CN103803540B - A kind of preparation method of coal-based graphene quantum dot - Google Patents
A kind of preparation method of coal-based graphene quantum dot Download PDFInfo
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- CN103803540B CN103803540B CN201410056637.2A CN201410056637A CN103803540B CN 103803540 B CN103803540 B CN 103803540B CN 201410056637 A CN201410056637 A CN 201410056637A CN 103803540 B CN103803540 B CN 103803540B
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Abstract
The present invention relates to a kind of preparation method of coal-based graphene quantum dot, the method comprises the following steps: using natural coal cinder as starting material, pulverized 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; Ultrasonic pond supersound process is put into after being mixed with strong acid by coal dust material, then put into refrigerator freezing to spend the night, slowly add SODIUMNITRATE after taking-up and continue to stir 30min, reaction unit is placed in ice bath, slowly add potassium permanganate and stir 30min, reaction unit is placed in 35 DEG C of water-baths again, add deionized water and hydrogen peroxide, reaction stirring is spent the night, finally by above-mentioned reaction soln centrifugation, get supernatant liquor to add alkaline reactant and be neutralized to neutrality, after dialysis desalination, namely obtain water miscible graphene quantum dot.Compared with prior art, the present invention adopts natural coal cinder to prepare the method for graphene quantum dot as starting material, abundant raw materials, low price, and preparation technology is simple, and output is large, is applicable to large-scale commercial and produces.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, specifically a kind of is raw material with raw coal, utilizes and improves the novel method of Hummers legal system for coal-based graphene quantum dot.
Background technology
Graphene quantum dot is as the accurate zero dimensional nanometer materials of one, 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.Current graphene quantum dot has been applied to the aspects such as photodiode, solar cell, photochemical catalysis, bioprobe, fluorescent mark, nanometer electronic device.
The preparation method of graphene quantum dot has: hydrothermal method, electrochemical process, ultrasonic method, microwave method, electron beam lithography etc.But these methods are prepared graphene quantum dot and are all had that such as starting material are expensive, equipment requirements is harsh, energy expenditure is high, graphene quantum dot productive rate is low, the low inferior shortcoming of preparation efficiency.Through finding existing literature search, the people such as ChangshengXiang, at NATURECOMMUNICATIONS, 2013,4:2943 have delivered " Coalasanabundantsourceofgraphenequantumdots ".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, and accelerated oxidation is reacted.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, the graphene quantum dot dimensional homogeneity prepared is poor.
Summary of the invention
Object of the present invention is exactly provide a kind of abundant raw materials, low price to overcome 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 is produced.
Object of the present invention can be achieved through the following technical solutions: a kind of preparation method of coal-based graphene quantum dot, and it 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, pulverizes into the powder of different size by mechanical force, utilize the sieve of different meshes, obtains 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 being mixed with strong acid by coal dust material, put into ultrasonic pond supersound process, then put into refrigerator freezing to spend the night, slowly add SODIUMNITRATE after taking-up and continue to stir 30min, reaction unit is placed in ice bath, slowly add potassium permanganate and stir 30min, reaction unit is placed in 35 DEG C of water-baths again, add deionized water and hydrogen peroxide, reaction stirring is spent the night, finally by above-mentioned reaction soln centrifugation, get supernatant liquor to add alkaline reactant and be neutralized to neutrality, namely water miscible graphene quantum dot is obtained after dialysis desalination.
Described coal dust material is of a size of 100 ~ 1000 orders.
Described strong acid is one in the vitriol oil, concentrated nitric acid or both mixtures, and its add-on is that every gram of coal powder material adds 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.
By regulate the size of coal dust raw material, temperature of reaction and time, centrifugation speed and time and dialysis tubing interception obtain the controlled water-soluble graphene quantum dots of size.
Compared with prior art, the present invention is by controlling the size of coal dust raw material, temperature of reaction and time, dialysis tubing interception, and obtain the water-soluble graphene quantum dots of low cost, 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;
The absorption spectrum of Fig. 2 graphene quantum dot prepared by embodiment 1.
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 and obtains 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.Slowly add 1.0g SODIUMNITRATE after taking-up, stir 30min, reaction unit is placed in ice bath, slowly adds 2.0g potassium permanganate, stir 2h, then reaction unit is placed in water-bath 35 DEG C, add 60ml water and 20ml hydrogen peroxide, reaction stirring 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 interception be 2000 dialysis tubing 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 and obtains 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.Slowly add 0.6g SODIUMNITRATE after taking-up, stir 30min, reaction unit is placed in ice bath, slowly adds 3.0g potassium permanganate, stir 2h, then reaction unit is placed in water-bath 35 DEG C, add 50ml water and 30ml hydrogen peroxide, reaction stirring 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, adopt interception be 3000 dialysis tubing dialyse 3 days, obtain water miscible graphene quantum dot.
Embodiment 3
Natural coal cinder is pulverized to sieve by mechanical force and obtains 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.Slowly add 0.4g SODIUMNITRATE after taking-up, stir 30min, reaction unit is placed in ice bath, slowly adds 4.0g potassium permanganate, stir 2h, then reaction unit is placed in water-bath 35 DEG C, add 40ml water and 20ml hydrogen peroxide, reaction stirring 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, adopt interception be 1000 dialysis tubing dialyse 3 days, obtain water miscible graphene quantum dot.
Embodiment 4
Natural coal cinder is pulverized to sieve by mechanical force and obtains 100 powder materials, get 1g coal dust and mix in beaker with the 0.8mol vitriol oil/concentrated nitric acid (V/V=3: 1) and put into the ultrasonic 30min in ultrasonic pond, then put into refrigerator freezing and spend the night.Slowly add 1.0g SODIUMNITRATE after taking-up, stir 30min, reaction unit is placed in ice bath, slowly adds 8.0g potassium permanganate, stir 2h, then reaction unit is placed in water-bath 35 DEG C, add 100ml water and 40ml hydrogen peroxide, reaction stirring 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 interception be 2000 dialysis tubing dialyse 3 days, obtain water miscible graphene quantum dot.
Embodiment 5
Natural coal cinder is pulverized to sieve by mechanical force and obtains 800 powder materials, get 1g coal dust and mix in beaker with the 0.6mol vitriol oil/concentrated nitric acid (V/V=3: 1) and put into the ultrasonic 30min in ultrasonic pond, then put into refrigerator freezing and spend the night.Slowly add 0.6g SODIUMNITRATE after taking-up, stir 30min, reaction unit is placed in ice bath, slowly adds 8.0g potassium permanganate, stir 2h, then reaction unit is placed in water-bath 35 DEG C, add 60ml water and 40ml hydrogen peroxide, reaction stirring 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 interception be 2000 dialysis tubing dialyse 3 days, obtain water miscible graphene quantum dot.
Claims (8)
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, pulverizes into the powder of different size by mechanical force, utilize the sieve of different meshes, obtains 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 being mixed with strong acid by coal dust material, put into ultrasonic pond supersound process, then put into refrigerator freezing to spend the night, slowly add SODIUMNITRATE after taking-up and continue to stir 30min, reaction unit is placed in ice bath, slowly add potassium permanganate and stir 30min, reaction unit is placed in 35 DEG C of water-baths again, add deionized water and hydrogen peroxide, reaction stirring is spent the night, finally by above-mentioned reaction soln centrifugation, get supernatant liquor to add alkaline reactant and be neutralized to neutrality, namely water miscible graphene quantum dot is obtained after dialysis desalination,
By regulate the size of coal dust raw material, temperature of reaction and time, centrifugation speed and time and dialysis tubing interception obtain the controlled water-soluble graphene quantum dots of size.
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 one in the vitriol oil, concentrated nitric acid or both mixtures, and its add-on is that every gram of coal powder material adds 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 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.
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| CN104946252B (en) * | 2015-07-15 | 2017-01-18 | 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 |
| 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 |
| CN108172409B (en) * | 2018-01-10 | 2020-05-12 | 西北师范大学 | Preparation method of graphene quantum dot/manganese hydroxide composite material with three-dimensional flower-like structure |
| CN108455578A (en) * | 2018-03-17 | 2018-08-28 | 宁夏大学 | Graphene quantum dot and preparation method and application |
| CN109941988B (en) * | 2019-04-24 | 2021-01-26 | 铜仁学院 | Preparation method and application of graphene quantum dots, and device or apparatus containing graphene quantum dots |
| 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 |
| 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 |
| 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 |
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