CN113025325B - Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source - Google Patents
Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source Download PDFInfo
- Publication number
- CN113025325B CN113025325B CN202110320107.4A CN202110320107A CN113025325B CN 113025325 B CN113025325 B CN 113025325B CN 202110320107 A CN202110320107 A CN 202110320107A CN 113025325 B CN113025325 B CN 113025325B
- Authority
- CN
- China
- Prior art keywords
- room temperature
- carbon
- based composite
- preparation
- composite material
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
Abstract
The invention discloses a preparation method of a room temperature phosphorescent carbon-based composite material capable of changing color under a single excitation source, which utilizes a hydrogen bond interaction cocrystallization compounding strategy of a carbon quantum dot and a common room temperature induced aromatic compound to obtain the carbon-based composite material with the room temperature phosphorescent color changing performance under the single excitation source, and the yield is 75.3% -90.7%. The invention effectively overcomes the condition limitation that the existing color-changing room temperature phosphorescent material needs to be under the combined action of different excitation sources or the blending of a plurality of compounds, realizes that the color-changing room temperature phosphorescent material of the carbon-based composite material can be seen by naked eyes in the range of orange, yellow, yellowish green and green under a single excitation source, and has the service life of 91ms to 582ms. The preparation route is green and environment-friendly, economical and convenient, the change range of the phosphorescence color and the service life are adjustable, and the method has wide application prospect in the fields of high-grade anti-counterfeiting and digital encryption.
Description
Technical Field
The invention belongs to the field of material preparation and luminescent materials, and particularly relates to a preparation method and application of a carbon-based composite material capable of realizing color change room temperature phosphorescent performance under a single excitation source.
Background
The long-life room temperature phosphorescent material is a light-storing luminescent material, can slowly emit macroscopic long-life phosphorescence after light source irradiation is stopped, and is widely applied to the fields of information safety, digital encryption, life science, photoelectric devices and the like. The long-life room temperature phosphorescent material reported at present mainly comprises sulfide doped lanthanide elements, oxides doped with heavy metal ions or heterocyclic conjugated organic matters doped with heteroatoms. It is expensive, has a certain biological toxicity, and is complex to prepare or purify. More importantly, the functional application of the compounds is almost based on the attenuation of single emission peak intensity along with time, so that the application of the compounds in the aspects of high-density information storage and high-grade multi-dimensional anti-counterfeiting is limited. Therefore, a new generation of green intelligent materials which are composed of multiple emission centers and have room temperature phosphorescence and continuously change color along with time are developed, and the green intelligent materials have important significance for the development of modern information technology materials.
CN201911304592.5 discloses an application of hydantoin and its derivatives as color-changing room temperature phosphorescent materials. The preparation method takes hydantoin and formaldehyde or acetaldehyde as raw materials, prepares organic non-aromatic micromolecule hydantoin derivatives under the acidic condition, and obtains crystal products with the excitation wavelength depending on room temperature phosphorescence performance through a method of cooling hot saturated aqueous solution. It shows long afterglow of different colors under different excitation sources, such as sky blue afterglow after the removal of the 312nm ultraviolet lamp (tau =1.54 s), and yellow green afterglow after the removal of the 365nm ultraviolet lamp (tau =1.74 s).
CN202010522766.1 discloses an organic ultralong room temperature phosphorescent material, a triple anti-counterfeiting organic ink and an application thereof, wherein three phosphonium salt crystals with the same luminescence color and different luminescence lives are dissolved by ethanol and then are respectively placed in three ink boxes of a printer as a security ink for printing anti-counterfeiting patterns. Namely, the color-changing afterglow is realized by mixing three compounds.
The carbon nano material is a novel optical material developed in recent years, has the advantages of good light stability, photobleaching resistance, adjustable emission and excitation wavelength, low toxicity, easy preparation and the like, and has wide application prospect in the fields of biomedicine, photoelectric devices and the like. By embedding the carbon quantum dots into the outer substrate, the carbon quantum dots not only isolate oxygen and block water, but also can anchor the vibration or rotation of the sub-emitting groups on the surface, such as C = O/C = N, and the like, so that the triplet excitons can be stabilized stably, the non-radiative energy dissipation is inhibited, and the generation of long-life room-temperature phosphorescence is promoted. The invention compounds the carbon quantum dots and the aromatic substance with crystallization induction through the hydrogen bond self-assembly function, adjusts and activates the optical performance of the dual-room-temperature phosphor center through crystallization, and realizes the color-changing afterglow characteristic of the composite material by utilizing different luminescent colors and different luminescent lives of the carbon quantum dots and the aromatic substance under the same excitation source.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a preparation method and application of a room temperature phosphorescent carbon-based composite material capable of changing color under a single excitation source, aiming at overcoming the phenomenon that the existing color-changing room temperature phosphorescent material needs to be realized under the combined action of different excitation sources or under the condition of blending of a plurality of compounds.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of room temperature phosphorescent carbon-based composite material with color changing under a single excitation source comprises the following steps:
(1) Uniformly stirring and dissolving melamine and amino acid containing sulfur or selenium in a solvent to obtain a solution; preferably, the concentration of the melamine is 0.01 mol/L-0.05 mol/L;
(2) Transferring the solution obtained in the step (1) into a reaction kettle, sealing, then naturally cooling to room temperature after high-temperature reaction in an oven, centrifuging at high speed, refrigerating the obtained clear liquid, centrifuging at high speed, dialyzing, and freeze-drying to obtain powder, namely the yellow fluorescent emission carbon quantum dots; preferably, it is refrigerated at 4 ℃ and lyophilized at 55 ℃;
(3) And (3) dissolving the carbon quantum dots in the step (2) in a solvent, preferably, adding an aromatic compound with crystallization-induced room temperature phosphorescence performance into the solvent to perform heating reflux self-assembly and natural cooling cocrystallization precipitation, then filtering, washing with the solvent, performing vacuum drying, preferably, performing vacuum drying at 50 ℃, and obtaining the crystal, namely the room temperature phosphorescent carbon-based composite material.
Wherein, the amino acid containing sulfur or selenium in the step (1) is any one of cystine, cysteine, selenocysteine and selenocysteine.
The aromatic compound in the step (3) is any one of isophthalic acid, phthalic acid, terephthalic acid and melamine.
Preferably, the solvent in step (1) and step (3) is water or ethanol.
Preferably, the reaction kettle in the step (2) is a polytetrafluoroethylene-lined high-pressure reaction kettle.
Preferably, in the step (2), the reaction is carried out in an oven at 160-200 ℃ for 4-6 h.
Preferably, in the step (3), the temperature is increased to 80-130 ℃ and the self-assembly time is 0.5-2 h under reflux.
More preferably, the molar ratio of the melamine to the amino acid containing sulfur or selenium is 1.
More preferably, the mass ratio of the carbon quantum dots to the aromatic compound is 1.
Preferably, the high-speed centrifugation rotating speed in the step (2) is 10000-16000 r/min, and the adopted dialysis bag is a ready-to-use dialysis bag 3500D.
The filter paper used in the filtration in the step (3) is medium-speed filter paper, and the aperture is 30-50 μm.
Wherein, the yield of the carbon-based compound prepared by the method is 75.3-90.7%, the color change range of the color-changing afterglow is orange-yellow-yellowish green-green, and the afterglow life is 91 ms-582 ms.
The invention further provides application of the room-temperature phosphorescent carbon-based composite material prepared by the preparation method in preparation of high-grade anti-counterfeiting icons.
Specifically, the prepared carbon-based composite material is dissolved according to a conventional method to prepare ink, and an anti-counterfeiting icon is prepared by using a printer for anti-counterfeiting application.
Has the advantages that: compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The carbon quantum dots and common organic compounds are adopted to be combined by cocrystallization through hydrogen bond action, so that the method is green, environment-friendly, economical and convenient;
(2) The color-changing room temperature phosphorescent carbon-based composite material prepared by the invention can realize continuous luminescence under a single material and the same excitation source;
(3) The material can regulate and control the room temperature phosphorescence color change range and the duration time by adjusting the types of the carbon quantum dots or the aromatic substances.
Drawings
FIG. 1 is a transmission electron microscope image of the carbon quantum dots prepared in example 1;
FIG. 2 is a size distribution of carbon quantum dots prepared in example 1;
FIG. 3 is an XPS map of carbon quantum dots prepared in example 1, wherein (a) the XPS survey spectrum; (b) high resolution XPS (X-ray diffraction) spectrum of carbon, nitrogen, oxygen and sulfur elements;
FIG. 4 is a 3D fluorescence emission plot of the carbon quantum dots prepared in example 1;
FIG. 5 is a transmission electron microscope and elemental distribution plots of (a) a carbon-based composite prepared in example 1;
FIG. 6 is a color change room temperature phosphorescence photograph of the carbon-based composites prepared in examples 1-4;
FIG. 7 is a graph of room temperature phosphorescent emission of a carbon-based composite prepared in example 1 and its Gaussian fit;
FIG. 8 is a graph of the phosphorescence emission at room temperature for different time delays for the carbon-based composite prepared in example 1;
FIG. 9 is a CIE chromaticity diagram of color change room temperature phosphorescence of the carbon-based composite prepared in example 1;
FIG. 10 is a graph of the room temperature phosphorescence lifetime of the carbon-based composite prepared in example 1 at different peak positions;
FIG. 11 is a color-changing room temperature phosphorescence image of an anti-counterfeit icon fabricated from the carbon-based composite prepared in examples 1-4;
FIG. 12 is a transmission electron micrograph of a carbon-based composite prepared according to example 2;
FIG. 13 is a graph of room temperature phosphorescent emission and Gaussian fit of a carbon-based composite prepared in example 2;
FIG. 14 is a graph of room temperature phosphorescence emission of a carbon-based composite prepared in example 2 at different time delays;
FIG. 15 is a CIE chromaticity diagram of color change room temperature phosphorescence of the carbon-based composite prepared in example 2;
FIG. 16 is a graph of the room temperature phosphorescence lifetime of the carbon-based composite prepared in example 2 at different peak positions;
FIG. 17 is a 3D fluorescence plot of carbon quantum dots prepared in example 4;
fig. 18 is a transmission electron micrograph of a carbon-based composite prepared according to example 4.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The examples will help to understand the present invention given the detailed embodiments and the specific operation procedures, but the scope of the present invention is not limited to the examples described below.
Example 1
0.2522g of melamine and 0.4802g of cystine are weighed and added into 15mL of water, stirred for 10min, the mixed solution is transferred into a 25mL reaction kettle, sealed and put into an oven to react for 4h at the temperature of 180 ℃. Naturally cooling to room temperature after reaction, centrifuging at a high speed of 10000r/min, refrigerating the obtained clear liquid in a refrigerator at 4 ℃ for 12h, centrifuging at a high speed of 10000r/min, dialyzing by a dialysis bag (3500D), and freeze-drying at-55 ℃, wherein the obtained powder is the yellow fluorescent light-emitting carbon quantum dot. And then 0.0450g of the carbon quantum dots are weighed and dispersed in 30mL of water, 0.3000g of melamine is added, the temperature is raised to 100 ℃, reflux is carried out for 2h, self-assembly is carried out, the temperature is naturally reduced after reaction, massive crystals are separated out, and the target carbon-based compound is obtained through washing, filtering and vacuum drying at 50 ℃, and the yield is 75.3%. Upon removal of the excitation with a 365nm UV lamp, a color-changing afterglow of orange to orange-yellow to green was observed (τ =101 ms). The prepared carbon-based composite material is prepared into ink according to a conventional method, an anti-counterfeiting icon is printed by using a printer, the ink is filled in the icon printed by the printer to prepare the anti-counterfeiting icon, and the anti-counterfeiting color-changing afterglow observation can be carried out by using a 365nm ultraviolet lamp.
Fig. 1 and 2 are transmission electron microscope and size distribution pictures of the carbon quantum dots prepared in example 1, and it can be seen that the obtained carbon quantum dots have an average particle size of 2.5nm, are spherical, and have uniform size distribution. FIG. 3 is an XPS plot of carbon quantum dots in example 1, showing the content of each element as C52.9 wt%, O20.95 wt%, N17.87wt%, S8.28 wt%, COOH, OH, NH present on the surface2S = O, C = N, etc. FIG. 4 is a 3D fluorescence emission graph of the carbon quantum dots of example 1, with an optimal emission wavelength of 542nm. Fig. 5 is a transmission electron microscope and element distribution picture of the carbon-based composite of example 1, showing that the carbon quantum dots are uniformly embedded in the melamine matrix. FIG. 6 is a photograph of a color-changing afterglow luminance in 7s after the 365nm UV lamp is turned off of the carbon-based composite of example 1, which is seen to undergo a phosphorescent transition at room temperature from orange to yellow to green. FIG. 7 is a graph of the room temperature phosphorescent emission of the carbon-based composite of example 1 and a Gaussian fit, where two phosphorescent emission centers are shown, corresponding to the phosphorescent emission of the carbon quantum dot at 567nm and the phosphorescent emission of the melamine at 532 nm. FIG. 8 is a graph of the phosphorescence emission at room temperature of the carbon-based composite of example 1 at 0.1,1,10,50,100,500ms respectively, where it is clearly observed that the phosphorescence emission at room temperature is blue-shifted from around 570nm to around 530nm with the passage of time, which is consistent with the CIE graph (FIG. 9) and the change in afterglow color observed with the naked eye. Fig. 10 is a graph of the phosphorescence lifetimes at room temperature for a carbon quantum dot and a melamine-based two-optical center, respectively, showing that the decay lifetimes of the carbon quantum dot at the orange luminescence center (τ =81 ms) and the melamine at the blue-green luminescence center (τ =101 ms) are different, resulting in a color-shifting afterglow. The resulting security icon is shown in fig. 11, where the "pigeon" pattern turns from orange to yellow and finally to green with continuous illumination.
Example 2
0.2522g of melamine and 0.4802g of cystine are weighed and added into 15mL of water, stirred for 10min, the mixed solution is transferred into a 25mL reaction kettle, sealed and put into an oven to react for 4h at the temperature of 180 ℃. Naturally cooling to room temperature after reaction, centrifuging at a high speed of 10000r/min, refrigerating the obtained clear liquid in a refrigerator at 4 ℃ for 12 hours, centrifuging at a high speed of 10000r/min, dialyzing by a dialysis bag (3500D), and freeze-drying at-55 ℃, thus obtaining the powder, namely the yellow fluorescent emission carbon quantum dots. And then 0.0450g of the carbon quantum dots are weighed and dispersed in 30mL of water, 0.4500g of isophthalic acid is added, the temperature is raised to 120 ℃, reflux is carried out for 2 hours, self-assembly is carried out, the temperature is naturally reduced after reaction, needle-shaped crystals are separated out, washing, filtering and vacuum drying are carried out at 50 ℃, and the target carbon-based compound is obtained, wherein the yield is 90.7%. Upon removal of the excitation with a 365nm UV lamp, a color-changing afterglow of orange to yellow to green was observed (τ =582 ms). And dissolving the prepared carbon-based composite material to prepare ink, printing an anti-counterfeiting icon by using a printer, and observing the anti-counterfeiting color-changing afterglow by using a 365nm ultraviolet lamp.
Fig. 12 is a transmission electron micrograph of the carbon-based composite of example 2 showing that the carbon quantum dots are uniformly embedded in the isophthalic acid matrix. FIG. 6 is a photograph of a color-changing afterglow of the carbon-based composite of example 2 after turning off the 365nm UV light for 7s, which is seen to undergo a phosphorescence transition at room temperature (τ =582 ms) from orange to yellow to green. FIG. 13 is a graph of the room temperature phosphorescent emission of the carbon-based composite of example 2 and a Gaussian fit showing two phosphorescent emission centers, corresponding to the phosphorescent emission of the carbon quantum dot at 574nm and the phosphorescent emission of isophthalic acid at 525 nm. FIG. 14 is a graph of the phosphorescence emission at room temperature of the carbon-based composite of example 2 at 0.1,1,10,50,100,500ms time delay, respectively, and it is clearly observed that the phosphorescence emission at room temperature is blue-shifted from around 570nm to around 530nm over time, which is consistent with the CIE graph (FIG. 15) and the afterglow color change observed with the naked eye. Fig. 16 is a graph of the phosphorescence lifetimes at room temperature of a carbon quantum dot and an isophthalic acid matrix bi-optic center, respectively, showing that the decay lifetimes of the carbon quantum dot (τ =395 ms) at the orange luminescence center and the isophthalic acid (τ =686 ms) at the green luminescence center are different, resulting in a color-changing afterglow. The resulting security icon is shown in fig. 11, where the "pigeon" pattern turns from orange to yellow and finally to green with continuous illumination.
Example 3
0.2522g of melamine and 0.4802g of cystine are weighed and added into 15mL of water, stirred for 10min, the mixed solution is transferred into a 25mL reaction kettle, sealed and put into an oven to react for 4h at the temperature of 180 ℃. Naturally cooling to room temperature after reaction, centrifuging at a high speed of 10000r/min, refrigerating the obtained clear liquid in a refrigerator at 4 ℃ for 12h, centrifuging at a high speed of 10000r/min, dialyzing by a dialysis bag (3500D), and freeze-drying at-55 ℃, wherein the obtained powder is the yellow fluorescent light-emitting carbon quantum dot. And then 0.0450g of the carbon quantum dots are weighed and dispersed in 30mL of water, 0.4500g of phthalic acid is added, the temperature is increased to 120 ℃, reflux is carried out for 2h, self-assembly is carried out, the temperature is naturally reduced after reaction, needle-shaped crystals are separated out, and the target carbon-based compound is obtained after washing, filtering and vacuum drying at 50 ℃, and the yield is 89.8%. Upon removal of the excitation with a 365nm UV lamp as in FIG. 6, a color-changing afterglow of orange to yellow-green color (τ =212 ms) was observed. And dissolving the prepared carbon-based composite material to prepare ink, printing an anti-counterfeiting icon by using a printer, filling the ink in the icon printed by the printer to prepare the anti-counterfeiting icon, and observing the anti-counterfeiting color-changing afterglow by using a 365nm ultraviolet lamp.
Example 4
0.2522g of melamine and 0.6720g of selenocysteine are weighed and added into 15mL of water, stirred for 10min, the mixed solution is transferred into a 25mL reaction kettle, sealed and put into an oven to react for 4h at the temperature of 180 ℃. Naturally cooling to room temperature after reaction, centrifuging at a high speed of 12000r/min, refrigerating the obtained clear liquid in a refrigerator at the temperature of 4 ℃ for 12h, centrifuging at a high speed of 12000r/min, dialyzing by a dialysis bag (3500D), and freeze-drying at the temperature of-55 ℃ to obtain the powder, namely the yellow fluorescent light-emitting carbon quantum dots. And then 0.0450g of the carbon quantum dots are weighed and dispersed in 30mL of water, 0.4500g of isophthalic acid is added, the temperature is increased to 130 ℃, reflux is carried out for 2h, self-assembly is carried out, the temperature is naturally reduced after reaction, needle-shaped crystals are separated out, and the target carbon-based compound is obtained after washing, filtering and vacuum drying at 50 ℃, and the yield is 88.1%. Upon removal of the excitation with a 365nm UV lamp, a color-changing afterglow of orange to yellow to green was observed (τ =511 ms). And dissolving the prepared carbon-based composite material to prepare ink, printing an anti-counterfeiting icon by using a printer, filling the ink in the icon printed by the printer, and observing the anti-counterfeiting color-changing afterglow by using a 365nm ultraviolet lamp.
FIG. 17 is a 3D fluorescence emission diagram of the carbon quantum dots of example 4, with the optimal emission wavelength being 551nm, located in the yellow fluorescence region. Fig. 18 is a transmission electron micrograph of the carbon-based composite of example 4 showing that the carbon quantum dots are uniformly embedded in the isophthalic acid matrix. FIG. 6 is a photograph of a color-changing afterglow luminance in 7s after the 365nm UV lamp is turned off of the carbon-based composite of example 4, which is seen to undergo a phosphorescent transition at room temperature from orange to yellow to green. The resulting security icon is shown in fig. 11, where the "pigeon" pattern turns from orange to yellow and finally to green with continuous illumination.
The invention provides a preparation idea and a preparation method of a room temperature phosphorescent carbon-based composite material capable of changing color under a single excitation source. While there have been shown and described what are at present considered to be the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (6)
1. A preparation method of room temperature phosphorescent carbon-based composite material with color changing under a single excitation source is characterized by comprising the following steps:
(1) Evenly stirring melamine and amino acid containing sulfur or selenium in a solvent to obtain a solution;
(2) Transferring the solution obtained in the step (1) into a reaction kettle, sealing, then naturally cooling to room temperature after high-temperature reaction in an oven, centrifuging at high speed, refrigerating the obtained clear liquid, centrifuging at high speed, dialyzing, and freeze-drying to obtain powder, namely the yellow fluorescent emission carbon quantum dots;
(3) Dissolving the carbon quantum dots obtained in the step (2) in a solvent, adding an aromatic compound with crystallization-induced room temperature phosphorescence performance, carrying out heating reflux self-assembly and natural cooling cocrystallization precipitation, then filtering, washing with the solvent, and drying in vacuum to obtain crystals, namely the room temperature phosphorescent carbon-based composite material; the amino acid containing sulfur or selenium is cystine; the aromatic compound in the step (3) is any one of isophthalic acid, phthalic acid, terephthalic acid and melamine; the solvent in the step (1) and the step (3) is water; in the step (3), the reflux temperature is 80 to 130 ℃, and the self-assembly time under reflux is 0.5 to 2 hours.
2. The preparation method according to claim 1, wherein in the step (2), the reaction is carried out in an oven at 160 to 200 ℃ for 4 to 6 hours.
3. The preparation method according to claim 1, wherein in the step (1), the molar ratio of the melamine to the sulfur-containing or selenium-containing amino acid is 1.
4. The preparation method according to claim 1, wherein in the step (3), the mass ratio of the carbon quantum dots to the aromatic compound is 1 to 5 to 1.
5. Use of the room temperature phosphorescent carbon-based composite material prepared by the preparation method of any one of claims 1 to 4 in the preparation of anti-counterfeiting icons.
6. The application of the room temperature phosphorescent carbon-based composite material as claimed in claim 5, wherein the room temperature phosphorescent carbon-based composite material prepared by the preparation method as claimed in any one of claims 1 to 4 is dissolved to be used as anti-counterfeiting ink, and the anti-counterfeiting ink is filled in a mark printed by a printer to obtain a color-changing afterglow anti-counterfeiting picture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110320107.4A CN113025325B (en) | 2021-03-25 | 2021-03-25 | Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110320107.4A CN113025325B (en) | 2021-03-25 | 2021-03-25 | Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113025325A CN113025325A (en) | 2021-06-25 |
| CN113025325B true CN113025325B (en) | 2022-11-01 |
Family
ID=76473843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110320107.4A Active CN113025325B (en) | 2021-03-25 | 2021-03-25 | Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113025325B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113913186B (en) * | 2021-08-23 | 2022-11-22 | 华南农业大学 | Carbon dot-based room-temperature phosphorescent composite material capable of stably emitting afterglow and preparation method, application and use method thereof |
| CN113943570B (en) * | 2021-10-26 | 2023-11-10 | 江苏大学 | Carbon nano dot/boric acid composite phosphorescent material and preparation method and application thereof |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199724A (en) * | 2015-10-10 | 2015-12-30 | 北京化工大学 | Carbon quantum dots with room-temperature phosphorescence and delayed fluorescence properties, and synthesis and application thereof |
| CN105237551A (en) * | 2015-10-09 | 2016-01-13 | 北京师范大学 | Zinc-based metal organic framework materials having room temperature phosphorescence characteristic and preparation method thereof |
| CN106497560A (en) * | 2016-08-29 | 2017-03-15 | 北京化工大学 | Controllable carbon point based compound nano material of luminescent properties and preparation method and application |
| CN108130078A (en) * | 2018-01-15 | 2018-06-08 | 清华大学 | A kind of organic room temperature phosphorimetry material and preparation method and application under water of long-life |
| CN109385273A (en) * | 2017-08-09 | 2019-02-26 | 中国科学院宁波材料技术与工程研究所 | Extra long life room temperature phosphorimetry material, preparation method and application |
| CN109652058A (en) * | 2019-01-11 | 2019-04-19 | 南京大学 | A kind of preparation method of carbon quantum dot and its phosphorescence composite material |
| CN111154480A (en) * | 2018-11-06 | 2020-05-15 | 华南农业大学 | Long-afterglow material and preparation method and application thereof |
| CN111253933A (en) * | 2020-03-27 | 2020-06-09 | 中山大学 | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof |
| CN111518553A (en) * | 2019-12-24 | 2020-08-11 | 江南大学 | Preparation method and application of water-phase room-temperature phosphorescent carbon dot material |
| CN111607394A (en) * | 2020-06-17 | 2020-09-01 | 太原理工大学 | Room temperature phosphorescent carbon dot compound and preparation method thereof |
| CN112442244A (en) * | 2019-08-27 | 2021-03-05 | 天津大学 | Room-temperature phosphorescent quantum dot material and preparation method and application thereof |
| CN112500740A (en) * | 2020-10-30 | 2021-03-16 | 江苏大学 | Time-response color-changing phosphorescent carbon dot ink and preparation method and application thereof |
| CN112521931A (en) * | 2020-12-15 | 2021-03-19 | 四川大学 | Room temperature phosphorescence test strip based on carbon dots and preparation method and application thereof |
-
2021
- 2021-03-25 CN CN202110320107.4A patent/CN113025325B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237551A (en) * | 2015-10-09 | 2016-01-13 | 北京师范大学 | Zinc-based metal organic framework materials having room temperature phosphorescence characteristic and preparation method thereof |
| CN105199724A (en) * | 2015-10-10 | 2015-12-30 | 北京化工大学 | Carbon quantum dots with room-temperature phosphorescence and delayed fluorescence properties, and synthesis and application thereof |
| CN106497560A (en) * | 2016-08-29 | 2017-03-15 | 北京化工大学 | Controllable carbon point based compound nano material of luminescent properties and preparation method and application |
| CN109385273A (en) * | 2017-08-09 | 2019-02-26 | 中国科学院宁波材料技术与工程研究所 | Extra long life room temperature phosphorimetry material, preparation method and application |
| CN108130078A (en) * | 2018-01-15 | 2018-06-08 | 清华大学 | A kind of organic room temperature phosphorimetry material and preparation method and application under water of long-life |
| CN111154480A (en) * | 2018-11-06 | 2020-05-15 | 华南农业大学 | Long-afterglow material and preparation method and application thereof |
| CN109652058A (en) * | 2019-01-11 | 2019-04-19 | 南京大学 | A kind of preparation method of carbon quantum dot and its phosphorescence composite material |
| CN112442244A (en) * | 2019-08-27 | 2021-03-05 | 天津大学 | Room-temperature phosphorescent quantum dot material and preparation method and application thereof |
| CN111518553A (en) * | 2019-12-24 | 2020-08-11 | 江南大学 | Preparation method and application of water-phase room-temperature phosphorescent carbon dot material |
| CN111253933A (en) * | 2020-03-27 | 2020-06-09 | 中山大学 | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof |
| CN111607394A (en) * | 2020-06-17 | 2020-09-01 | 太原理工大学 | Room temperature phosphorescent carbon dot compound and preparation method thereof |
| CN112500740A (en) * | 2020-10-30 | 2021-03-16 | 江苏大学 | Time-response color-changing phosphorescent carbon dot ink and preparation method and application thereof |
| CN112521931A (en) * | 2020-12-15 | 2021-03-19 | 四川大学 | Room temperature phosphorescence test strip based on carbon dots and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Induction of long-lived room temperature phosphorescence of carbon dots by water in hydrogen-bonded matrices;Qijun Li et al.;《NATURE COMMUNICATIONS》;20180221;第9卷;第734（1-8）页 * |
| Strategy for Activating Room-Temperature Phosphorescence of Carbon Dots in Aqueous Environments;Yifang Gao et al.;《Chem. Mater.》;20190911;第31卷;第7979-7986页 * |
| 一种具有室温磷光的碳量子点基复合材料;刘武 等;《功能材料》;20181231;第49卷(第08期);第8001-8008页 * |
| 碳量子点及其复合材料的制备与光学性能研究;谈静;《中国博士学位论文全文数据库工程科技I辑》;20180215(第02期);第B015-15页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113025325A (en) | 2021-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Mn-Doped CsPbCl 3 perovskite nanocrystals: solvothermal synthesis, dual-color luminescence and improved stability | |
| CN113025325B (en) | Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source | |
| JP3763719B2 (en) | Phosphors based on oxynitride glass | |
| CN108865116B (en) | Film with room temperature phosphorescence and preparation method thereof | |
| CN101855492A (en) | Lighting system | |
| CN101092563A (en) | Phosphor powder in use for light emitting diode (LED), and preparation method | |
| Jia et al. | Recent advances in synthesis and applications of room temperature phosphorescence carbon dots | |
| CN106544021B (en) | The borate fluorescent powder and preparation method thereof that a kind of cerium, terbium are co-doped with | |
| Yin et al. | The thermal stability performances of the color rendering index of white light emitting diodes with the red quantum dots encapsulation | |
| WO2010024480A1 (en) | Red phosphor and forming method thereof for use in solid state lighting | |
| US20070090327A1 (en) | Novel red fluorescent powder | |
| Wang et al. | Research advances on human-eye-sensitive long persistent luminescence materials | |
| Liu et al. | Brightly luminescent and color-tunable green-violet-emitting halide perovskite CH 3 NH 3 PbBr 3 colloidal quantum dots: an alternative to lighting and display technology | |
| Xie et al. | Tunable photoluminescence and energy transfer of novel phosphor Sr 9 La 2 W 4 O 24: Sm 3+, Eu 3+ for near-UV white LEDs | |
| Xue et al. | Ce3+/Tb3+‐coactived NaMgBO3 phosphors toward versatile applications in white LED, FED, and optical anti‐counterfeiting | |
| CN114410304A (en) | Novel rare earth-based lead-free perovskite nanocrystalline material and preparation method and application thereof | |
| TWI266563B (en) | Compound, phosphor composition and light-emitting device containing the same | |
| Chang et al. | Correlating doping with the stability and color rendition of red phosphors | |
| CN114574206B (en) | Fluorescent powder for white light-emitting diode and synthesis method and application thereof | |
| CN111944522B (en) | Preparation method and application of single-component carbon-based solid white luminescent nano material | |
| CN114045165A (en) | Method for realizing multi-color variable pattern by long afterglow/quantum dot composite luminescent material | |
| Liu et al. | Thermal stable cyan-emitting Ba9 (Lu1. 5Ga0. 5) Si6O24: Ce3+ for high color-rendering white LEDs | |
| CN101210181A (en) | Fluorescent material, white light luminescent device and false proof coating | |
| CN106978174A (en) | A kind of tungsten boric acid lanthanum fluorescent material of doping and preparation method and application | |
| CN106634972A (en) | Single-phase phosphor for white LED and preparation method of single-phase phosphor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |