CN114479833B - Carbon dot room temperature phosphorescent material and preparation method and application thereof - Google Patents
Carbon dot room temperature phosphorescent material and preparation method and application thereof Download PDFInfo
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- CN114479833B CN114479833B CN202210124364.5A CN202210124364A CN114479833B CN 114479833 B CN114479833 B CN 114479833B CN 202210124364 A CN202210124364 A CN 202210124364A CN 114479833 B CN114479833 B CN 114479833B
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004202 carbamide Substances 0.000 claims abstract description 44
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 235000011399 aloe vera Nutrition 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 50
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 235000002961 Aloe barbadensis Nutrition 0.000 claims description 5
- 244000186892 Aloe vera Species 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 241001116389 Aloe Species 0.000 abstract description 3
- 150000001721 carbon Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 29
- 239000004327 boric acid Substances 0.000 description 28
- 239000000976 ink Substances 0.000 description 19
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
-
- 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
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- 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
Abstract
The invention discloses a carbon dot room temperature phosphorescent material, a preparation method and application thereof, wherein citric acid and urea are used as starting materials, nitrogen doped carbon dots (NCD) are prepared by a microwave method, and the NCD is combined with a solid matrix to prepare the room temperature phosphorescent material. The synthesis method is simple and convenient, is easy to synthesize and is suitable for mass production and application, and the phosphorescence life of the prepared three room temperature phosphorescence materials is 300 milliseconds to 1.5 seconds. The series of carbon dot room temperature phosphorescent materials have long-life room temperature phosphorescent properties, and the series of materials are applied to multicolor and time-resolved anti-counterfeiting materials. The anti-counterfeiting ink is obtained by uniformly mixing the anti-counterfeiting ink with aloe gel, multicolor and time-related multiple anti-counterfeiting can be effectively realized, the anti-counterfeiting grade is improved, and the anti-counterfeiting ink is difficult to forge.
Description
Technical Field
The invention belongs to the technical field of material synthesis, relates to a carbon point room temperature phosphorescent material, a preparation method and application thereof, and in particular relates to a preparation method and application of a series of carbon point room temperature phosphorescent materials with multicolor and time-resolved multiple anti-counterfeiting functions.
Background
Counterfeiting exists widely throughout the world, and while governments and enterprises have made efforts to prevent counterfeiting by issuing laws, a large number of counterfeit products in the food, medicine, clothing and electronics fields are still spread in our daily lives, severely affecting property safety, social stability and even threatening human health. To prevent counterfeit counterfeiting, various anti-counterfeiting strategies have been explored, including watermarks, holograms, luminescence, bar codes, and two-dimensional codes.
However, conventional anti-counterfeiting strategies are easily duplicated, and it is difficult to effectively prevent counterfeit counterfeiting. At present, the technology based on optical anti-counterfeiting is mostly in a single mode, and can only be used for simply anti-counterfeiting through different patterns displayed under sunlight and ultraviolet lamps, so that the technology is easy to forge and forge, and high-grade anti-counterfeiting is difficult to realize.
However, room temperature phosphorescence anti-counterfeiting technology has been reported, such as room temperature phosphorescence materials based on small organic molecules reported in the Nature Photonics journal in 2019, but the synthesis of the method is difficult, and the large-scale production and use are difficult.
Disclosure of Invention
The purpose is as follows: in order to overcome the defects in the prior art, the invention provides the room temperature phosphorescent material with the carbon dots and the preparation method of the room temperature phosphorescent material with the multicolor and time-resolved multiple anti-counterfeiting functions based on the carbon dots.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the preferable technical scheme that:
in a first aspect, a method for preparing a carbon dot room temperature phosphorescent material is provided, including:
step (1), mixing citric acid and urea in deionized water, reacting for 2-10 minutes under 600-750W microwaves, cooling, filtering, dialyzing, and freeze-drying to obtain nitrogen-doped carbon point NCD;
uniformly mixing the nitrogen-doped carbon point NCD prepared in the step (1) with a solid matrix source and water to obtain a mixed solution of the NCD and the solid matrix source; and (3) reacting or calcining the mixed solution of the NCD and the solid matrix source at a set temperature to obtain the NCD/solid matrix composite material, namely the carbon point room temperature phosphorescent material, wherein the solid matrix is one or more of urea, boric acid or silicon dioxide.
In some embodiments, the carbon dot room temperature phosphorescent material is an NCD/urea composite, an NCD/boric acid composite, or an NCD/silica composite.
The preparation method of the NCD/urea composite material comprises the following steps:
adding the nitrogen doped carbon point NCD into deionized water, uniformly mixing and stirring with urea for 5-30 minutes to obtain NCD/urea mixed solution, reacting the mixed solution at 120-180 ℃ for 4-10 hours, and cooling to obtain the NCD/urea composite material.
Further, the mass ratio of NCD to urea is 1 (300-500), and the mass volume ratio of NCD to deionized water is 1 mg: 2-4 ml.
The preparation method of the NCD/boric acid composite material comprises the following steps: adding the nitrogen-doped carbon point NCD into deionized water, uniformly mixing and stirring with boric acid for 5-30 minutes to obtain NCD/boric acid mixed solution, reacting the mixed solution at 120-200 ℃ for 4-10 hours, and cooling to obtain the NCD/boric acid composite material.
Further, the mass ratio of NCD to boric acid is 1:100-300, and the mass volume ratio of NCD to deionized water is 1 mg: 15-25 ml.
The preparation method of the NCD/silicon dioxide composite material comprises the following steps:
Tetraethyl orthosilicate, ethanol, water and hydrochloric acid with pH=2 react for 110-150 minutes at 75-100 ℃ to obtain a mixed solution;
Adding the nitrogen-doped carbon point NCD into the mixed solution, stirring at room temperature until uniform gel is formed, and drying to obtain gel powder; calcining the dried gel powder at 400-650 ℃ for 1-3 hours to obtain the NCD/silicon dioxide composite material.
Further, the molar ratio of tetraethyl orthosilicate, ethanol, water and hydrochloric acid is 1 (3-5): 4-6): 0.1-0.3; the mass volume ratio of NCD to the mixed solution is 1 mg: 10-15 ml.
In a second aspect, a carbon point room temperature phosphorescent material is provided, wherein the carbon point room temperature phosphorescent material is at least one of an NCD/urea composite material, an NCD/boric acid composite material or an NCD/silicon dioxide composite material; the preparation method is used for preparing the composite material.
In a third aspect, the application of the carbon point room temperature phosphorescent material in multicolor and time-resolved multiple anti-counterfeiting is provided.
The application comprises: and uniformly mixing the carbon point room temperature phosphorescent material with aloe vera gel to prepare the anti-counterfeiting ink.
Further, the anti-counterfeiting ink is printed with an anti-counterfeiting pattern through screen printing.
In some embodiments, the mass ratio of carbon point room temperature phosphorescent material to aloe vera gel is preferably 1: (3-5).
The beneficial effects are that: according to the invention, citric acid and urea are used as starting materials, nitrogen doped carbon dots (NCD) are prepared by a microwave method, and three room temperature phosphorescent materials are prepared by combining NCD with a solid matrix. The series of carbon dot room temperature phosphorescent materials have long-life room temperature phosphorescent properties, and the series of materials are applied to multicolor and time-resolved anti-counterfeiting materials. The synthesis method is simple and convenient, is easy to synthesize and is suitable for mass production and application, and the phosphorescence life of the prepared three room temperature phosphorescence materials is 300 milliseconds to 1.5 seconds. The anti-counterfeiting ink is obtained by uniformly mixing the anti-counterfeiting ink with aloe gel, multicolor and time-related multiple anti-counterfeiting can be effectively realized, the anti-counterfeiting grade is improved, and the anti-counterfeiting ink is difficult to forge. The preparation method provided by the invention is energy-saving, environment-friendly, non-toxic, free from the influence of water and oxygen in the air and excellent in stability.
Drawings
FIG. 1 is a high resolution transmission electron microscope of NCD carbon dots prepared in example 1;
FIG. 2 is an x-ray photoelectron spectroscopy (XPS) analysis of NCD carbon dots prepared in example 1;
FIG. 3 is an XPS analysis chart of the NCD/urea composite material prepared in example 2;
FIG. 4 is fluorescence and phosphorescence emission spectra of the NCD/urea composite prepared in example 2;
FIG. 5 is an attenuation curve of the NCD/urea composite prepared in example 2;
FIG. 6 is an XPS analysis chart of the NCD/boric acid composite material prepared in example 3;
FIG. 7 is fluorescence and phosphorescence emission spectra of the NCD/boric acid composite material prepared in example 3;
FIG. 8 is an attenuation curve of the NCD/boric acid composite material prepared in example 3;
FIG. 9 is an XPS analysis chart of the NCD/silica composite material prepared in example 4;
FIG. 10 is fluorescence and phosphorescence emission spectra of the NCD/silica composite prepared in example 4;
FIG. 11 is an attenuation curve for the NCD/silica composite prepared in example 4;
FIGS. 12 and 13 are graphs showing the effects of patterns printed by screen printing using a fluorescent dye and NCD/silica composite as inks before and after the ultraviolet lamp is turned off at 254 nm;
FIGS. 14 and 15 are graphs showing the effect of patterns printed by screen printing using NCD/urea composite material as ink before and after the ultraviolet lamp is turned off at 254 nm; FIG. 16 is a pattern shown in FIG. 14 after 365 nm UV lamps are turned off 365 nm UV lamps;
FIGS. 17 and 18 are graphs showing the effects of patterns printed by screen printing using an NCD/urea composite material and an NCD/boric acid composite material as inks before and after the ultraviolet lamp is turned off at 254 nm; FIG. 19 is a pattern shown in FIG. 18 after the ultraviolet lamp is turned off for 1 second; fig. 20 shows the pattern of fig. 18 after the uv lamp is turned off for 2 seconds.
Detailed Description
The invention will be further described with reference to the drawings and examples.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
For the purposes of this specification and the appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, as used in the specification and the appended claims, are to be understood as being modified in all instances by the term "about". Furthermore, all ranges disclosed herein are inclusive of the endpoints and independently combinable.
Example 1
(1) The preparation method of the carbon dots comprises the following steps:
3 g of citric acid and 6g of urea are uniformly mixed in 20ml of deionized water, reacted for 5 minutes under 650W microwaves, cooled to room temperature, filtered by filter paper, the obtained liquid is centrifuged three times by a centrifugal machine 8000 revolutions to remove larger particles, the obtained liquid is dialyzed for 2 days by a dialysis bag with 3500 molecular weight cut-off, and the obtained liquid is subjected to freeze drying to obtain nitrogen-doped carbon dot (NCD) powder.
(2) Characterization of NCD:
High resolution transmission electron microscopy as in figure 1, the ncd carbon dots have good uniformity and quasi-spherical morphology, an average diameter of about 2.8 nm, and are seen as lattice fringes. To further understand the composition of the NCD, x-ray photoelectron spectroscopy (XPS) analysis was performed. XPS results (FIG. 2) show that NCD consists essentially of carbon, nitrogen, and oxygen.
Example 2
(1) The preparation method of the NCD/urea composite material comprises the following steps:
The synthesized NCD (20 mg) is added into 60 milliliters of deionized water, evenly mixed with 8 grams of urea and stirred for 20 minutes to obtain a NCD/urea mixed solution, the mixed solution is placed into an oven to react for 6 hours at 160 ℃, and the mixed solution is cooled to room temperature to obtain the NCD/urea composite material.
(2) Characterization of NCD/Urea composite:
To further understand the composition of the NCD/urea composite, x-ray photoelectron spectroscopy (XPS) analysis was performed. XPS results (FIG. 3) show that the NCD/urea composite is composed mainly of carbon, nitrogen, oxygen.
(3) Photoluminescent properties of NCD/urea composites:
excitation is carried out by 373 nm wavelength under the room temperature condition, and fluorescence and phosphorescence emission spectra of the NCD/urea composite material are respectively obtained. The results are shown in FIG. 4. As can be seen from fig. 4, the NCD/urea composite material fluorescence emission peak is at 436 nm and the phosphorescence emission peak is at 501 nm.
Excitation at 373 nm wavelength at room temperature gave an attenuation curve (fig. 5) of the NCD/urea composite, calculated to have an average lifetime of 332.26 ms.
Example 3
(1) The preparation method of the NCD/boric acid composite material comprises the following steps:
The synthesized NCD (10 mg) is added into 160 milliliters of deionized water, evenly mixed with 2 grams of boric acid and stirred for 20 minutes to obtain NCD/boric acid mixed solution, the mixed solution is placed into an oven to react for 5 hours at 180 ℃, and the NCD/boric acid composite material is obtained after cooling to room temperature.
(2) Characterization of NCD/boric acid composite materials
To further understand the composition of the NCD/boric acid composite, x-ray photoelectron spectroscopy (XPS) analysis was performed. XPS results (FIG. 6) show that NCD/boric acid consists essentially of carbon, nitrogen, oxygen, boron.
(3) Photoluminescent properties of NCD/boric acid composite:
Excitation is carried out under the room temperature condition and the wavelength of 273 nm, so that fluorescence and phosphorescence emission spectra of the NCD/boric acid composite material are respectively obtained. The results are shown in FIG. 7. As can be seen from fig. 7, the NCD/boric acid composite material has a fluorescence emission peak at 408 nm and a phosphorescence emission peak at 453 nm.
Excitation at room temperature at 273 nm wavelength gave an attenuation curve for the NCD/boric acid composite (fig. 8), calculated to have an average lifetime of 652.05 ms.
Example 4
(1) The preparation method of the NCD/silicon dioxide composite material comprises the following steps:
Tetraethyl orthosilicate, ethanol, water and hydrochloric acid (ph=2) were uniformly mixed in a molar ratio of 1:4:5:0.2 and reacted at 80 ℃ for 120 minutes. The synthesized NCD (10 mg) was added to 100 ml of the mixed solution and stirred at room temperature until a homogeneous gel formed. The dried gel powder was calcined at 600 ℃ for 90 minutes to obtain the final NCD/silica composite.
(2) Characterization of NCD/silica composite:
To further understand the composition of the NCD/silica composite, x-ray photoelectron spectroscopy (XPS) analysis was performed. XPS results (FIG. 9) show that NCD/silica composites consist essentially of carbon, nitrogen, oxygen, silicon.
(3) Photoluminescent properties of NCD/silica composites:
Excitation is carried out at the wavelength of 290 nm under the room temperature condition, and fluorescence and phosphorescence emission spectra of the NCD/silicon dioxide composite material are respectively obtained. The results are shown in FIG. 10. As can be seen from fig. 10, the NCD/silica composite material has a fluorescence emission peak at 400 nm and a phosphorescence emission peak at 474 nm.
Excitation at room temperature at 290 nm wavelength gave an attenuation curve for the NCD/silica composite (fig. 11), calculated to have an average lifetime of 1587.22 ms.
Example 5
The preparation method of the anti-counterfeiting ink comprises the following steps:
Respectively mixing the NCD/urea composite material, the NCD/boric acid composite material, the NCD/silicon dioxide composite material and aloe vera gel according to the mass ratio of 1 g: 3 g of the anti-counterfeiting ink is prepared by uniformly mixing.
Example 6
The numbers "2" and "3" were printed by screen printing, wherein the ink of "2" was a fluorescent dye and the ink of "3" was NCD/silica composite, as shown in fig. 12. Fig. 13 is a photograph of the pattern exhibited by the 254 nm uv lamp of fig. 12 after shut down, the number "3" being visible after shut down of the uv lamp due to the room temperature phosphorescent properties of the NCD/silica composite.
Example 7
The NCD/urea composite was screen printed as an ink in a pattern of strands as shown in fig. 14. FIG. 15 is a pattern that appears after the UV lamp of 254 nm of FIG. 14 has been turned off, and the pattern of flowers can still be seen after the UV lamp has been turned off because the NCD/urea composite has room temperature phosphorescent properties; fig. 16 shows a pattern of fig. 14 after the 365, 365 nm ultraviolet lamp is turned off after the 365, 365 nm ultraviolet lamp is irradiated, and compared with a pattern of fig. 254, 254 nm ultraviolet lamp being turned off, the color of the pattern is changed from blue to green, so that multicolor anti-counterfeiting can be realized.
Example 8
Two numbers "8" obtained by screen printing NCD/urea composite and NCD/boric acid composite as inks, wherein the ink of the first "8" from the left is carbon dot/urea, and the ink of the second "8" is NCD/boric acid, as shown in fig. 17; FIG. 18 is a photograph of the pattern presented by FIG. 17 after the ultraviolet lamp 254 nm was turned off, and two numbers "8" were still visible after the ultraviolet lamp was turned off because the NCD/urea composite and the NCD/boric acid composite both had room temperature phosphorescent properties; FIG. 19 is a pattern exhibited by the UV lamp of FIG. 18 after being turned off for 1 second, the first digit "8" being progressively dimmed due to the differing phosphorescent lifetimes of NCD/urea and NCD/boric acid; FIG. 20 shows the pattern of FIG. 18 after the UV lamp is turned off for 2 seconds, and the first number "8" is lost and only the second number "8" is visible due to the different phosphorescent lifetimes of the NCD/urea and NCD/boric acid composites, thus achieving time dependent multiple anti-counterfeiting.
The embodiment shows that the three composite materials prepared by the embodiment of the invention have long-life room-temperature phosphorescence property, and the series of materials can be applied to multicolor and time-resolved anti-counterfeiting materials. The synthesis method is simple and convenient, is easy to synthesize and is suitable for mass production and application, and the phosphorescence life of the prepared three room temperature phosphorescence materials is 300 milliseconds to 1.5 seconds. The anti-counterfeiting ink is obtained by uniformly mixing the anti-counterfeiting ink with aloe gel, multicolor and time-related multiple anti-counterfeiting can be effectively realized, the anti-counterfeiting grade is improved, and the anti-counterfeiting ink is difficult to forge. The preparation method provided by the invention is energy-saving, environment-friendly, non-toxic, free from the influence of water and oxygen in the air and excellent in stability.
Claims (8)
1. The preparation method of the carbon dot room temperature phosphorescent material is characterized by comprising the following steps of:
step (1), mixing citric acid and urea in deionized water, reacting for 2-10 minutes under 600-750W microwaves, cooling, filtering, dialyzing, and freeze-drying to obtain nitrogen-doped carbon point NCD;
Uniformly mixing the nitrogen-doped carbon point NCD prepared in the step (1) with a solid matrix source and water to obtain a mixed solution of the NCD and the solid matrix source; reacting or calcining the mixed solution of NCD and a solid matrix source at a set temperature to obtain an NCD/solid matrix composite material, namely a carbon point room temperature phosphorescent material, wherein the solid matrix is urea or silicon dioxide; the carbon point room temperature phosphorescent material is an NCD/urea composite material or an NCD/silicon dioxide composite material;
The preparation method of the NCD/urea composite material comprises the following steps: adding the nitrogen-doped carbon point NCD into deionized water, uniformly mixing and stirring with urea for 5-30 minutes to obtain NCD/urea mixed solution, reacting the mixed solution at 120-180 ℃ for 4-10 hours, and cooling to obtain NCD/urea composite material;
the preparation method of the NCD/silicon dioxide composite material comprises the following steps: tetraethyl orthosilicate, ethanol, water and hydrochloric acid with pH=2 react for 110-150 minutes at 75-100 ℃ to obtain a mixed solution; adding the nitrogen-doped carbon point NCD into the mixed solution, stirring at room temperature until uniform gel is formed, and drying to obtain gel powder; calcining the dried gel powder at 400-650 ℃ for 1-3 hours to obtain the NCD/silicon dioxide composite material.
2. The preparation method according to claim 1, wherein the mass ratio of NCD to urea is 1 (300-500), and the mass volume ratio of NCD to deionized water is 1 mg: 2-4 ml.
3. The preparation method according to claim 1, wherein the molar ratio of tetraethyl orthosilicate, ethanol, water and hydrochloric acid is 1 (3-5): 4-6): 0.1-0.3.
4. The preparation method according to claim 1, wherein the mass-to-volume ratio of NCD to the mixed solution is 1 mg: 10-15 ml.
5. The carbon point room temperature phosphorescent material is characterized in that the carbon point room temperature phosphorescent material is an NCD/urea composite material or an NCD/silicon dioxide composite material; a process according to any one of claims 1 to 4.
6. The use of the carbon dot room temperature phosphorescent material according to claim 5 in multicolor and time-resolved multiple anti-counterfeiting.
7. The use according to claim 6, characterized in that it comprises: and uniformly mixing the carbon point room temperature phosphorescent material with aloe vera gel to prepare the anti-counterfeiting ink.
8. The use according to claim 7, wherein the mass ratio of carbon point room temperature phosphorescent material to aloe vera gel is 1: (3-5).
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