CN103803540A - Preparation method of coal-based graphene quantum dot - Google Patents
Preparation method of coal-based graphene quantum dot Download PDFInfo
- Publication number
- CN103803540A CN103803540A CN201410056637.2A CN201410056637A CN103803540A CN 103803540 A CN103803540 A CN 103803540A CN 201410056637 A CN201410056637 A CN 201410056637A CN 103803540 A CN103803540 A CN 103803540A
- Authority
- CN
- China
- Prior art keywords
- coal
- graphene quantum
- quantum dot
- preparation
- add
- 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.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a coal-based graphene quantum dot. The method comprises the steps: mechanically crushing natural coal into powder differing in size, and sieving through sieves differing in mesh to obtain coal powder differing in size, wherein the coal powder serves as a raw material; mixing the coal powder and strong acid, implementing ultrasonic treatment to the mixture in an ultrasonic pond, freezing the treated mixture in a refrigerator overnight, taking out the mixture, slowly adding sodium nitrate and continuing stirring for 30min, placing a reaction device in ice bath, slowly adding potassium permanganate and stirring for 30min, placing the reaction device in water bath at 35 DEG C, adding de-ionized water and hydrogen peroxide, reacting and stirring overnight, centrifuging a reaction solution, neutralizing a supernatant liquid to be neutral through adding an alkaline reactant, dialyzing and desalting to obtain the water-soluble graphene quantum dot. The method disclosed by the invention for preparing the graphene quantum dot from the natural coal, compared to the prior art, is rich in raw material, low in price, simple in preparation process, high in yield and applicable to commercial production on a large scale.
Description
Technical field
The invention belongs to nano material preparing technical field, specifically a kind of take raw coal as raw material, utilize and improve the novel method of Hummers legal system for coal-based graphene quantum dot.
Background technology
Graphene quantum dot is as the accurate zero-dimension nano material of one, except having the characteristics such as the electrons transport property of Graphene uniqueness and the unreactiveness of carbon quantum dot, hypotoxicity, good biocompatibility, anti-photobleaching, also there are the many new features that caused by quantum confinement and side effect.Graphene quantum dot has been applied to the aspects such as photodiode, solar cell, photochemical catalysis, bioprobe, fluorescent mark, nanometer electronic device at present.
The preparation method of graphene quantum dot has: hydrothermal method, electrochemical process, ultrasonic method, microwave method, electron beam lithography etc.But prepared by these methods, graphene quantum dot all exists such as starting material costliness, equipment requirements harshness, energy expenditure is high, graphene quantum dot productive rate is low, the low inferior shortcoming of preparation efficiency.Through existing literature search is found, the people such as Changsheng Xiang, at NATURE COMMUNICATIONS, have delivered " Coal as an abundant source of graphene quantum dots " on 2013,4:2943.This research team selects these resourceful starting material of coal, and coal is rich in minerals, and has the internal structure of porous, is conducive to the infiltration of chemical reagent, accelerated oxidation reaction.But in this research process, the vitriol oil of employing and the treatment process of concentrated nitric acid are destroyed serious to texture of coal, introduce too many defect, and the graphene quantum dot dimensional homogeneity preparing is poor.
Summary of the invention
Object of the present invention is exactly to provide a kind of abundant raw materials, low price in order to overcome the defect that above-mentioned prior art exists, and preparation technology is simple, and output is large, is applicable to the preparation method of the coal-based graphene quantum dot that large-scale commercial produces.
Object of the present invention can be achieved through the following technical solutions: a kind of preparation method of coal-based graphene quantum dot, it is characterized in that, and the method comprises the following steps:
(1) raw materials pretreatment
The grinding of coal cinder: using natural coal cinder as starting material, pulverize into the powder of different size by mechanical force, utilize the sieve of different meshes, obtain the coal dust material of different size as starting material;
(2) preparation of water-soluble graphene quantum dots
Use and improve Hummers legal system for graphene quantum dot: after coal dust material is mixed with strong acid, put into ultrasonic pond supersound process, then putting into refrigerator freezing spends the night, after taking-up, slowly add SODIUMNITRATE and continue to stir 30min, reaction unit is placed in to ice bath, slowly add potassium permanganate and stir 30min, again reaction unit is placed in to 35 ℃ of water-baths, add deionized water and hydrogen peroxide, reaction is stirred and is spent the night, finally by above-mentioned reaction soln centrifugation, getting supernatant liquor adds alkaline reactant and is neutralized to neutrality, after dialysis desalination, obtain water miscible graphene quantum dot.
Described coal dust material is of a size of 100～1000 orders.
Described strong acid is a kind of or both mixtures in the vitriol oil, concentrated nitric acid, and its add-on is that every gram of coal powder material is added 0.1～0.8mol.
The add-on of described SODIUMNITRATE is that every gram of coal powder material adds 0.2～1.0g, and the add-on of described potassium permanganate is that every gram of coal powder material adds 2.0～8.0g.
The add-on of described deionized water is that every gram of coal powder material adds 40～100ml, and the add-on of described hydrogen peroxide water is that every gram of coal powder material adds 5～40ml hydrogen peroxide.
The speed of described centrifugation is 8000～20000rpm, and the time is 10～60min.
Described alkaline reactant is NaCO
3, NaOH or KOH.
Described dialysis tubing interception is 1000～3000Da.
The interception of size, temperature of reaction and time, centrifugation speed and time and dialysis tubing by regulating coal dust raw material obtains the controlled water-soluble graphene quantum dots of size.
Compared with prior art, the present invention, by controlling size, temperature of reaction and time, the dialysis tubing interception of coal dust raw material, obtains water-soluble graphene quantum dots cheaply, and preparation manipulation is simple, reacts gentleer, is applicable to commercially producing.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of graphene quantum dot of the present invention;
Fig. 2 is the absorption spectrum of embodiment 1 prepared graphene quantum dot.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Natural coal cinder is pulverized to sieve by mechanical force obtain 500 powder materials, get 1g coal dust and mix in beaker with the 0.5mol vitriol oil and put into the ultrasonic 30min in ultrasonic pond, then put into refrigerator freezing and spend the night.After taking-up, slowly add 1.0g SODIUMNITRATE, stir 30min, reaction unit is placed in to ice bath, slowly add 2.0g potassium permanganate, stir 2h, then reaction unit is placed in to 35 ℃ of water-baths, add 60ml water and 20ml hydrogen peroxide, reaction is stirred and is spent the night.By above-mentioned reaction soln centrifugation, centrifugation rate is 10000rpm, and the time is 30min, gets supernatant liquor and adds Na
2cO
3be neutralized to neutrality, adopt the dialysis tubing that interception is 2000 to dialyse 3 days, obtain water miscible graphene quantum dot.Its uv-visible absorption spectroscopy as shown in Figure 2.
Embodiment 2
Natural coal cinder is pulverized to sieve by mechanical force obtain 200 powder materials, get 1g coal dust and mix in beaker with 0.5mol concentrated nitric acid and put into the ultrasonic 30min in ultrasonic pond, then put into refrigerator freezing and spend the night.After taking-up, slowly add 0.6g SODIUMNITRATE, stir 30min, reaction unit is placed in to ice bath, slowly add 3.0g potassium permanganate, stir 2h, then reaction unit is placed in to 35 ℃ of water-baths, add 50ml water and 30ml hydrogen peroxide, reaction is stirred and is spent the night.By above-mentioned reaction soln centrifugation, centrifugation rate is 4000rpm, and the time is 60min, gets supernatant liquor and adds KOH and be neutralized to neutrality, adopts the dialysis tubing dialysis 3 days that interception is 3000, obtains water miscible graphene quantum dot.
Embodiment 3
Natural coal cinder is pulverized to sieve by mechanical force obtain 1000 powder materials, get 1g coal dust and mix in beaker with the 0.1mol vitriol oil and put into the ultrasonic 30min in ultrasonic pond, then put into refrigerator freezing and spend the night.After taking-up, slowly add 0.4g SODIUMNITRATE, stir 30min, reaction unit is placed in to ice bath, slowly add 4.0g potassium permanganate, stir 2h, then reaction unit is placed in to 35 ℃ of water-baths, add 40ml water and 20ml hydrogen peroxide, reaction is stirred and is spent the night.By above-mentioned reaction soln centrifugation, centrifugation rate is 14000rpm, and the time is 10min, gets supernatant liquor and adds NaOH and be neutralized to neutrality, adopts the dialysis tubing dialysis 3 days that interception is 1000, obtains water miscible graphene quantum dot.
Embodiment 4
Natural coal cinder is pulverized to sieve by mechanical force obtain 100 powder materials, get 1g coal dust and the 0.8mol vitriol oil/concentrated nitric acid (V/V=3: 1) mix and put into the ultrasonic 30min in ultrasonic pond, then putting into refrigerator freezing and spend the night in beaker.After taking-up, slowly add 1.0g SODIUMNITRATE, stir 30min, reaction unit is placed in to ice bath, slowly add 8.0g potassium permanganate, stir 2h, then reaction unit is placed in to 35 ℃ of water-baths, add 100ml water and 40ml hydrogen peroxide, reaction is stirred and is spent the night.By above-mentioned reaction soln centrifugation, centrifugation rate is 8000rpm, and the time is 30min, gets supernatant liquor and adds Na
2cO
3be neutralized to neutrality, adopt the dialysis tubing that interception is 2000 to dialyse 3 days, obtain water miscible graphene quantum dot.
Embodiment 5
Natural coal cinder is pulverized to sieve by mechanical force obtain 800 powder materials, get 1g coal dust and the 0.6mol vitriol oil/concentrated nitric acid (V/V=3: 1) mix and put into the ultrasonic 30min in ultrasonic pond, then putting into refrigerator freezing and spend the night in beaker.After taking-up, slowly add 0.6g SODIUMNITRATE, stir 30min, reaction unit is placed in to ice bath, slowly add 8.0g potassium permanganate, stir 2h, then reaction unit is placed in to 35 ℃ of water-baths, add 60ml water and 40ml hydrogen peroxide, reaction is stirred and is spent the night.By above-mentioned reaction soln centrifugation, centrifugation rate is 10000rpm, and the time is 20min, gets supernatant liquor and adds Na
2cO
3be neutralized to neutrality, adopt the dialysis tubing that interception is 2000 to dialyse 3 days, obtain water miscible graphene quantum dot.
Claims (9)
1. a preparation method for coal-based graphene quantum dot, is characterized in that, the method comprises the following steps:
(1) raw materials pretreatment
The grinding of coal cinder: using natural coal cinder as starting material, pulverize into the powder of different size by mechanical force, utilize the sieve of different meshes, obtain the coal dust material of different size as starting material:
(2) preparation of water-soluble graphene quantum dots
Use and improve Hummers legal system for graphene quantum dot: after coal dust material is mixed with strong acid, put into ultrasonic pond supersound process, then putting into refrigerator freezing spends the night, after taking-up, slowly add SODIUMNITRATE and continue to stir 30min, reaction unit is placed in to ice bath, slowly add potassium permanganate and stir 30min, again reaction unit is placed in to 35 ℃ of water-baths, add deionized water and hydrogen peroxide, reaction is stirred and is spent the night, finally by above-mentioned reaction soln centrifugation, getting supernatant liquor adds alkaline reactant and is neutralized to neutrality, after dialysis desalination, obtain water miscible graphene quantum dot.
2. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, is characterized in that, described coal dust material is of a size of 100～1000 orders.
3. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, is characterized in that, described strong acid is a kind of or both mixtures in the vitriol oil, concentrated nitric acid, and its add-on is that every gram of coal powder material is added 0.1～0.8mol.
4. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, it is characterized in that, the add-on of described SODIUMNITRATE is that every gram of coal powder material adds 0.2～1.0g, and the add-on of described potassium permanganate is that every gram of coal powder material adds 2.0～8.0g.
5. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, it is characterized in that, the add-on of described deionized water is that every gram of coal powder material adds 40～100ml, and the add-on of described hydrogen peroxide water is that every gram of coal powder material adds 5～40ml hydrogen peroxide.
6. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, is characterized in that, the speed of described centrifugation is 8000～20000rpm, and the time is 10～60min.
7. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, is characterized in that, described alkaline reactant is NaCO
3, NaOH or KOH.
8. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, is characterized in that, described dialysis tubing interception is 1000～3000Da.
9. the preparation method of a kind of coal-based graphene quantum dot according to claim 1, it is characterized in that, the interception of size, temperature of reaction and time, centrifugation speed and time and dialysis tubing by regulating coal dust raw material obtains the controlled water-soluble graphene quantum dots of size.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410056637.2A CN103803540B (en) | 2014-02-19 | 2014-02-19 | A kind of preparation method of coal-based graphene quantum dot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410056637.2A CN103803540B (en) | 2014-02-19 | 2014-02-19 | A kind of preparation method of coal-based graphene quantum dot |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103803540A true CN103803540A (en) | 2014-05-21 |
| CN103803540B CN103803540B (en) | 2015-12-02 |
Family
ID=50700992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410056637.2A Expired - Fee Related CN103803540B (en) | 2014-02-19 | 2014-02-19 | A kind of preparation method of coal-based graphene quantum dot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103803540B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946252A (en) * | 2015-07-15 | 2015-09-30 | 中北大学 | Method for preparing fluorescent carbon dots by using coal |
| CN106010517A (en) * | 2016-05-18 | 2016-10-12 | 武汉科技大学 | Carbon quantum dot fluorescent-labeled material with coke powder serving as carbon source and preparation method of carbon quantum dot fluorescent-labeled material |
| CN106744913A (en) * | 2017-03-28 | 2017-05-31 | 上海理工大学 | A kind of method that utilization cryptocrystalline graphite largely prepares graphene oxide quantum dot |
| CN108172409A (en) * | 2018-01-10 | 2018-06-15 | 西北师范大学 | A kind of preparation method of three-dimensional flower-shaped structure graphite alkene quantum dot/manganous hydroxide composite material |
| CN108455578A (en) * | 2018-03-17 | 2018-08-28 | 宁夏大学 | Graphene quantum dot and preparation method and application |
| CN109941988A (en) * | 2019-04-24 | 2019-06-28 | 铜仁学院 | A kind of preparation method and application of graphene quantum dot and device or device comprising it |
| CN111686810A (en) * | 2020-06-28 | 2020-09-22 | 西北师范大学 | Preparation method of layer-by-layer self-assembled GQDs/3D-G/PANI composite film |
| CN114105124A (en) * | 2021-11-12 | 2022-03-01 | 新疆大学 | Preparation method and application of graphene quantum dot and polyphenylene sulfide/graphene quantum dot composite material |
| CN114426270A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Coal-based graphene quantum dot and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660270A (en) * | 2012-05-03 | 2012-09-12 | 吉林大学 | Method for preparing fluorescent graphene quantum dots by solvothermal method |
| CN102849724A (en) * | 2012-10-12 | 2013-01-02 | 上海交通大学 | Preparation method of water-soluble carbon quantum dots |
-
2014
- 2014-02-19 CN CN201410056637.2A patent/CN103803540B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660270A (en) * | 2012-05-03 | 2012-09-12 | 吉林大学 | Method for preparing fluorescent graphene quantum dots by solvothermal method |
| CN102849724A (en) * | 2012-10-12 | 2013-01-02 | 上海交通大学 | Preparation method of water-soluble carbon quantum dots |
Non-Patent Citations (2)
| Title |
|---|
| YE R ET AL: "Coal as an abundant source of graphene quantum dots", 《NATURE COMMUNICATIONS》, 6 December 2013 (2013-12-06) * |
| 洪菲等: "改进Hummers法化学合成石墨烯及其表征", 《化学与生物工程》, vol. 29, no. 5, 31 May 2012 (2012-05-31) * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106010517B (en) * | 2016-05-18 | 2018-09-07 | 武汉科技大学 | Using coke powder as carbon quantum dot fluorescence labeling material of carbon source and preparation method thereof |
| CN106010517A (en) * | 2016-05-18 | 2016-10-12 | 武汉科技大学 | Carbon quantum dot fluorescent-labeled material with coke powder serving as carbon source and preparation method of carbon quantum dot fluorescent-labeled material |
| CN106744913A (en) * | 2017-03-28 | 2017-05-31 | 上海理工大学 | A kind of method that utilization cryptocrystalline graphite largely prepares graphene oxide quantum dot |
| WO2018177267A1 (en) * | 2017-03-28 | 2018-10-04 | University Of Shanghai For Science And Technology | Method for preparing graphene oxide quantum dots in a large scale with cryptocrystalline graphite |
| CN108172409A (en) * | 2018-01-10 | 2018-06-15 | 西北师范大学 | A kind of preparation method of three-dimensional flower-shaped structure graphite alkene quantum dot/manganous hydroxide composite material |
| CN108455578A (en) * | 2018-03-17 | 2018-08-28 | 宁夏大学 | Graphene quantum dot and preparation method and application |
| CN109941988A (en) * | 2019-04-24 | 2019-06-28 | 铜仁学院 | A kind of preparation method and application of graphene quantum dot and device or device comprising it |
| CN111686810A (en) * | 2020-06-28 | 2020-09-22 | 西北师范大学 | Preparation method of layer-by-layer self-assembled GQDs/3D-G/PANI composite film |
| CN114426270A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Coal-based graphene quantum dot and preparation method thereof |
| 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 |
| CN114105124A (en) * | 2021-11-12 | 2022-03-01 | 新疆大学 | Preparation method and application of graphene quantum dot and polyphenylene sulfide/graphene quantum dot composite material |
| CN114105124B (en) * | 2021-11-12 | 2023-10-10 | 新疆大学 | Preparation method and application of graphene quantum dot and polyphenylene sulfide/graphene quantum dot composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103803540B (en) | 2015-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103803540B (en) | A kind of preparation method of coal-based graphene quantum dot | |
| CN103480399B (en) | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof | |
| CN106882796B (en) | Preparation method of three-dimensional graphene structure/high-quality graphene | |
| CN108686697B (en) | Alginate-based composite carbon nitride photocatalytic aerogel material and preparation method and application thereof | |
| CN103570010B (en) | A kind of preparation method of graphene powder material | |
| CN103787319A (en) | Large-scale preparation method of graphene quantum dots | |
| CN103769604A (en) | Green and quick method for preparing lignin-nanosilver sol | |
| CN103480398A (en) | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof | |
| CN103086356A (en) | Method for preparing carbon quantum dots | |
| CN104209538A (en) | Method for preparing silver nanowires in aqueous medium | |
| CN102515244B (en) | Hollow cuprous oxide nanometre material and preparation method for same | |
| CN106475100A (en) | The preparation method and application of Graphene/ferroferric oxide magnetic nano composite | |
| CN102718209B (en) | Method for preparing graphene based on reduction of divalent iron ion | |
| Alshamkhani et al. | Effect of graphite exfoliation routes on the properties of exfoliated graphene and its photocatalytic applications | |
| CN106348281A (en) | Method for preparing bifluorescence graphene quantum dots hydrothermally | |
| CN104525202A (en) | Preparation method of alpha-Fe2O3 mesoporous nanorod/nitrogen-doped graphene composite | |
| CN111036243A (en) | Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof | |
| CN104607227A (en) | Preparation method for alpha-Fe2O3 mesoporous nanosheet/nitrogen-doped graphene composite material | |
| CN103626169A (en) | Preparation method of graphene quantum dot | |
| CN104724697A (en) | New microwave assisted preparation method of graphene oxide | |
| CN103539106A (en) | Preparation method of carbon material | |
| CN104128180B (en) | The method of Electron Beam Irradiation synthesis cuprous oxide/Graphene photocatalysis composite nano materials | |
| CN104759282B (en) | A kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst | |
| CN113731395A (en) | Zinc stannate photocatalyst rich in oxygen vacancies, preparation method and application | |
| CN112537783A (en) | W18O49Modified g-C3N4Application of material in photocatalysis nitrogen fixation |
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: 20151202 Termination date: 20190219 |