CN102180459B - Method for preparing carbon quantum dots - Google Patents
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- CN102180459B CN102180459B CN201110049051.XA CN201110049051A CN102180459B CN 102180459 B CN102180459 B CN 102180459B CN 201110049051 A CN201110049051 A CN 201110049051A CN 102180459 B CN102180459 B CN 102180459B
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Abstract
The invention relates to the technical field of quantum dot preparation, in particular to a method for preparing carbon quantum dots, and solves the problems that mass production cannot be realized because raw materials are difficult to obtain, and the fluorescence quantum yield of the obtained carbon quantum dots is low in the conventional method for preparing the carbon quantum dots. The method for preparing the carbon quantum dots comprises the following steps of: heating dried plant stalks in a tubular electric heating furnace, introducing air through an air lead-in pipe of the tubular electric heating furnace, and leading flue gas generated by reaction in a water tank through a flue gas lead-out pipe to obtain soot; adding the obtained soot into nitric acid solution for refluxing and acid boiling, regulating the pH value of reaction solution to be between 6 and 8, and removing water to obtain a solid product; and mixing the solid product and polyethylene glycol in a mass ratio of 3:(2-1) in deionized water, and centrifuging to obtain the carbon quantum dots. The process is easy to operate and can be widely applied to the fields of biological detection, sensing, photoelectric conversion, catalysis, optical amplitude limiting and the like.
Description
Technical field
The present invention relates to quantum dot preparing technical field, be specially a kind of preparation method of carbon quantum dot.
Background technology
Carbon quantum dot is another Novel Carbon Nanomaterials after soccerballene, carbon nanotube and Graphene, it is that size is generally less than 10 nm and has the spherical fluorescent carbon nano particle of good dispersion, it not only has the fluorescence quantum yield comparing favourably with conventional semiconductors quantum dot (as CdS, CdSe and nucleocapsid structure thereof), and there is nontoxic (or low toxicity), good biocompatibility and be easy to many advantages such as surface-functionalized, so there is important application at numerous areas such as biological detection, sensing, radiographies; Carbon quantum dot also can be used as electron donor(ED) or acceptor produces photic transfer transport, makes efficient photoelectricity treater switching device thereby can be used as interpolation component in organic semiconductor material; In addition, carbon quantum dot has also shown very high potential using value in the field such as nonlinear optics, catalysis.
The method of preparing at present carbon quantum dot has multiple, but can be divided into from top to bottom generally and two classes from bottom to up.Class methods are to utilize the means such as arc-over, laser and electrochemistry directly from the carbon material of bulk or carbon nanotube, to obtain from top to bottom, these class methods often need strict experiment condition or the special energy, cost is high, and the fluorescence quantum yield of acquisition carbon quantum dot is less; Class methods are from organism, to obtain thin small and scattered carbon quantum dot by means such as chemical oxidation, microwave treatment, organic charings from bottom to up, but the raw material of selecting due to these class methods is all Nonrenewable energy resources and needs strict aftertreatment technology, so be also unfavorable for continuing and scale production carbon quantum dot.
Summary of the invention
The present invention be for solve existing carbon quantum dot preparation method because of raw material is difficult to obtain cannot large-scale production and obtain the less problem of fluorescence quantum yield of carbon quantum dot, a kind of preparation method of carbon quantum dot has been proposed.
The present invention adopts following technical scheme to realize: a kind of preparation method of carbon quantum dot comprises the following steps:
(1) by quality be
mg and being processed into is less than the fritter of 10 mm or the dried plant stem stalk of thinner powder and puts into tubular type electric heater and heat, and temperature of reaction maintains 350 ~ 450 ℃, passes into volume to be by the air leading-in conduit per minute of tubular type electric heater simultaneously
vthe air of L, makes
v:
m=0.5 ~ 6, the flue gas that reaction generates imports in tank by flue gas delivery line, can obtain soot;
(2) soot obtained above is joined and in the salpeter solution of 2.5 ~ 3.6 mol/L, carry out returned acid and boil, the reaction times is 10 ~ 12 hours, and the pH value of solution after reaction is adjusted into 6 ~ 8, then removes after anhydrating and obtains solid product;
(3) in deionized water, mix take mass ratio as 3:2 ~ 1 with polyoxyethylene glycol and put into thermostat container except the solid product obtaining after anhydrating above-mentioned, temperature of reaction maintains 105 ~ 135 ℃, reaction times is 48 ~ 72 hours, then centrifugal with the centrifugation rate of 4500 ~ 6000 revs/min, can obtain carbon quantum dot.
The molecular weight of described polyoxyethylene glycol is 200 ~ 3000.
Described plant haulm comprises common poplar, ash, various fruit tree and cotton stalk etc.These raw materials are all renewable resourcess, and cost is low, and can scale operation.
The critical nature of the carbon quantum dot that the present invention is obtained is measured: make transmission electron microscope and detect, result shows that carbon quantum dot is dispersion state, and the grain size of carbon quantum dot is mainly distributed in 2 ~ 7 nm; Carry out Micro-Structure Analysis with transmission electron microscope, result shows that carbon quantum dot provided by the invention has part to be crystalline structure; The fluorescent emission nature examination of the carbon quantum dot that the present invention is obtained: the ultraviolet lamp that with wavelength is 365 nm irradiates carbon quantum dot aqueous sample, can obviously observe strong blue light; Detect with spectrophotofluorometer, result shows the fluorescent emission wavelength of the carbon quantum dot wavelength affects that is stimulated, and has the characteristic of multiple VISIBLE LIGHT EMISSION.
The fluorescence quantum yield of carbon quantum dot provided by the invention adopts conventional reference method to measure, under identical shooting conditions, measure respectively the integration fluorescence intensity of reference fluorescence standard material of fluorescence sample to be measured, known quantum yield and the optical density of the incident light of same excitation wavelength, then by these value substitutions below formula:
In formula,
q x with
q st be respectively the fluorescence quantum yield of test substance and reference material;
i x with
i st be respectively the Fluorescence integral intensity of test substance and reference material;
a x with
a st for test substance and reference material are in the optical density of the incident light of this excitation wavelength;
η x with
η st be respectively the specific refractory power of testing sample and standard model.
Using Quinine Sulphate Di HC as reference substance, the fluorescence quantum yield of carbon quantum dot provided by the invention is 20 ~ 36% after measured, can be satisfied with biological detection, sensing, optical limiter part and can be used as and add component to the application that improves photoelectric transformation efficiency in organic semiconductor material.
In a word; technological operation of the present invention is simple, without any particular energy source; and the carbon quantum dot fluorescence quantum yield obtaining is higher; solved existing carbon quantum dot preparation method because of raw material is difficult to obtain cannot large-scale production and obtain the less problem of fluorescence quantum yield of carbon quantum dot, can be widely used in the fields such as biological detection, sensing, opto-electronic conversion, catalysis and light amplitude limit.
Accompanying drawing explanation
Fig. 1 prepares soot device schematic diagram.In figure: 1-air leading-in conduit; 2-tubular type electric heater; 3-vegetable stem stem; 4-flue gas delivery line; 5-tank.
In Fig. 2, (a) is low power transmission electron microscope photo, and illustration is the high-resolution-ration transmission electric-lens photo of a carbon quantum dot; (b) be carbon quantum point grain diameter distribution plan.
Fig. 3 is carbon quantum dot aqueous solution sample photo before and after ultra violet lamp.In figure: the 1st, carbon quantum dot aqueous solution sample photo, is white in color; The 2nd, the sample photo under wavelength 365 nm length ultraviolet light irradiations, is blue.
Fig. 4 is the photoluminescence spectrum of carbon quantum dot.In figure: 1 is the fluorescence spectrum that 400 nm wavelength excite lower collection; 2 is fluorescence spectrums that 440 nm wavelength excite lower collection; 3 is fluorescence spectrums of collecting under 480 nm wavelength lasers; 4 is fluorescence spectrums of collecting under 520 nm wavelength lasers; 5 is fluorescence spectrums of collecting under 560 nm wavelength lasers.
Embodiment
Embodiment 1: a kind of preparation method of carbon quantum dot comprises the following steps: be by quality
mthe dry poplar wood chip of=500 g is put into tubular type electric heater and is heated, and temperature of reaction is 350 ℃, passes into volume to be by the air leading-in conduit per minute of tubular type electric heater simultaneously
vthe air of=250 L, makes
v:
m=0.5, the flue gas that reaction generates imports in tank by flue gas delivery line, can obtain soot; Soot obtained above is joined and in the salpeter solution of 2.5 mol/L, carry out returned acid and boil, the reaction times is 10 hours, and the pH value of solution after reaction is adjusted into 6 ~ 8, then removes after anhydrating and obtains solid product; The above-mentioned polyoxyethylene glycol that is 200 except the solid product obtaining after anhydrating with molecular weight is mixed in deionized water take mass ratio as 3:2 and put into thermostat container, temperature of reaction maintains 105 ℃, reaction times is 48 hours, then with the centrifugal carbon quantum dot that obtains of centrifugation rate of 4500 revs/min.As shown in Figure 2, carbon quantum dot is dispersion state and size distribution is 2 ~ 7 nm, and part carbon quantum dot is crystalline structure; As shown in Figure 3, under the ultra violet lamp of 365 nm wavelength, can produce strong blue emission; As shown in Figure 4, photoluminescence spectrum shows the wavelength size impact that is stimulated of carbon quantum dot fluorescence emission wavelength, has the characteristic of multiple VISIBLE LIGHT EMISSION.
Embodiment 2: a kind of preparation method of carbon quantum dot comprises the following steps: be by quality
mthe dry ash wood chip of=600 g is put into tubular type electric heater and is heated, and temperature of reaction is 450 ℃, passes into volume to be by the air leading-in conduit per minute of tubular type electric heater simultaneously
vthe air of=3600 L, makes
v:
m=6, the flue gas that reaction generates imports in tank by flue gas delivery line, can obtain soot; Soot obtained above is joined and in the salpeter solution of 3.6 mol/L, carry out returned acid and boil, the reaction times is 12 hours, and the pH value of solution after reaction is adjusted into 6 ~ 8, then removes after anhydrating and obtains solid product; The above-mentioned polyoxyethylene glycol that is 3000 except the solid product obtaining after anhydrating with molecular weight is mixed in deionized water take mass ratio as 3:1 and put into thermostat container, temperature of reaction maintains 135 ℃, reaction times is 72 hours, then with the centrifugal carbon quantum dot that obtains of centrifugation rate of 6000 revs/min.Carbon quantum dot is dispersion state and size distribution is 3 ~ 7 nm, and part carbon quantum dot is crystalline structure; Under the ultra violet lamp of 365 nm wavelength, can produce strong blue emission; Photoluminescence spectrum shows the wavelength size impact that is stimulated of carbon quantum dot fluorescence emission wavelength, has the characteristic of multiple VISIBLE LIGHT EMISSION.
Embodiment 3: a kind of preparation method of carbon quantum dot comprises the following steps: be by quality
mthe dried cotton bar bits of=650 g are put into tubular type electric heater and are heated, and temperature of reaction is 400 ℃, passes into volume to be by the air leading-in conduit per minute of tubular type electric heater simultaneously
vthe air of=1950 L, makes
v:
m=3, the flue gas that reaction generates imports in tank by flue gas delivery line, can obtain soot; Soot obtained above is joined and in the salpeter solution of 3 mol/L, carry out returned acid and boil, the reaction times is 11 hours, and the pH value of solution after reaction is adjusted into 6 ~ 8, then removes after anhydrating and obtains solid product; The above-mentioned polyoxyethylene glycol that is 1500 except the solid product obtaining after anhydrating with molecular weight is mixed in deionized water take mass ratio as 3:1.5 and put into thermostat container, temperature of reaction maintains 120 ℃, reaction times is 60 hours, then with the centrifugal carbon quantum dot that obtains of centrifugation rate of 5250 revs/min.Carbon quantum dot is dispersion state and size distribution is 3 ~ 6 nm, and part carbon quantum dot is crystalline structure; Under the ultra violet lamp of 365 nm wavelength, can produce strong blue emission; Photoluminescence spectrum shows the wavelength size impact that is stimulated of carbon quantum dot fluorescence emission wavelength, has the characteristic of multiple VISIBLE LIGHT EMISSION.
Embodiment 4: a kind of preparation method of carbon quantum dot comprises the following steps: be by quality
mthe dry apple bar bits of=400 g are put into tubular type electric heater and are heated, and temperature of reaction is 420 ℃, passes into volume to be by the air leading-in conduit per minute of tubular type electric heater simultaneously
vthe air of=800 L, makes
v:
m=2, the flue gas that reaction generates imports in tank by flue gas delivery line, can obtain soot; Soot obtained above is joined and in the salpeter solution of 2.8mol/L, carry out returned acid and boil, the reaction times is 11.5 hours, and the pH value of solution after reaction is adjusted into 6 ~ 8, then removes after anhydrating and obtains solid product; The above-mentioned polyoxyethylene glycol that is 2000 except the solid product obtaining after anhydrating with molecular weight is mixed in deionized water take mass ratio as 3:1.2 and put into thermostat container, temperature of reaction maintains 115 ℃, reaction times is 55 hours, then with the centrifugal carbon quantum dot that obtains of centrifugation rate of 5500 revs/min.Carbon quantum dot is dispersion state and size distribution is 2 ~ 6 nm, and part carbon quantum dot is crystalline structure; Under the ultra violet lamp of 365 nm wavelength, can produce strong blue emission; Photoluminescence spectrum shows the wavelength size impact that is stimulated of carbon quantum dot fluorescence emission wavelength, has the characteristic of multiple VISIBLE LIGHT EMISSION.
Embodiment 5: a kind of preparation method of carbon quantum dot comprises the following steps: be by quality
mthe dry shaddock bar bits of=350 g are put into tubular type electric heater and are heated, and temperature of reaction is 400 ℃, passes into volume to be by the air leading-in conduit per minute of tubular type electric heater simultaneously
vthe air of=1350 L, makes
v:
m=4.5, the flue gas that reaction generates imports in tank by flue gas delivery line, can obtain soot; Soot obtained above is joined and in the salpeter solution of 3.3 mol/L, carry out returned acid and boil, the reaction times is 10.5 hours, and the pH value of solution after reaction is adjusted into 6 ~ 8, then removes after anhydrating and obtains solid product; The above-mentioned polyoxyethylene glycol that is 1000 except the solid product obtaining after anhydrating with molecular weight is mixed in deionized water take mass ratio as 3:1.7 and put into thermostat container, temperature of reaction maintains 130 ℃, reaction times is 66 hours, then with the centrifugal carbon quantum dot that obtains of centrifugation rate of 4900 revs/min.Carbon quantum dot is dispersion state and size distribution is 3 ~ 6 nm, and part carbon quantum dot is crystalline structure; Under the ultra violet lamp of 365 nm wavelength, can produce strong blue emission; Photoluminescence spectrum shows the wavelength size impact that is stimulated of carbon quantum dot fluorescence emission wavelength, has the characteristic of multiple VISIBLE LIGHT EMISSION.
Claims (3)
1. a preparation method for carbon quantum dot, is characterized in that comprising the following steps:
(1) by quality be
mg and being processed into is less than the fritter of 10 mm or the dried plant stem stalk of thinner powder and puts into tubular type electric heater and heat, and temperature of reaction maintains 350 ~ 450 ℃, passes into volume to be by the air leading-in conduit per minute of tubular type electric heater simultaneously
vthe air of L, makes
v:
m=0.5 ~ 6, the flue gas that reaction generates imports in tank by flue gas delivery line, can obtain soot;
(2) soot obtained above is joined and in the salpeter solution of 2.5 ~ 3.6 mol/L, carry out returned acid and boil, the reaction times is 10 ~ 12 hours, and the pH value of solution after reaction is adjusted into 6 ~ 8, then removes after anhydrating and obtains solid product;
(3) in deionized water, mix take mass ratio as 3:2 ~ 1 with polyoxyethylene glycol and put into thermostat container except the solid product obtaining after anhydrating above-mentioned, temperature of reaction maintains 105 ~ 135 ℃, reaction times is 48 ~ 72 hours, then centrifugal with the centrifugation rate of 4500 ~ 6000 revs/min, can obtain carbon quantum dot.
2. the preparation method of a kind of carbon quantum dot according to claim 1, is characterized in that: the molecular weight of described polyoxyethylene glycol is 200 ~ 3000.
3. the preparation method of a kind of carbon quantum dot according to claim 1 and 2, is characterized in that: described plant haulm comprises common poplar, ash, various fruit tree and cotton stalk etc.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103160279A (en) * | 2011-12-12 | 2013-06-19 | 中国科学院大连化学物理研究所 | Functional carbon dots, and preparation and application thereof |
| CN102675565A (en) * | 2012-05-09 | 2012-09-19 | 天津大学 | Carbon quantum dot-poly N-isopropylacrylamide composite material and preparation method thereof |
| WO2014023097A1 (en) * | 2012-08-06 | 2014-02-13 | 中国科学院理化技术研究所 | Preparation method of heteroatom doped multifunctional carbon quantum dot and application thereof |
| CN102816567B (en) * | 2012-08-21 | 2014-10-22 | 中国人民解放军军事医学科学院卫生装备研究所 | Method for preparing high-yield carbon quantum dots |
| CN102942170B (en) * | 2012-10-22 | 2014-04-30 | 上海交通大学 | Preparation method of carbon quantum dots based on atmospheric pressure micro-plasma technology |
| CN102911664A (en) * | 2012-11-09 | 2013-02-06 | 吉林大学 | Fluorescent polymer dot, hydrothermal synthesis method through linear non-conjugated polymers and application thereof |
| CN103086356A (en) * | 2013-02-19 | 2013-05-08 | 复旦大学 | Method for preparing carbon quantum dots |
| CN103100725B (en) * | 2013-02-28 | 2015-03-04 | 江苏大学 | Preparation method of silver/carbon quantum dot composite nanometer materials |
| CN103332676B (en) * | 2013-07-07 | 2015-01-28 | 上海科润光电技术有限公司 | Preparation method of carbon quantum dot fluorescent material |
| CN103344756B (en) * | 2013-07-15 | 2015-09-09 | 中南大学湘雅二医院 | A kind of preparation method of the carbon quantum dot test strips for detecting P24 antigen |
| CN103447058A (en) * | 2013-09-18 | 2013-12-18 | 中北大学 | Preparation method for chlorine element modified carbon quantum dot |
| CN105236386A (en) * | 2015-11-10 | 2016-01-13 | 东华大学 | Method for preparing carbon nanoparticles through corncob |
| CN106167256B (en) * | 2016-07-07 | 2018-06-01 | 中北大学 | The method that multicolor luminous adjustable carbon dots is prepared using coal quality pitch |
| CN106497562A (en) * | 2016-10-20 | 2017-03-15 | 广西壮族自治区林业科学研究院 | A kind of preparation method of carbon quantum dot |
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| CN101973541A (en) * | 2010-10-11 | 2011-02-16 | 福州大学 | Method for extracting carbon quantum dots from activated carbon |
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| CN101973541A (en) * | 2010-10-11 | 2011-02-16 | 福州大学 | Method for extracting carbon quantum dots from activated carbon |
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