CN103803538B - The magnanimity method of coal-based graphene quantum dot - Google Patents
The magnanimity method of coal-based graphene quantum dot Download PDFInfo
- Publication number
- CN103803538B CN103803538B CN201410041931.6A CN201410041931A CN103803538B CN 103803538 B CN103803538 B CN 103803538B CN 201410041931 A CN201410041931 A CN 201410041931A CN 103803538 B CN103803538 B CN 103803538B
- Authority
- CN
- China
- Prior art keywords
- coal
- graphene quantum
- quantum dot
- peel
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a kind of magnanimity method of coal-based graphene quantum dot, comprise the following steps: after pulverizing coal dust with peel off solvent, peel off promotor and mix also ultrasonic disperse; Then proceed to autoclave and carry out hydro-thermal reaction under continuous magnetic agitation effect; Namely graphene quantum dot is obtained after unstripped macrobead is removed in centrifugation after cooling.The present invention is by controlling coal dust and the preparation in macroscopic quantity peeling off solvent and the parameter such as ratio, hydrothermal temperature, time of peeling off promotor and can realize graphene quantum dot, compared with prior art, the present invention adopts organic solvent directly to peel off coal to prepare graphene quantum dot, not only there is good water solubility, advantage that fluorescence efficiency is high, and preparation cost is cheap, technique is simple, and productive rate is high, is convenient to industrial volume production.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, especially relate to a kind of magnanimity method of coal-based graphene quantum dot.
Background technology
Graphene quantum dot (Graphene quantum dots, GQDs) as a kind of grapheme material of accurate zero dimension, except the unreactiveness of the electrons transport property and carbon quantum dot with Graphene uniqueness, hypotoxicity, the preferably characteristic such as biocompatibility, anti-light bleaching, also there are the many new features caused by quantum confinement and side effect: (1) GQDs has the bandgap structure relevant to its size, surface group and photoluminescence property; (2) GQDs has conversion characteristic on wavelength, and also namely GQDs effectively can catch the energy photons of near-infrared region, can realize absorbing the broad band of sunlight; (3) in GQDs, hot carrier has lower relaxation rate, and this just means the efficiency of conversion that GQDs more effectively can catch hot carrier and then improve solar cell.Current GQDs has been widely used in the numerous areas such as opto-electronic conversion, sensor, photochemical catalysis, fluorescent mark.
The preparation method of GQDs mainly comprises hydrothermal method, nitration mixture oxidation style, ultraviolet Fenton's reaction method, electrochemical oxidation process, microwave-assisted oxidation style and organic molecule synthesis method etc.Although use aforesaid method can carry out magnanimity, the controlled synthesis of GQDs, but the existence of these methods such as needs, and graphene oxide sheet makes raw material, experimentation is complicated, higher to ingredient requirement, to shortcomings such as matching requirements are higher, prepared by a large amount of, the low cost that limit GQDs thus.Through finding existing literature search, the people such as Ruquan Ye have delivered and have been entitled as " Coal as an abundant source of graphene quantum dots " (NatureCommunications for 2013 on " Nature Communications ", 2013, research report 4:2943), the document utilizes coal itself to form this feature by the acyclic carbochain of nano junction wafer and centre, uses nitration mixture (H2SO4/HNO3) oxidation style to carry out reflow treatment to coal dust and within 24 hours, has prepared water-soluble and fluorescent characteristic GQDs all preferably.When but the long-time the oxidation reflux process of this nitration mixture prepares GQDs major part GQDs can oxidized fall, reduction productive rate; Be oxidized the experimentations such as backflow, acid-base neutralisation and dialysis treatment on the other hand comparatively complicated, and a large amount of waste liquid can be produced, be difficult to carry out industrial volume production.
Summary of the invention
Object of the present invention is exactly provide a kind of magnanimity method of coal-based graphene quantum dot to overcome defect that above-mentioned prior art exists, and the direct volume production of method that the present invention adopts organic solvent to peel off coal dust prepares good water solubility, graphene quantum dot that fluorescence efficiency is high.
Object of the present invention can be achieved through the following technical solutions:
The present invention relates to a kind of magnanimity method of coal-based graphene quantum dot, comprise the following steps: after pulverizing coal dust with peel off solvent, peel off promotor and mix also ultrasonic disperse; Then proceed to autoclave and carry out hydro-thermal reaction under continuous magnetic agitation condition; Namely graphene quantum dot is obtained after unstripped macrobead is removed in centrifugation after cooling.
Preferably, described coal dust is one or more mixtures in hard coal, bituminous coal, brown coal, coking coal.
Preferably, after described pulverizing the particle size of coal dust at 0.1 ~ 200 μm.Preferred, described stripping solvent is one or more mixtures in METHYLPYRROLIDONE, methyl-sulphoxide, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE.Preferred further, described stripping promotor is one or more mixtures in trisodium citrate, sodium tartrate, sodium-potassium tartrate, sodium hydroxide.
Preferably, the power of described ultrasonic disperse is 50 ~ 200W, and the time is 10 ~ 120min.
Preferably, described coal dust, to peel off solvent and peel off the ratio of promotor be 1.0g:(50 ~ 500ml): (0.0 ~ 5.0g).
Preferably, the temperature of described hydro-thermal reaction is 100 ~ 250 DEG C, and the time is 2 ~ 24h.
Preferably, the rotating speed of described centrifugation is 10000 ~ 14000rpm, and the time is 2 ~ 30min.
Compared with prior art, the present invention has following beneficial effect: the present invention is by controlling coal dust, peeling off the preparation in macroscopic quantity that the parameter such as ratio, hydrothermal temperature, time of solvent and stripping promotor can realize graphene quantum dot.The present invention adopts organic solvent directly to peel off coal to prepare graphene quantum dot, and not only have good water solubility, advantage that fluorescence efficiency is high, and preparation cost is cheap, technique is simple, and productive rate is high, is convenient to industrial volume production.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the schematic diagram of graphene quantum dot preparation process;
Fig. 2 is the uv-visible absorption spectra figure that the present invention prepares graphene quantum dot.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment relates to a kind of magnanimity method of coal-based graphene quantum dot, comprises the following steps:
As shown in Figure 1, by pulverized anthracite 0.1g, 20ml METHYLPYRROLIDONE of 200 μm of sizes and 0.2g trisodium citrate, mixed being incorporated in ultrasonic pond in beaker disperses 30min(power 100W); Then mixed solution to be proceeded in the hydrothermal reaction kettle of 50ml 200 DEG C of reaction 8h under continuous magnetic agitation condition, after cooling, the centrifugal 10min of 14000rpm removes macrobead and namely obtains water-soluble graphene quantum dots.Its uv-visible absorption spectroscopy as shown in Figure 2.
embodiment 2
The present embodiment relates to a kind of magnanimity method of coal-based graphene quantum dot, comprises the following steps:
As shown in Figure 1, by brown coal powder 0.2g, 60ml methyl-sulphoxide of 100 μm of sizes and 0.6g sodium tartrate, mixed being incorporated in ultrasonic pond in beaker disperses 30min(power 200W); Then mixed solution to be proceeded in the hydrothermal reaction kettle of 100ml 200 DEG C of reaction 10h under continuous magnetic agitation condition, after cooling, the centrifugal 20min of 13000rpm removes macrobead and namely obtains water-soluble graphene quantum dots.Its uv-visible absorption spectroscopy as shown in Figure 2.
embodiment 3
The present embodiment relates to a kind of magnanimity method of coal-based graphene quantum dot, comprises the following steps:
As shown in Figure 1, by pulverized anthracite 0.1g, 30ml METHYLPYRROLIDONE of 0.1 μm of size and 0.0g trisodium citrate, mixed being incorporated in ultrasonic pond in beaker disperses 10min(power 200W); Then mixed solution to be proceeded in the hydrothermal reaction kettle of 50ml 200 DEG C of reaction 2h under continuous magnetic agitation condition, after cooling, the centrifugal 2min of 14000rpm removes macrobead and namely obtains water-soluble graphene quantum dots.Its uv-visible absorption spectroscopy as shown in Figure 2.
embodiment 4
The present embodiment relates to a kind of magnanimity method of coal-based graphene quantum dot, comprises the following steps:
As shown in Figure 1, coking coal powder 1.0g, 500ml N of 2 μm of sizes, dinethylformamide and 3.0g sodium tartrate mixed being incorporated in ultrasonic pond in beaker is disperseed 120min(power 150W); Then mixed solution to be proceeded in the hydrothermal reaction kettle of 1000ml 250 DEG C of reaction 8h under continuous magnetic agitation condition, after cooling, the centrifugal 10min of 12000rpm removes macrobead and namely obtains water-soluble graphene quantum dots.Its uv-visible absorption spectroscopy as shown in Figure 2.
embodiment 5
The present embodiment relates to a kind of magnanimity method of coal-based graphene quantum dot, comprises the following steps:
As shown in Figure 1, by bituminous coal powder 0.2g, 60ml METHYLPYRROLIDONE of 100 μm of sizes/N, N-N,N-DIMETHYLACETAMIDE (V/V=1:1) and 0.2g sodium hydroxide, mixed being incorporated in ultrasonic pond in beaker disperses 90min(power 200W); Then mixed solution to be proceeded in the hydrothermal reaction kettle of 100ml 180 DEG C of reaction 12h under continuous magnetic agitation condition, after cooling, the centrifugal 30min of 10000rpm removes macrobead and namely obtains water-soluble graphene quantum dots.Its uv-visible absorption spectroscopy as shown in Figure 2.
embodiment 6
The present embodiment relates to a kind of magnanimity method of coal-based graphene quantum dot, comprises the following steps:
As shown in Figure 1, by pulverized anthracite 0.1g, 40ml N, N-N,N-DIMETHYLACETAMIDE of 5 μm of sizes and 0.3g sodium-potassium tartrate, mixed being incorporated in ultrasonic pond in beaker disperses 60min(power 50W); Then mixed solution to be proceeded in the hydrothermal reaction kettle of 100ml 200 DEG C of reaction 10h under continuous magnetic agitation condition, after cooling, the centrifugal 10min of 14000rpm removes macrobead and namely obtains water-soluble graphene quantum dots.Its uv-visible absorption spectroscopy as shown in Figure 2.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (2)
1. a magnanimity method for coal-based graphene quantum dot, is characterized in that, comprise the following steps: after pulverizing coal dust with peel off solvent, peel off promotor and mix also ultrasonic disperse; Then proceed to autoclave and carry out hydro-thermal reaction under continuous magnetic agitation condition; Namely graphene quantum dot is obtained after unstripped macrobead is removed in centrifugation after cooling;
Wherein, after described pulverizing, the particle size of coal dust is at 0.1 ~ 200 μm;
Described stripping solvent is one or more mixtures in METHYLPYRROLIDONE, methyl-sulphoxide, dimethyl formamide, N,N-DIMETHYLACETAMIDE;
Described stripping promotor is one or more mixtures in trisodium citrate, sodium tartrate, sodium-potassium tartrate, sodium hydroxide;
The power of described ultrasonic disperse is 50 ~ 200W, and ultrasonic time is 10 ~ 120min;
The temperature of described hydro-thermal reaction is 100 ~ 200 DEG C, and the time of reaction is 2 ~ 24h;
The rotating speed of described centrifugation is 10000 ~ 14000rpm, and the time is 2 ~ 30min.
2. the magnanimity method of coal-based graphene quantum dot according to claim 1, is characterized in that, described coal dust is one or more mixtures in hard coal, bituminous coal, brown coal, coking coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410041931.6A CN103803538B (en) | 2014-01-28 | 2014-01-28 | The magnanimity method of coal-based graphene quantum dot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410041931.6A CN103803538B (en) | 2014-01-28 | 2014-01-28 | The magnanimity method of coal-based graphene quantum dot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103803538A CN103803538A (en) | 2014-05-21 |
| CN103803538B true CN103803538B (en) | 2015-11-04 |
Family
ID=50700990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410041931.6A Expired - Fee Related CN103803538B (en) | 2014-01-28 | 2014-01-28 | The magnanimity method of coal-based graphene quantum dot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103803538B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105271411B (en) * | 2015-11-04 | 2017-03-08 | 太原理工大学 | A kind of preparation method of molybdenum bisuphide quantum dot |
| CN105289421B (en) * | 2015-11-28 | 2017-09-05 | 西安科技大学 | Graphene macroscopic material photo catalytic reduction CO2Prepare the device and method of methanol |
| CN105600773A (en) * | 2015-12-18 | 2016-05-25 | 上海交通大学 | Preparation method of graphene quantum point by using graphite nanoparticle liquid phase stripping |
| CN106938842A (en) * | 2016-01-04 | 2017-07-11 | 天津工业大学 | It is a kind of to be pyrolyzed the method that citric acid prepares graphene quantum dot |
| CN105586036B (en) * | 2016-01-25 | 2017-12-26 | 大连理工大学 | A kind of preparation method of N doping fluorescent carbon point |
| US10081550B2 (en) * | 2016-06-26 | 2018-09-25 | Nanotek Instruments, Inc. | Direct ultrasonication production of graphene sheets from coke or coal |
| CN106281319B (en) * | 2016-07-25 | 2018-01-12 | 桂林理工大学 | The preparation method of fluorescence carbon nano-particle based on stratiform transition metal carbide |
| CN106744861B (en) * | 2017-03-01 | 2019-02-05 | 西安科技大学 | A kind of preparation method of coal base graphene quantum dot |
| 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 |
| CN114426270B (en) * | 2020-10-29 | 2023-09-05 | 中国石油化工股份有限公司 | Coal-based graphene quantum dot and preparation method thereof |
| CN112421015A (en) * | 2020-12-02 | 2021-02-26 | 山东丰元化学股份有限公司 | Preparation method of graphene quantum dot coated ternary cathode material |
| 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 |
| CN113528133B (en) * | 2021-07-07 | 2022-09-16 | 安徽工业大学 | Preparation method of brown coal-based white fluorescent carbon dots |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190296A (en) * | 2011-06-15 | 2011-09-21 | 昆明物理研究所 | Hydrothermal method for preparing water-soluble graphene quantum dots |
| CN102225758A (en) * | 2011-04-13 | 2011-10-26 | 昆明物理研究所 | Supersonic chemical preparation method for grapheme quantum dots |
| CN102320597A (en) * | 2011-07-15 | 2012-01-18 | 天津大学 | A kind of preparation method of graphene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5150883B2 (en) * | 2007-08-03 | 2013-02-27 | 独立行政法人産業技術総合研究所 | Carbon nanosheet / titanate nanotube composite, carbon nanosheet / titania nanorod composite, production method thereof and use thereof |
| KR101475928B1 (en) * | 2012-06-11 | 2014-12-23 | 서울대학교산학협력단 | A fabrication method of graphene quantum dot using thermal plasma |
-
2014
- 2014-01-28 CN CN201410041931.6A patent/CN103803538B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225758A (en) * | 2011-04-13 | 2011-10-26 | 昆明物理研究所 | Supersonic chemical preparation method for grapheme quantum dots |
| CN102190296A (en) * | 2011-06-15 | 2011-09-21 | 昆明物理研究所 | Hydrothermal method for preparing water-soluble graphene quantum dots |
| CN102320597A (en) * | 2011-07-15 | 2012-01-18 | 天津大学 | A kind of preparation method of graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103803538A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103803538B (en) | The magnanimity method of coal-based graphene quantum dot | |
| Zhang et al. | A green and facile synthesis of TiO2/graphene nanocomposites and their photocatalytic activity for hydrogen evolution | |
| CN103769187A (en) | Preparation method of graphene/g-C3N4 compound photocatalyst | |
| CN104449693B (en) | The preparation method of the fluorescent carbon quantum dot of nitrogen sulfur doping | |
| Zhou et al. | Synthesis and enhanced photocatalytic performance of WO3 nanorods@ graphene nanocomposites | |
| CN104923211B (en) | A kind of Bi of visible light catalysis activity2O3/(BiO)2CO3Hetero-junctions catalyst and preparation method thereof | |
| CN103803540B (en) | A kind of preparation method of coal-based graphene quantum dot | |
| CN104056620B (en) | A kind of visible light catalyst and preparation method and application | |
| CN104724694A (en) | Preparation method of rice straw biochar | |
| CN103433077B (en) | Three-element composite photocatalyst and preparation method thereof | |
| CN105664159A (en) | Transition metal disulfide compound nano sheet layer with good biocompatibility as well as preparation method and application thereof | |
| CN105618087A (en) | Transition metal dithio compound nanometer sheet layer compound and preparation method thereof | |
| CN104277219A (en) | Photocatalytic material polyimide, as well as preparation method and applications thereof | |
| CN102671676A (en) | Preparation method for SnO2/SnS2 heterostructure photocatalyst | |
| CN105565362A (en) | Preparation method of reduced graphene oxide/cuprous oxide nano composite material | |
| CN104059644A (en) | Simple and quick preparation method of nitrogen-doped carbon quantum dots | |
| CN104760945A (en) | Preparation method of wheat straw charcoal | |
| CN101649245A (en) | Method for extracting peppermint oil by microwave radiation | |
| CN104148099A (en) | Preparation method for MoS2-BiPO4 composite photocatalyst | |
| CN105060346B (en) | The self-stabilization dispersion molybdenum trioxide nano preparation method with colloid in a kind of water | |
| CN107308927A (en) | A kind of preparation method of titanium dioxide homojunction nano-photocatalyst | |
| CN110922967A (en) | Method for synthesizing high-fluorescence boron-nitrogen co-doped graphene quantum dots by one-pot hydrothermal method | |
| CN106268887A (en) | A kind of composite photo-catalyst CdS/LaPO4and its preparation method and application | |
| CN101591339A (en) | A kind of is the method for feedstock production chlorophyll copper sodium with the watermelon outer peel | |
| CN108993558A (en) | A kind of preparation method of high-performance titanium dioxide optical catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151104 Termination date: 20190128 |