CN110669513A - Method for preparing white fluorescent carbon dots through solid-phase reaction - Google Patents
Method for preparing white fluorescent carbon dots through solid-phase reaction Download PDFInfo
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- CN110669513A CN110669513A CN201911008986.6A CN201911008986A CN110669513A CN 110669513 A CN110669513 A CN 110669513A CN 201911008986 A CN201911008986 A CN 201911008986A CN 110669513 A CN110669513 A CN 110669513A
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 24
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229960001230 asparagine Drugs 0.000 claims abstract description 16
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000502 dialysis Methods 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000003086 colorant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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Abstract
The invention provides a method for preparing white fluorescent carbon dots through solid-phase reaction, and belongs to the technical field of preparation of fluorescent nano materials. Firstly, fully grinding 1, 6-naphthalenediol and L-asparagine solid powder in a mass ratio of 1:1 at room temperature, and directly putting the solid powder into a polytetrafluoroethylene reaction kettle without adding a solvent; secondly, heating to 140-200 ℃, reacting for 4-10 h, naturally cooling to room temperature, dialyzing by using a dialysis bag, and freeze-drying; finally, the product was dissolved in DMF to give a white fluorescent carbon dot. Compared with other multicolor fluorescent carbon dots, the carbon dots capable of emitting white fluorescence can be directly obtained, do not need complicated processes, and can be directly applied to white LEDs.
Description
Technical Field
The invention relates to a method for preparing a carbon dot emitting white fluorescence through a solid-phase reaction, belonging to the technical field of preparation of fluorescent nano materials.
Background
The carbon dot is a spheroidal or spherical fluorescent nanoparticle which takes carbon as a main constituent element, has a plurality of polyfunctional groups on the surface and has the size of less than 10 nm. The luminescent material is expected to be a new fluorescent base material due to the advantages of good light stability, low cost, low toxicity, adjustable fluorescence, easy preparation and the like.
The most common preparation method of the carbon dots at present is a hydrothermal method or a solvothermal method. In order to avoid the participation of a solvent in the reaction, a solid-phase reaction is adopted, and a product can be finally obtained through dehydration, polymerization and carbonization in the reaction process, so that the yield of the obtained product is higher.
In recent years, carbon dots have attracted more attention as color conversion phosphors by researchers at home and abroad. The Light-Emitting diode has the advantages of low cost, photobleaching resistance, easy functionalization, low toxicity, mild reaction conditions, high thermal stability and chemical stability, environmental friendliness and the like, so that the Light-Emitting diode is applied to the field of white Light-Emitting Diodes (LEDs). At present, there are two main ways for carbon dots as LEDs made of luminescent materials: one is that blue LEDs excite yellow carbon dots to produce white light; the other is ultraviolet LEDs that excite a red, green, blue (RGB) three primary color carbon dot to produce white light. The former method is most commonly used to produce white light at present, but its luminous efficiency is insufficient. The latter type of recent light emission has higher luminous efficiency than blue light. And the process is complicated and fussy because the proportion of the RGB three-primary-color fluorescent powder needs to be adjusted.
The solid carbon dots are prepared through solid-phase reaction, so that the carbon dots emitting white fluorescence can be directly obtained, and the cost and the time can be saved when the carbon dots are applied to white LEDs.
Disclosure of Invention
The invention directly obtains the white fluorescent carbon dots through solid-phase reaction, overcomes the problem that white light is obtained by adjusting three primary colors or complementary colors, and solves the problems of high cost and complex preparation process of the fluorescent powder in the application aspect of white LEDs.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing a white fluorescent carbon dot through a solid-phase reaction, which can directly obtain the white fluorescent carbon dot, comprises the following steps:
fully grinding 1, 6-naphthalenediol and L-asparagine solid powder in a mass ratio of 1:1 at room temperature, directly putting the solid powder into a polytetrafluoroethylene reaction kettle, reacting for 4-10 h at 140-200 ℃ without adding a solvent (without adding other solvents), naturally cooling to room temperature, dialyzing for 12-24 h by using a 1K dialysis bag, freeze-drying, and dissolving in N, N-dimethylformamide DMF to obtain white fluorescent carbon dots.
The reaction time of the 1, 6-naphthalenediol and the L-asparagine solid powder is preferably 180 ℃;
the reaction time of the 1, 6-naphthalenediol and the L-asparagine solid powder is preferably 6 h.
The invention has the beneficial effects that: the invention utilizes a new preparation method-a solid phase reaction one-step method to prepare the carbon dots emitting white fluorescence. The method can be directly applied to white light LEDs without adjusting the proportion of RGB three primary colors.
Drawings
FIG. 1 shows fluorescence emission spectra of the carbon dots synthesized in example 1.
FIG. 2 is a transmission electron micrograph of the carbon dots synthesized in example 1.
FIG. 3 is an IR spectrum of the carbon dots synthesized in example 1.
Fig. 4 is a uv absorption spectrum of the carbon dots synthesized in example 1.
FIG. 5 is a fluorescence spectrum of carbon dots synthesized in examples 1-4 at different reaction temperatures.
FIG. 6 is a fluorescence spectrum of carbon spots synthesized in examples 5-8 at different reaction times.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Examples 1 to 4
Mixing 1, 6-naphthalenediol and L-asparagine according to the mass ratio of 1:1, fully grinding, directly adding into a polytetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, cooling to room temperature, dissolving in DMF, dialyzing for 12h by using a 1K dialysis bag, freeze-drying, and dissolving in DMF again.
FIG. 1 is a fluorescence emission spectrum of the carbon dot solution obtained in example 1, and it can be seen that the fluorescence emission spectrum of the carbon dot prepared by us has two peaks under 360nm excitation, one with a wavelength of 430nm and the other with a wavelength of 550nm, and covers most of the visible light region as complementary light, which indicates that the carbon dot emitting white fluorescence is successfully prepared. FIG. 2 is a transmission electron microscope photograph of the obtained carbon dots, and it can be seen that the size distribution of the obtained carbon dots is around 3 nm. FIG. 3 is an IR spectrum of the carbon dot obtained in example 1, from which it can be seen that the surface of the carbon dot has abundant radicals at 3200cm-1Has strong hydroxyl stretching vibration absorption peak and no amino characteristic peak on the L-asparagine, which indicates that the amino participates in the reaction in the formation process of the carbon dots. Fig. 4 shows the uv absorption spectrum of the carbon dot obtained in example 1, where the C ═ C bond pi-pi transition at 280nm and the C ═ O bond n-pi transition at 350 nm. FIG. 5 shows fluorescence emission spectra of carbon dots obtained in examples 1 to 4, and it was found that the fluorescence intensity is the strongest when the reaction temperature of only 1, 6-naphthalenediol and L-asparagine is 180 ℃.
TABLE 1 EXAMPLES 1 TO 4 reaction temperatures of 1, 6-naphthalenediol and L-asparagine as solid powders
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Reaction temperature (. degree.C.) | 140 | 160 | 180 | 200 |
Examples 5 to 8
Mixing 1, 6-naphthalenediol and L-asparagine according to the mass ratio of 1:1, fully grinding, directly adding into a polytetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, cooling to room temperature, dissolving in DMF, dialyzing for 12h by using a 1K dialysis bag, freeze-drying, and dissolving in DMF again.
TABLE 2 examples 5 to 8 are reaction times of 1, 6-naphthalenediol and L-asparagine as solid powders
| Example 5 | Example 6 | Example 7 | Example 8 | |
| Reaction time (h) | 4 | 6 | 8 | 10 |
Example 9
Mixing 1, 6-naphthalenediol and L-asparagine according to the mass ratio of 1:1, fully grinding, directly adding into a polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 6h, cooling to room temperature, dissolving in DMF, dialyzing with a 1K dialysis bag for 24h, freeze-drying, and dissolving in DMF again.
Example 10
Mixing 1, 6-naphthalenediol and L-asparagine according to the mass ratio of 1:1, fully grinding, directly adding into a polytetrafluoroethylene reaction kettle, reacting for 6h at 180 ℃, cooling to room temperature, dissolving in DMF, dialyzing for 18h by using a 1K dialysis bag, freeze-drying, and dissolving in DMF again.
Example 11
Mixing 1, 6-naphthalenediol and L-asparagine according to the mass ratio of 1:1, fully grinding, directly adding into a polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 6h, cooling to room temperature, dissolving in DMF, dialyzing with a 1K dialysis bag for 16h, freeze-drying, and dissolving in DMF again.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (3)
1. A method for preparing a white fluorescent carbon dot through a solid-phase reaction is characterized in that the method can directly obtain the white fluorescent carbon dot, and the steps are as follows:
firstly, fully grinding 1, 6-naphthalenediol and L-asparagine solid powder in a mass ratio of 1:1 at room temperature, and directly putting the solid powder into a reaction kettle without adding a solvent; secondly, heating to 140-200 ℃, reacting for 4-10 h, naturally cooling to room temperature, dialyzing for 12-24 h by using a 1K dialysis bag, and freeze-drying; finally, the product was dissolved in N, N-dimethylformamide as a solvent to obtain a white fluorescent carbon dot.
2. The method for preparing a white fluorescent carbon dot by a solid phase reaction according to claim 1, wherein the reaction time of the 1, 6-naphthalenediol with the L-asparagine solid powder is preferably 180 ℃.
3. The method for preparing a white fluorescent carbon dot by a solid-phase reaction according to claim 1 or 2, wherein the reaction time of the 1, 6-naphthalenediol and the L-asparagine solid powder is preferably 6 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117342543A (en) * | 2023-10-07 | 2024-01-05 | 中北大学 | Carbon-based light conversion nano material, light conversion adhesive film for crystalline silicon solar cell and light conversion backboard material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987863A (en) * | 2015-06-25 | 2015-10-21 | 西安交通大学 | Nitrogen, phosphorus and sulphur doping or co-doping carbon dot and batch controllable preparing method and application thereof |
| CN106268715A (en) * | 2016-09-12 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of green synthesis method of carbon quantum dot bonded silica gel chromatograph packing material |
| CN106957050A (en) * | 2017-03-17 | 2017-07-18 | 山西大学 | A kind of fluorescent carbon quantum dot and its preparation method and application |
| CN109399606A (en) * | 2018-12-21 | 2019-03-01 | 北京工业大学 | A kind of preparation method of efficient photothermal conversion carbon dots base foam |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104987863A (en) * | 2015-06-25 | 2015-10-21 | 西安交通大学 | Nitrogen, phosphorus and sulphur doping or co-doping carbon dot and batch controllable preparing method and application thereof |
| CN106268715A (en) * | 2016-09-12 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of green synthesis method of carbon quantum dot bonded silica gel chromatograph packing material |
| CN106957050A (en) * | 2017-03-17 | 2017-07-18 | 山西大学 | A kind of fluorescent carbon quantum dot and its preparation method and application |
| CN109399606A (en) * | 2018-12-21 | 2019-03-01 | 北京工业大学 | A kind of preparation method of efficient photothermal conversion carbon dots base foam |
Non-Patent Citations (1)
| Title |
|---|
| HAIJUAN ZHANG等: "Preparation and characterization of carbon dot-decorated silica", 《ANAL BIOANAL CHEM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117342543A (en) * | 2023-10-07 | 2024-01-05 | 中北大学 | Carbon-based light conversion nano material, light conversion adhesive film for crystalline silicon solar cell and light conversion backboard material |
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