CN117126662A - Carbon quantum dot-based organic long afterglow composite material and preparation method thereof - Google Patents
Carbon quantum dot-based organic long afterglow composite material and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004202 carbamide Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 24
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 27
- 238000003723 Smelting Methods 0.000 abstract 1
- 230000005284 excitation Effects 0.000 description 47
- 239000007787 solid Substances 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000005838 radical anions Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 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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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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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- 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
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The application provides a carbon quantum dot-based organic long afterglow composite material and a preparation method thereof, belonging to the technical field of luminescent materials, wherein the preparation method of the carbon quantum dot-based organic long afterglow composite material comprises the following steps: mixing carbon source and urea in the mass ratio of 0.001-0.5 to 2, and smelting and reacting at 175-235 deg.c for 1-6 hr to obtain the organic long afterglow composite material. The preparation method can generate the carbon dot-based organic long afterglow composite material in one step, so that the preparation process is simplified, the prepared material can generate blue afterglow when excited by ultraviolet rays with the wavelength of 275-310 nm, and the afterglow time can reach 1.6h at most, which is far longer than the existing long afterglow luminescent material.
Description
Technical Field
The application belongs to the technical field of luminescent materials, and particularly relates to a carbon quantum dot-based organic long afterglow composite material and a preparation method thereof.
Background
A long afterglow luminescent (long persistent luminescence, LPL) material refers to a material that can undergo long-term afterglow emission after the excitation source is stopped. The LPL material, which is a so-called "noctilucent" material, is widely used in various fields such as bioimaging, anti-counterfeiting, data encryption, light emitting diodes, etc., and is capable of storing excitation energy in an excited state and slowly releasing the energy in the form of light. In 1996, the green inorganic LPL material SrAl 2 O 4 :Eu 2+ ,Dy 3+ It was first discovered that since the development of inorganic LPL materials, the light emission time in the dark is changed from seconds, minutes to hours or even days, and the LPL intensity, efficiency and emission wavelength range are more widely studied. However, rare elements (such as europium and dysprosium) are required to be added in the preparation process of the material, and the synthesis conditions are harsh, which clearly increases the use cost of the inorganic LPL material. In order to solve the problem, organic LPL materials are developed, compared with the traditional inorganic LPL materials, the organic LPL materials do not need to be added with rare elements, the luminous color is adjustable, the processing and the synthesis are easy, and the popularization and application difficulty is reduced.
The method of achieving an ionised separation state by a binary donor-acceptor complex system is the most successful system to date for the generation of organic LPLs in which photoexcited electrons from the donor molecule are transferred from its Lowest Unoccupied Molecular Orbital (LUMO) to the LUMO of the acceptor molecule, and then the acceptor radical anions diffuse, separating the donor radical cations from the acceptor radical anions, forming a charge-separated state. Such binary donor-acceptor complex systems are not limited to pure organic systems, and organic donor-polymer acceptor systems, carbon-point donor-organic acceptor systems, are all currently being developed.
Carbon dots are quasi-spherical carbon nano materials with the size smaller than 10nm, and since the fact that the carbon dots are discovered accidentally through an arc discharge method in 2004, the carbon dots have been widely researched and interesting due to the advantages of excellent photophysical properties, low cost, convenient preparation, environmental friendliness and the like. On this basis, carbon spot afterglow materials having various properties have been developed in recent years.
However, current carbon dot-based organic LPL materials require the preparation of a carbon dot material separately and then embedding it in an organic electron acceptor material, which undoubtedly complicates the reproducibility and mass production of the carbon dot-based organic LPL material. If it were possible to directly produce carbon dot-based organic LPL materials in a one-step process, the overall production process would be greatly simplified.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The application aims to provide a carbon quantum dot-based organic long afterglow composite material and a preparation method thereof, wherein the preparation method can be used for generating a carbon dot-based organic LPL material in one step, and the problem that the existing preparation method of the carbon dot-based organic LPL material is complicated is solved.
In order to achieve the above object, the present application provides the following technical solutions:
the preparation method of the carbon quantum dot-based organic long afterglow composite material comprises the following steps: and mixing a carbon source with urea, and performing a melting reaction to obtain the carbon quantum dot-based organic long afterglow composite material.
Preferably, the carbon source comprises a compound represented by the following formula (I):
wherein R1, R2, R3, R4, R5, R6 are each independently selected from hydrogen, carboxyl or amino, and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 At least 2 of which are independently selected from carboxyl or amino groups.
Preferably, the carbon source and urea are mixed and sufficiently ground, and then the melting reaction is performed, and after the melting reaction is completed, the cooled product is ground again into powder.
Preferably, the carbon source includes at least one of isophthalic acid, trimesic acid, phthalic acid, terephthalic acid, 3-aminobenzoic acid, and m-phenylenediamine.
Preferably, the mass ratio of the carbon source to urea is (0.001-0.5): 2.
Preferably, the temperature of the melting reaction is 175-235 ℃ and the reaction time is 1-6 h.
Preferably, the carbon source is isophthalic acid.
Preferably, the mass ratio of the carbon source to urea is (0.006-0.1): 2.
Preferably, the temperature of the melting reaction is 195℃and the reaction time is 5 hours.
The application also provides a carbon quantum dot-based organic long afterglow composite material prepared by any one of the methods.
The beneficial effects are that:
(1) The carbon quantum dot-based organic long afterglow composite material is a solid afterglow-emitted carbon quantum dot-based organic long afterglow composite material, does not contain rare elements, and has a simple preparation process.
(2) The carbon quantum dot-based organic long afterglow composite material prepared by the preparation method provided by the application has strong LPL performance, and the blue afterglow luminescence time can reach an hour level under the ultraviolet wavelength of 275nm wavelength, which is far more than that of the existing carbon dot-based organic LPL material.
(3) The preparation of the carbon quantum dot-based organic long afterglow composite material is carried out under the melting condition, and the preparation method is simple in process, short in time and easy to popularize and apply.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Wherein:
FIG. 1 is an afterglow emission spectrum of CDs@CA-1 provided in example 1 at excitation of 275 nm.
FIG. 2 is a graph showing the long afterglow decay curve of CDs@CA-1 provided in example 1 after excitation of an ultraviolet lamp at an excitation wavelength of 275nm for 1 minute.
FIG. 3 is a graph showing the long afterglow decay curves of CDs@CA-1 provided in example 1 corresponding to different durations (5 s,10s,20s,30s,1min and 3 min) of ultraviolet lamp excitation at an excitation wavelength of 275 nm.
FIG. 4 is an afterglow emission spectrum of CDs@CA-2 at 275nm excitation as provided in example 2.
FIG. 5 is a graph showing the long afterglow decay curve of CDs@CA-2 provided in example 2 after excitation of an ultraviolet lamp at an excitation wavelength of 275nm for 1 minute.
FIG. 6 is an afterglow emission spectrum of CDs@CA-3 at 275nm excitation as provided in example 3.
FIG. 7 is a graph showing the long afterglow decay curve of CDs@CA-3 provided in example 3 at an excitation wavelength of 275nm for 1 minute.
FIG. 8 is an afterglow emission spectrum of CDs@CA-4 at 275nm excitation as provided in example 4.
FIG. 9 is a graph showing the long afterglow decay curve of CDs@CA-4 provided in example 4 at an excitation wavelength of 275nm for 1 minute.
FIG. 10 is an afterglow emission spectrum of CDs@CA-a at excitation of 310nm as provided in example 5.
FIG. 11 is a graph showing the long afterglow decay curve of CDs@CA-a provided in example 5 at an excitation wavelength of 310nm for 1 minute.
FIG. 12 is an afterglow emission spectrum of CDs@CA-b provided in example 6 at excitation of 275 nm.
FIG. 13 is a graph showing the long afterglow decay curve of CDs@CA-b provided in example 6 at an excitation wavelength of 275nm for 1 minute.
FIG. 14 is an afterglow emission spectrum of CDs@CA-c at 275nm excitation, as provided in example 7.
FIG. 15 is a graph showing the long afterglow decay curve of CDs@CA-c provided in example 7 at an excitation wavelength of 275nm for 1 minute.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the application, fall within the scope of protection of the application.
The present application will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Aiming at the problem that the existing preparation method of the carbon dot-based organic LPL material is complicated, the application provides the preparation method of the carbon quantum dot-based organic long-afterglow composite material, and the carbon quantum dot-based organic long-afterglow composite material with afterglow time reaching 1.6h is obtained by mixing a carbon source and urea and then carrying out a melting reaction.
In a preferred embodiment of the application, the carbon source comprises a compound of formula (I):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, carboxyl or amino, and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 At least 2 (e.g., 2, 3, 4, 5, 6) of which are independently selected from carboxyl or amino groups.
In a preferred embodiment of the present application, the carbon source and urea are mixed and sufficiently ground, and then a melting reaction is performed, and after the melting reaction is completed, the cooled product is ground again into powder.
In a preferred embodiment of the present application, the carbon source includes at least one of isophthalic acid, trimesic acid, phthalic acid, terephthalic acid, 3-aminobenzoic acid, and m-phenylenediamine.
In a preferred embodiment of the application, the mass ratio of carbon source to urea is (0.001-0.5): 2 (e.g. 0.002:2, 0.005:2, 0.01:2, 0.05:2, 0.1:2, 0.2:2, 0.49:2).
In a preferred embodiment of the present application, the temperature of the melting reaction is 175℃to 235℃such as 176℃180℃185, 190℃195℃200℃205℃210℃215℃220℃225℃230℃and the reaction time is 1h to 6h (e.g.1.5 h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, 4.5h, 5.0h, 5.5 h).
In a preferred embodiment of the application, the carbon source is isophthalic acid.
In a preferred embodiment of the application, the mass ratio of carbon source to urea is (0.006-0.1): 2 (e.g. 0.01:2, 0.02:2, 0.04:2, 0.06:2, 0.08:2, 0.09:2).
In a preferred embodiment of the application, the temperature of the melting reaction is 195℃and the reaction time is 5 hours.
The application also provides a carbon quantum dot-based organic long afterglow composite material, which is prepared by any one of the methods.
The carbon quantum dot-based organic long afterglow composite material and the preparation method thereof are described in detail by specific examples.
The sources of the individual raw materials in the following examples are as follows:
isophthalic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
urea: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
trimesic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
phthalic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
terephthalic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
3-aminobenzoic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
m-phenylenediamine: analytically pure, purchased from Shanghai Taitan technologies Co.
Example 1
The embodiment provides a carbon quantum dot-based organic long afterglow composite material, and the preparation method comprises the following steps:
(1) Adding 6mg of isophthalic acid into 2g of urea, fully grinding and uniformly mixing at normal temperature to obtain white powder which is a mixture of isophthalic acid and urea;
(2) Placing the white powder into a 20mL ceramic crucible, placing into a baking oven, and carrying out melt reaction for 5h at the temperature of 195 ℃;
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the ceramic crucible, grinding the solid into powder by using a mortar, and obtaining the carbon quantum dot-based organic long afterglow composite material, which is named as CDs@CA-1.
As shown in FIG. 1, at room temperature, CDs@CA-1 excitation wavelength of 275nm corresponds to a peak position of 438nm, and blue afterglow emission can be generated.
As shown in FIG. 2, CDs@CA-1 emits afterglow for 1.6 hours at room temperature after excitation of an ultraviolet lamp at an excitation wavelength of 275nm for 1 minute.
As shown in FIG. 3, after the ultraviolet lamp with the excitation wavelength of 275nm of CDs@CA-1 is excited for different durations at room temperature, the afterglow emission durations are different, but the afterglow emission durations are far longer than the excitation durations.
Example 2
The embodiment provides a carbon quantum dot-based organic long afterglow composite material, and the preparation method comprises the following steps:
(1) Adding 100mg of isophthalic acid into 2g of urea, fully grinding and uniformly mixing at normal temperature to obtain white powder which is a mixture of isophthalic acid and urea;
(2) Placing the white powder into a 20mL ceramic crucible, placing into a baking oven, and carrying out melt reaction for 5h at the temperature of 195 ℃;
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the ceramic crucible, grinding the solid into powder by using a mortar, and obtaining the carbon quantum dot-based organic long afterglow composite material, which is named as CDs@CA-2.
As shown in FIG. 4, when the excitation wavelength of CDs@CA-2 is 275nm at room temperature, the corresponding emission peak position is 443nm, and blue afterglow emission can be generated.
As shown in FIG. 5, CDs@CA-2 emits afterglow for up to 30min at room temperature after excitation of an ultraviolet lamp at an excitation wavelength of 275nm for 1min.
Example 3
The embodiment provides a carbon quantum dot-based organic long afterglow composite material, and the preparation method comprises the following steps:
(1) Adding 250mg of isophthalic acid into 2g of urea, fully grinding and uniformly mixing at normal temperature to obtain white powder which is a mixture of isophthalic acid and urea;
(2) Placing the white powder into a 20mL ceramic crucible, placing into a baking oven, and carrying out melt reaction for 5h at the temperature of 195 ℃;
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the ceramic crucible, grinding the solid into powder by using a mortar, and obtaining the carbon quantum dot-based organic long afterglow composite material, which is named as CDs@CA-3.
As shown in FIG. 6, when the excitation wavelength of CDs@CA-3 is 275nm at room temperature, the corresponding emission peak position is 445nm, and blue afterglow emission can be generated.
As shown in FIG. 7, CDs@CA-3 emits afterglow for up to 10min at room temperature after excitation of an ultraviolet lamp at an excitation wavelength of 275nm for 1min.
Example 4
The embodiment provides a carbon quantum dot-based organic long afterglow composite material, and the preparation method comprises the following steps:
(1) Adding 500mg of isophthalic acid into 2g of urea, fully grinding and uniformly mixing at normal temperature to obtain white powder which is a mixture of isophthalic acid and urea;
(2) Placing the white powder into a 20mL ceramic crucible, placing into a baking oven, and carrying out melt reaction for 5h at the temperature of 195 ℃;
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the ceramic crucible, grinding the solid into powder by using a mortar, and obtaining the carbon quantum dot-based organic long afterglow composite material, which is named as CDs@CA-4.
As shown in FIG. 8, when the excitation wavelength of CDs@CA-4 is 275nm at room temperature, the corresponding emission peak position is 451nm, and blue afterglow emission can be generated.
As shown in FIG. 9, CDs@CA-4 emits afterglow for 3min at room temperature after excitation of an ultraviolet lamp at an excitation wavelength of 275nm for 1min.
Example 5
The embodiment provides a carbon quantum dot-based organic long afterglow composite material, and the preparation method comprises the following steps:
(1) Adding 6mg of phthalic acid into 2g of urea, fully grinding and uniformly mixing at normal temperature to obtain white powder which is a mixture of phthalic acid and urea;
(2) Placing the white powder into a 20mL ceramic crucible, placing into a baking oven, and carrying out melt reaction for 5h at the temperature of 195 ℃;
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the ceramic crucible, grinding the solid into powder by using a mortar, and obtaining the carbon quantum dot-based organic long afterglow composite material, which is named as CDs@CA-a.
As shown in FIG. 10, when CDs@CA-a excitation wavelength is 310nm at room temperature, the corresponding emission peak position is 453nm, and blue afterglow emission can be generated.
As shown in FIG. 11, CDs@CA-a was excited at room temperature for up to 20min after excitation of an ultraviolet lamp having an excitation wavelength of 310nm for 1min.
Example 6
The embodiment provides a carbon quantum dot-based organic long afterglow composite material, and the preparation method comprises the following steps:
(1) Adding 6mg of terephthalic acid into 2g of urea, fully grinding and uniformly mixing at normal temperature to obtain white powder which is a mixture of terephthalic acid and urea;
(2) Placing the white powder into a 20mL ceramic crucible, placing into a baking oven, and carrying out melt reaction for 5h at the temperature of 195 ℃;
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the ceramic crucible, grinding the solid into powder by using a mortar, and obtaining the carbon quantum dot-based organic long afterglow composite material, which is named as CDs@CA-b.
As shown in FIG. 12, when the excitation wavelength of CDs@CA-b is 275nm at room temperature, the corresponding emission peak position is 450nm, and blue afterglow emission can be generated.
As shown in FIG. 13, CDs@CA-b was excited at room temperature for up to 25min after excitation by an ultraviolet lamp having an excitation wavelength of 275 nm.
Example 7
The embodiment provides a carbon quantum dot-based organic long afterglow composite material, and the preparation method comprises the following steps:
(1) Adding 6mg of 3-aminobenzoic acid into 2g of urea, and fully grinding and uniformly mixing at normal temperature to obtain white powder which is a mixture of 3-aminobenzoic acid and urea;
(2) Placing the white powder into a 20mL ceramic crucible, placing into a baking oven, and carrying out melt reaction for 5h at the temperature of 195 ℃;
(3) And after the preparation, cooling to room temperature, taking out the solid in the ceramic crucible, and grinding the solid into powder by using a mortar to obtain the carbon quantum dot-based organic long afterglow composite material, which is named as CDs@CA-c.
As shown in FIG. 14, when the excitation wavelength of CDs@CA-c is 275nm at room temperature, the corresponding emission peak position is 446nm, and blue afterglow emission can be generated.
As shown in FIG. 15, CDs@CA-c emits afterglow for 25min at room temperature after excitation of an ultraviolet lamp at an excitation wavelength of 275nm for 1min.
Examples 8 to 16
Different carbon sources are used for replacing carbon sources such as isophthalic acid, terephthalic acid and the like, the ratio of the carbon sources to urea, the reaction temperature and the reaction time are adjusted, the carbon quantum dot-based organic long afterglow composite material is prepared, an ultraviolet lamp is used for excitation for 1min, and the emission wavelength and the afterglow emission time are tested as follows:
comparative example 1
On the basis of the embodiment 1, the ratio of isophthalic acid to urea is adjusted to be 0:2, other conditions are unchanged, the carbon quantum dot-based organic long afterglow composite material is prepared, an ultraviolet lamp with the wavelength of 275nm is used for excitation for 1min, the emission wavelength of the ultraviolet lamp is 434nm, and the afterglow emission duration is less than 1min.
Comparative example 2
On the basis of the embodiment 1, the ratio of isophthalic acid to urea is adjusted to be 0.9:2, other conditions are unchanged, the carbon quantum dot-based organic long afterglow composite material is prepared, an ultraviolet lamp with the wavelength of 275nm is used for excitation for 1min, the emission wavelength is 471nm, and the afterglow emission time is less than 1min.
Comparative example 3
On the basis of the embodiment 1, the ratio of isophthalic acid to urea is adjusted to be 1.2:2, other conditions are unchanged, the carbon quantum dot-based organic long afterglow composite material is prepared, an ultraviolet lamp with the wavelength of 275nm is used for excitation for 1min, the emission wavelength is 492nm, and the afterglow emission duration is less than 1min.
In summary, the application uses benzene series as carbon source, and takes fusion reaction with urea according to mass ratio of (0.001-0.5): 2, when the reaction temperature is 175-235 ℃ and the reaction time is 1-5 hours, a carbon quantum dot-based organic long afterglow composite material capable of generating long afterglow emission under the irradiation of 275nm wavelength ultraviolet ray can be prepared, the material does not contain rare elements, the preparation process is simple, and has strong long afterglow emission performance, blue afterglow can be generated after the irradiation of 275-310 nm wavelength ultraviolet ray, and the luminous duration can reach the level of hours and far exceeds the prior carbon dot-based organic LPL material.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the carbon quantum dot-based organic long afterglow composite material is characterized by comprising the following steps of: and mixing a carbon source with urea, and performing a melting reaction to obtain the carbon quantum dot-based organic long afterglow composite material.
2. The method for preparing the carbon quantum dot-based organic long afterglow composite material according to claim 1, characterized in that the carbon source comprises a compound represented by the following formula (i):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, carboxyl or amino, and R 1 、R 2 、R 3 、R 4 、R 5 、R 6 At least 2 of which are independently selected from carboxyl or amino groups.
3. The method for preparing a carbon quantum dot-based organic long afterglow composite material according to claim 1, characterized in that a carbon source and urea are mixed and sufficiently ground, then a melting reaction is performed, and after the melting reaction is finished, the cooled product is ground again into powder.
4. The method for preparing a carbon quantum dot-based organic long afterglow composite material according to claim 2, characterized in that the carbon source comprises at least one of isophthalic acid, trimesic acid, phthalic acid, terephthalic acid, 3-aminobenzoic acid and m-phenylenediamine.
5. The method for producing a carbon quantum dot based organic long afterglow composite material according to any one of claims 1 to 4, characterized in that the mass ratio of the carbon source to urea is (0.001 to 0.5): 2.
6. The method for preparing a carbon quantum dot based organic long afterglow composite material according to any one of claims 1 to 4, characterized in that the temperature of the melting reaction is 175 ℃ to 235 ℃ and the reaction time is 1h to 6h.
7. The method for preparing a carbon quantum dot based organic long afterglow composite material according to claim 2 or 4, characterized in that the carbon source is isophthalic acid.
8. The method for preparing a carbon quantum dot based organic long afterglow composite material according to claim 5, characterized in that the mass ratio of the carbon source to urea is (0.006-0.1): 2.
9. The method for preparing the carbon quantum dot-based organic long afterglow composite material according to claim 6, characterized in that the temperature of the melting reaction is 195 ℃ and the reaction time is 5 hours.
10. A carbon quantum dot based organic long afterglow composite material, characterized in that it is prepared by the method according to any one of claims 1 to 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154480A (en) * | 2018-11-06 | 2020-05-15 | 华南农业大学 | Long-afterglow material 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 |
| CN114381261A (en) * | 2022-01-24 | 2022-04-22 | 齐鲁工业大学 | Phosphorescent carbon dot-metal organic framework composite material and preparation method and application thereof |
| CN114774119A (en) * | 2022-03-28 | 2022-07-22 | 太原理工大学 | Phosphorescent carbon quantum dot matrix composite material and preparation method thereof |
| CN115197699A (en) * | 2022-08-30 | 2022-10-18 | 广东先导稀材股份有限公司 | Bluish violet phosphorescent carbon quantum dot and preparation method thereof |
| CN115806819A (en) * | 2022-11-21 | 2023-03-17 | 太原理工大学 | Room-temperature phosphorescent afterglow luminescent carbon quantum dot and solid-phase one-step preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154480A (en) * | 2018-11-06 | 2020-05-15 | 华南农业大学 | Long-afterglow material 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 |
| CN114381261A (en) * | 2022-01-24 | 2022-04-22 | 齐鲁工业大学 | Phosphorescent carbon dot-metal organic framework composite material and preparation method and application thereof |
| CN114774119A (en) * | 2022-03-28 | 2022-07-22 | 太原理工大学 | Phosphorescent carbon quantum dot matrix composite material and preparation method thereof |
| CN115197699A (en) * | 2022-08-30 | 2022-10-18 | 广东先导稀材股份有限公司 | Bluish violet phosphorescent carbon quantum dot and preparation method thereof |
| CN115806819A (en) * | 2022-11-21 | 2023-03-17 | 太原理工大学 | Room-temperature phosphorescent afterglow luminescent carbon quantum dot and solid-phase one-step preparation method and application thereof |
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