about the individual layer of 0.5 nanometer.In the GQDs of Raman spectrum, X-ray powder diffraction collection of illustrative plates, x-ray photoelectron energy spectrogram and infrared spectra (see figure 2) illustrative experiment gained, contain a large amount of graphite-structures, and its surface is with a large amount of carboxyls.Prepared GQDs has good optical property, comprising there is the fluorescence activity (see figure 3) of the wavelength affects that is significantly stimulated and have Smoke go out mechanism (see Fig. 4 a) and the electrogenerated chemiluminescence(ECL) of coreaction mechanism (seeing Fig. 4 b) active, the maximum emission wavelength of its electrogenerated chemiluminescence(ECL) is approximately 580 nanometers.
Embodiment 2
50.00 grams of dry hard coal powder are joined in the 12 mol/L hydrochloric acid of 100 mL, 30 h reflux under the condition of 200 ℃.After naturally cooling to room temperature, with filter paper filtering, remove hydrochloric acid and coal dust transferred in the 16 mol/L nitric acid of 100 mL, 30 h further reflux under the condition of 200 ℃.After solution naturally cools to room temperature, with filter paper filtering, take out filtrate, and control heater temperature be 200 ℃ gained filtrate evaporate to dryness, obtain reddish-brown GQDs powder.
Embodiment 3
25.00 grams of dry subbituminous coal powder are joined in the 1 mol/L hydrochloric acid of 100 mL, 30 h reflux under the condition of 20 ℃.After naturally cooling to room temperature, with filter paper filtering, remove hydrochloric acid and coal dust transferred in the 1 mol/L nitric acid of 100 mL, 30 h further reflux under the condition of 20 ℃.After solution naturally cools to room temperature, with filter paper filtering, take out filtrate, and control heater temperature be 200 ℃ gained filtrate evaporate to dryness, obtain reddish-brown GQDs powder.
Embodiment 4
0.5 gram of dry peat is joined in the 8 mol/L hydrochloric acid of 100 mL, 10 h reflux under the condition of 100 ℃.After naturally cooling to room temperature, with filter paper filtering, remove hydrochloric acid and coal dust transferred in the 8 mol/L nitric acid of 100 mL, 10 h further reflux under the condition of 100 ℃.After solution naturally cools to room temperature, with filter paper filtering, take out filtrate, and control heater temperature be 120 ℃ gained filtrate evaporate to dryness, obtain reddish-brown GQDs powder.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (10)
1. in coal, extract a method for graphene quantum dot, it is characterized in that: comprise the following steps:
A, coal dust is added and in hydrochloric acid soln, carries out stirring and refluxing;
B, stop refluxing, filter, with deionized water repetitive scrubbing coal dust, dry;
C, by dried coal dust and salpeter solution stirring and refluxing;
D, stop refluxing, cooling, to filter, dried filtrate, obtains graphene quantum dot powder.
2. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the coal described in step a comprises hard coal, bituminous coal, subbituminous coal, peat.
3. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the concentration of the hydrochloric acid soln described in step a is 1 ~ 12 mol/L.
4. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the coal dust described in step a and the usage ratio of hydrochloric acid soln are to add 0.5～50g coal dust in every 100mL hydrochloric acid soln.
5. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the reflux temperature described in step a is 20～200 ℃, return time is 10～30h.
6. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the concentration of the salpeter solution described in step c is 1 ~ 16 mol/L.
7. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the coal dust described in step c and the usage ratio of salpeter solution are to add 0.5～50g coal dust in every 100mL salpeter solution.
8. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the reflux temperature described in step c is 20～200 ℃, return time is 10～30h.
9. in coal according to claim 1, extract the method for graphene quantum dot, it is characterized in that: the filtrate drying temperature described in steps d is 20～200 ℃.
10. the graphene quantum dot that the method for claim 1 makes, is characterized in that: graphene quantum dot is that planar dimension is 1 ~ 100 nanometer, and thickness is the single or multiple lift graphene nanometer sheet of 0.3 ~ 10 nanometer.
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| CN104401981A (en) * | 2014-11-10 | 2015-03-11 | 朱熹 | Preparation method of nitrogen-containing oxidative graphene quantum dot capable of giving off fluorescence in three primary colors |
| CN104946252A (en) * | 2015-07-15 | 2015-09-30 | 中北大学 | Method for preparing fluorescent carbon dots by using coal |
| WO2016023041A3 (en) * | 2014-08-08 | 2016-03-31 | Tanimola Olanrewaju W | Methods for synthesis of graphene derivatives and functional materials from asphaltenes, graphene derivatives, 2d materials and applications of use |
| CN105820816A (en) * | 2015-11-19 | 2016-08-03 | 云南师范大学 | Method for preparing nitrogen-doped graphene quantum point by using reflux process |
| WO2016118214A3 (en) * | 2014-11-06 | 2016-09-29 | William Marsh Rice University | Methods of making graphene quantum dots from various carbon sources |
| CN106430173A (en) * | 2016-06-06 | 2017-02-22 | 重庆大学 | Preparation method of highly dispersed graphene oxide quantum dots |
| CN106556583A (en) * | 2016-10-25 | 2017-04-05 | 大连理工大学 | A kind of green of carbon quantum dot based on coal tar asphalt base is prepared and Fe3+Detection method |
| EP3178786A3 (en) * | 2015-09-29 | 2017-09-20 | Cromoz Inc. | Graphene oxide nanoparticle compositions and methods of making the same |
| CN107804840A (en) * | 2017-12-14 | 2018-03-16 | 北方民族大学 | The method that hydro-thermal cutting high yield prepares coal base graphene quantum dot |
| CN112608743A (en) * | 2020-12-24 | 2021-04-06 | 中国矿业大学(北京) | Preparation method of coal-based fluorescent carbon quantum dots |
| CN112909163A (en) * | 2021-01-08 | 2021-06-04 | 新疆大学 | Nonvolatile memory device based on resistance random memory characteristic of coal-based graphene quantum dot film and preparation method thereof |
| CN115285981A (en) * | 2022-09-01 | 2022-11-04 | 西安交通大学 | Preparation method and application of graphene quantum dot aerogel derived porous carbon |
| US11731875B2 (en) | 2020-01-15 | 2023-08-22 | University Of Wyoming | Methods for production of graphene oxide |
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| WO2016023041A3 (en) * | 2014-08-08 | 2016-03-31 | Tanimola Olanrewaju W | Methods for synthesis of graphene derivatives and functional materials from asphaltenes, graphene derivatives, 2d materials and applications of use |
| CN107108219A (en) * | 2014-08-08 | 2017-08-29 | 奥兰雷瓦朱·W·塔尼莫拉 | From asphaltene, Graphene derivative, the method for 2D materials synthesis paraffin derivatives and application |
| CN107431211A (en) * | 2014-11-06 | 2017-12-01 | 威廉马歇莱思大学 | By the method for various carbon sources manufacture graphene quantum dot |
| WO2016118214A3 (en) * | 2014-11-06 | 2016-09-29 | William Marsh Rice University | Methods of making graphene quantum dots from various carbon sources |
| CN104401981A (en) * | 2014-11-10 | 2015-03-11 | 朱熹 | Preparation method of nitrogen-containing oxidative graphene quantum dot capable of giving off fluorescence in three primary colors |
| CN104946252B (en) * | 2015-07-15 | 2017-01-18 | 中北大学 | Method for preparing fluorescent carbon dots by using coal |
| CN104946252A (en) * | 2015-07-15 | 2015-09-30 | 中北大学 | Method for preparing fluorescent carbon dots by using coal |
| US10988385B2 (en) | 2015-09-29 | 2021-04-27 | Sinon Therapeutics Inc. | Nanoparticle compositions and methods of making and using the same |
| EP3178786A3 (en) * | 2015-09-29 | 2017-09-20 | Cromoz Inc. | Graphene oxide nanoparticle compositions and methods of making the same |
| US11878910B2 (en) | 2015-09-29 | 2024-01-23 | Sinon Nano Sciences, Inc. | Ph-based structural change of water soluble carbon nanoparticles for encapsulation and release of therapeutic agents in biological systems |
| CN105820816A (en) * | 2015-11-19 | 2016-08-03 | 云南师范大学 | Method for preparing nitrogen-doped graphene quantum point by using reflux process |
| CN105820816B (en) * | 2015-11-19 | 2018-11-20 | 云南师范大学 | A method of nitrogen-doped graphene quantum dot is prepared using reflux technique |
| CN106430173A (en) * | 2016-06-06 | 2017-02-22 | 重庆大学 | Preparation method of highly dispersed graphene oxide quantum dots |
| CN106556583A (en) * | 2016-10-25 | 2017-04-05 | 大连理工大学 | A kind of green of carbon quantum dot based on coal tar asphalt base is prepared and Fe3+Detection method |
| CN106556583B (en) * | 2016-10-25 | 2019-03-05 | 大连理工大学 | A kind of green preparation of the carbon quantum dot based on coal tar asphalt base and the detection method of Fe3+ |
| CN107804840B (en) * | 2017-12-14 | 2019-10-15 | 北方民族大学 | The method that hydro-thermal cutting high yield prepares coal base graphene quantum dot |
| CN107804840A (en) * | 2017-12-14 | 2018-03-16 | 北方民族大学 | The method that hydro-thermal cutting high yield prepares coal base graphene quantum dot |
| US11731875B2 (en) | 2020-01-15 | 2023-08-22 | University Of Wyoming | Methods for production of graphene oxide |
| CN112608743A (en) * | 2020-12-24 | 2021-04-06 | 中国矿业大学(北京) | Preparation method of coal-based fluorescent carbon quantum dots |
| CN112608743B (en) * | 2020-12-24 | 2022-06-14 | 中国矿业大学(北京) | Preparation method of coal-based fluorescent carbon quantum dots |
| CN112909163A (en) * | 2021-01-08 | 2021-06-04 | 新疆大学 | Nonvolatile memory device based on resistance random memory characteristic of coal-based graphene quantum dot film and preparation method thereof |
| CN115285981A (en) * | 2022-09-01 | 2022-11-04 | 西安交通大学 | Preparation method and application of graphene quantum dot aerogel derived porous carbon |
| CN115285981B (en) * | 2022-09-01 | 2023-08-15 | 西安交通大学 | Preparation method and application of graphene quantum dot aerogel-derived porous carbon |
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Application publication date: 20140716 |