CN113201333A - Full-color room temperature phosphorescent carbon dot under ultraviolet excitation and composition thereof - Google Patents
Full-color room temperature phosphorescent carbon dot under ultraviolet excitation and composition thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 100
- 230000005284 excitation Effects 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 24
- 239000012043 crude product Substances 0.000 claims description 24
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 24
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 238000004108 freeze drying Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- 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
Abstract
The invention discloses a full-color room temperature phosphorescent carbon dot under ultraviolet excitation and a composition thereof. The carbon dots are used as a luminous source, the polyacrylamide is used as a base material, and the carbon dots are embedded into the polyacrylamide base to form a composite base to realize the discharge process of phosphorescence; phosphorescence is generated under the excitation of ultraviolet light, and the stability of room temperature phosphorescence emission is high and the service life is long.
Description
Technical Field
The invention relates to the technical field of luminescent material production, in particular to a full-color room temperature phosphorescent carbon dot under ultraviolet light excitation and a composition thereof.
Background
In recent years, Carbon Dots (CDs) have received much attention due to their excellent light stability, low toxicity, environmental protection, and excellent optical properties. The unique optical characteristics enable CDs to have potential application prospects in the fields of chemical sensing, biological fluorescent probes, light-emitting devices, photocatalytic devices and the like.
CDs have excellent uv absorption properties due to the singlet energy levels provided by the conjugated carbon network of their core and surface functions. Under ultraviolet irradiation, the ground state (S)0) The electrons in (a) are excited to a singlet excited state of the carbon core and surface function, and these photoexcited electrons are transferred to an emission site generated by a surface functional group through an internal conversion process from the lowest energy level (S) of the singlet excited state1) Radiating to the ground state (S)0) Fluorescence is generated.
Most research has focused on the use of fluorescent CDs due to their excellent properties, and furthermore, although the fluorescence of CDs has been widely recorded and studied, the development of phosphorescence of CDs is still in the early stages due to non-radiative deactivation of highly active excited states. Albeit in the triplet state T due to spin conservation1A large number of colonies were generated, but T1Radiative relaxation of the mesoelectrons is forbidden. Meanwhile, the oscillator corresponding to the transition has weak strength, so that the probability of radiation inactivation is extremely low, and T is accordingly1Non-radiative relaxation of the mesoelectron (either by collision with other molecules or by intermolecular vibrations) is the only de-excitation pathway. Embedding CDs in a composite matrix facilitates intersystem crossing, which is an effective way for CDs-based materials to generate room temperature phosphorescence.
To date, few reports have been made of CDs-based room temperature phosphorescent materials, and the phosphorescent lifetime is relatively low. For example, Han et al, (2019) radial Design of Oxygen-engineered Carbon Dots with Efficient Rom-Temperature phosphor Properties and High-Tech Security Protection application, ACS Sustainable Chemistry & Engineering 7, 19918-. The PVA is used as a matrix to synthesize the CDs @ PVA room temperature phosphorescent carbon dot-based material, and the phosphorescence lifetime of the material is 292 ms. The phosphorescent lifetime is relatively low and the phosphorescent emission is concentrated in only one green region, which is not advantageous for more applications.
Therefore, in order to obtain a significant effect of phosphorescence emission at room temperature and broaden the application field of phosphorescence at room temperature, a new matrix material must be sought.
In addition, the introduction of N is a key factor in room temperature phosphorescence synthesis, as it promotes N-pi + transitions, promotes intersystem crossing (ISC), enhances spin-orbit coupling, and thus saturates the triplet state with available excitons.
The substrate is important for stabilizing the long-life tristate fluorescent powder, and the tristate fluorescent powder is easily quenched by molecular vibration, oxygen molecules and high temperature. Therefore, the generation of self-protected CDs based room temperature phosphorescent materials using surface decoration and elemental doping is currently a key challenge.
Disclosure of Invention
The invention aims to provide a full-color room temperature phosphorescent carbon dot under ultraviolet excitation and a composition thereof, wherein the carbon dot is used as a luminous source, polyacrylamide is used as a matrix material, and the carbon dot is embedded into a polyacrylamide matrix to form a composite matrix to realize a phosphorescent emission process; phosphorescence is generated under the excitation of ultraviolet light, and the stability of room temperature phosphorescence emission is high and the service life is long.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a full-color room temperature phosphorescent carbon dot under ultraviolet excitation is formed by compounding a primary color carbon dot and polyacrylamide, wherein the primary color carbon dot is used as a main body, the polyacrylamide is used as a composite matrix, and the primary color carbon dot is uniformly dispersed in the polyacrylamide polymer matrix.
According to the invention, through research and exploration, the carbon dots are used as luminous sources, polyacrylamide is used as a matrix to prepare the carbon dot-based room-temperature phosphorescent material, and blue, green, yellow and red full-color room-temperature phosphorescence is generated under the excitation of ultraviolet light.
Related groups such as carbon-nitrogen single bond/triple bond are the main reasons of triplet-related emission, and triplet phosphorescence is easily quenched by oxygen (formation)1O2). Related groups such as carbon-nitrogen single bond/triple bond and the like are effective ways for inhibiting quenching of triplet excitons in the CDs-based room-temperature phosphorescent material and realizing self-protection room-temperature phosphorescence. This is an important factor in the present invention for producing full color room temperature phosphorescent carbon dots.
The hydrogen bonds may inhibit intramolecular movement of the CDs based material, may provide steric protection around the phosphor, and may effectively improve the stability of room temperature phosphorescent emission. This is a key factor in the long lifetime of the multi-color room temperature phosphorescent carbon dots of the present invention, wherein the lifetime of phosphorescence can reach 630ms at most. The invention can only be excited under ultraviolet light.
The invention selects a matrix composite strategy as a special method for constructing an aggregation state, and provides a special method for adjusting the optical and photophysical properties of the CDs-based material. Similar to the intramolecular movement mechanism that limits the aggregation-induced emission (AIE) phenomenon in terms of host recombination, host recombination can suppress non-radiative decay of excited states, form energy transfer, enhance photoluminescence of CDs, and even generate room temperature phosphorescence.
Preferably, the primary color carbon dot is selected from one of a blue carbon dot, a green carbon dot, a yellow carbon dot, and a red carbon dot (the color carbon dot is defined according to the corresponding phosphorescent color); the synthetic raw materials of the blue carbon dots are m-phenylenediamine and citric acid; the synthetic raw materials of the green carbon dots are m-phenylenediamine and sodium hydroxide; the synthetic raw materials of the yellow carbon dots are neutral red and sodium hydroxide; the synthetic raw materials of the red carbon dots are neutral red and glacial acetic acid. The four carbon dot materials themselves have no phosphorescent properties.
The preparation method of the blue carbon dots comprises the following steps: according to the mass ratio of m-phenylenediamine to citric acid to water of 1: 0.3-5: 60-200, placing m-phenylenediamine and citric acid in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The preparation method of the green carbon dots comprises the following steps: according to the mass ratio of m-phenylenediamine to sodium hydroxide to water of 1: 2-10: 50-200, placing m-phenylenediamine and sodium hydroxide in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The preparation method of the yellow carbon dots comprises the following steps: according to the mass ratio of neutral red to sodium hydroxide to water of 1: 2-10: 40-200, placing neutral red and sodium hydroxide in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The preparation method of the red carbon dots comprises the following steps: placing neutral red and glacial acetic acid in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution, wherein the final concentration of the neutral red is 0.8-2.4 wt%, and VGlacial acetic acid：VWater (W)= 1: 2-5; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The ultrasonic time is 5-25 minutes; the centrifugation parameters were: centrifuging for 5-20 minutes at the rotating speed of 1000-10000 rpm; the specification of the dialysis bag is 500 Da-3500 Da, and the dialysis time is 12-96 hours; the freeze drying time is 12-96 hours.
The mass ratio of the carbon dots of the primary color to the polyacrylamide is 1: 200 to 5000.
A full-color room temperature phosphorescent carbon dot composition under ultraviolet light excitation is formed by combining more than two of a blue phosphorescent carbon dot compounded by a blue carbon dot and polyacrylamide, a green phosphorescent carbon dot compounded by a green carbon dot and polyacrylamide, a yellow phosphorescent carbon dot compounded by a yellow carbon dot and polyacrylamide and a red phosphorescent carbon dot compounded by a red carbon dot and polyacrylamide.
An application of full-color room temperature phosphorescent carbon dots and a composition thereof as anti-counterfeiting and information encryption and decryption materials under ultraviolet light excitation.
The invention has the beneficial effects that:
(1) according to the invention, the blue, green, yellow and red full-color room-temperature phosphorescence can be generated after the four carbon dots (self non-phosphorus property) are reasonably selected and compounded with the polyacrylamide, the phosphorescence phenomenon of more than 10 seconds can be seen by naked eyes, wherein the phosphorescence service life can reach 630ms at most, and the composite material can be used for anti-counterfeiting and high-security level hiding of complex patterns.
(2) The full-color room temperature phosphorescent carbon dots under ultraviolet light excitation can combine two room temperature phosphorescent carbon dots, also can combine three room temperature phosphorescent carbon dots, even combines four room temperature phosphorescent carbon dots together to form a composition, can also generate room temperature phosphorescence, even can form heat-activated delayed fluorescence and room temperature phosphorescence to appear simultaneously, and greatly widens various applications.
(3) The full-color room temperature phosphorescent carbon dot and the composition under the excitation of ultraviolet light have the remarkable advantages of simple preparation, relatively low manufacturing cost, low toxicity and the like, and are incomparable with the traditional metal complex.
Drawings
Fig. 1 is a fluorescence emission spectrum of a full-color room temperature phosphorescent carbon dot under ultraviolet light excitation prepared in an example of the present invention, and fig. 1 (a) is a fluorescence emission spectrum of a blue carbon dot prepared in example 1 of the present invention; FIG. 1 (b) is a fluorescence emission spectrum of a green carbon dot prepared in example 2 of the present invention; FIG. 1 (c) is a fluorescence emission spectrum of a yellow carbon dot prepared in example 3 of the present invention; FIG. 1 (d) is a fluorescence emission spectrum of a red carbon dot prepared in example 4 of the present invention;
FIG. 2 is a photograph of a full-color room temperature phosphorescent carbon dot under excitation of ultraviolet light and a picture of blue phosphorescence in the composition prepared in example 1 of the present invention under the conditions that a 365nm ultraviolet lamp is turned on (FIG. 2 a) and turned off (FIG. 2 b), respectively, (FIG. 2 c) is a phosphorescence emission spectrum;
FIG. 3 is a photograph of a full color room temperature phosphorescent carbon dot under ultraviolet excitation and a picture of green phosphorescence in the composition prepared in example 2 of the present invention under the conditions of a 365nm ultraviolet lamp being on (FIG. 3 a) and off (FIG. 3 b), respectively, (FIG. 3 c) is a phosphorescence emission spectrum;
FIG. 4 is a photograph of a full-color room temperature phosphorescent carbon dot under excitation of ultraviolet light and yellow phosphorescence in the composition prepared in example 3 of the present invention under the conditions that a 365nm ultraviolet lamp is turned on (FIG. 4 a) and turned off (FIG. 4 b), respectively, and FIG. 4c is a phosphorescence emission spectrum.
FIG. 5 is a photograph of a full color room temperature phosphorescent carbon dot under UV excitation and a red phosphorescence image in the composition prepared in example 4 of the present invention under the conditions of a 365nm UV lamp being ON (FIG. 5 a) and OFF (FIG. 5 b), respectively, (FIG. 5 c) is a phosphorescence emission spectrum.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
General implementation:
a full-color room temperature phosphorescent carbon dot under ultraviolet excitation is formed by compounding a base color carbon dot and polyacrylamide, wherein the mass ratio of the base color carbon dot to the polyacrylamide is 1: 200 to 5000. The carbon dots with the primary color are used as a main body, the polyacrylamide is used as a composite matrix, and the carbon dots with the primary color are uniformly dispersed in the polyacrylamide polymer matrix.
The primary color carbon dots are selected from one of blue carbon dots, green carbon dots, yellow carbon dots and red carbon dots; the synthetic raw materials of the blue carbon dots are m-phenylenediamine and citric acid; the synthetic raw materials of the green carbon dots are m-phenylenediamine and sodium hydroxide; the synthetic raw materials of the yellow carbon dots are neutral red and sodium hydroxide; the synthetic raw materials of the red carbon dots are neutral red and glacial acetic acid.
The preparation method of the blue carbon dots comprises the following steps: according to the mass ratio of m-phenylenediamine to citric acid to water of 1: 0.3-5: 60-200, placing m-phenylenediamine and citric acid in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The preparation method of the green carbon dots comprises the following steps: according to the mass ratio of m-phenylenediamine to sodium hydroxide to water of 1: 2-10: 50-200, placing m-phenylenediamine and sodium hydroxide in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The preparation method of the yellow carbon dots comprises the following steps: according to the mass ratio of neutral red to sodium hydroxide to water of 1: 2-10: 40-200, placing neutral red and sodium hydroxide in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The preparation method of the red carbon dots comprises the following steps: placing neutral red and glacial acetic acid in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution, wherein the final concentration of the neutral red is 0.8-2.4 wt%, and VGlacial acetic acid：VWater (W)= 1: 2-5; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
The ultrasonic time is 5-25 minutes; the centrifugation parameters were: centrifuging for 5-20 minutes at the rotating speed of 1000-10000 rpm; the specification of the dialysis bag is 500 Da-3500 Da, and the dialysis time is 12-96 hours; the freeze drying time is 12-96 hours.
Example 1
Placing 0.1g of m-phenylenediamine and 0.08g of citric acid in a sample bottle, adding 10mL of distilled water, and fully stirring and mixing to obtain a precursor solution;
placing a sample bottle filled with the precursor solution into a 25mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle for 4 hours at 140 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after heating to obtain a product;
and (3) dissolving the product obtained in the step (2) by ultrasonic for 15 minutes, filtering, centrifuging the filtrate (rotating speed is 3000 r/min, centrifuging for 15 minutes), taking the supernatant, dialyzing (the specification of a dialysis bag is 500Da, and the dialysis time is 24 hours), and freeze-drying to obtain the blue carbon dots.
Adding composite matrix polyacrylamide into blue carbon dot solution (30 mL), and stirring at room temperature to form a blue carbon dot-polyacrylamide composite; heating the blue carbon dot-polyacrylamide compound (100 ℃, 6 hours), cooling and grinding to obtain the full-color room temperature phosphorescent carbon dot and the composition (blue phosphorescence) under the excitation of ultraviolet light. Among them, blue carbon dots (1 mg) and polyacrylamide (500 mg).
Example 2
Placing 0.1g of m-phenylenediamine and 0.08g of sodium hydroxide in a sample bottle, adding 10mL of distilled water, and fully stirring and mixing to obtain a precursor solution;
placing a sample bottle filled with the precursor solution into a 25mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle for 4 hours at 140 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after heating to obtain a product;
and (3) dissolving the product obtained in the step (2) by ultrasonic for 15 minutes, filtering, centrifuging the filtrate (rotating speed is 3000 r/min, centrifuging for 15 minutes), taking the supernatant, dialyzing (the specification of a dialysis bag is 500Da, and the dialysis time is 24 hours), and freeze-drying to obtain the green carbon dots.
Adding composite matrix polyacrylamide into a green carbon dot solution (30 mL), and stirring at room temperature to form a green carbon dot-polyacrylamide composite; the green carbon dot-polyacrylamide compound is heated (100 ℃ for 6 hours), cooled and ground to obtain the full-color room temperature phosphorescent carbon dot and the composition (green phosphorescence) under the excitation of ultraviolet light. Among them, green carbon dots (1 mg) and polyacrylamide (500 mg).
Example 3
Placing 0.1g of neutral red and 0.08g of sodium hydroxide in a sample bottle, adding 10mL of distilled water, and fully stirring and mixing to obtain a precursor solution;
placing a sample bottle filled with the precursor solution into a 25mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle for 4 hours at 140 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after heating to obtain a product;
and (3) dissolving the product obtained in the step (2) by ultrasonic for 15 minutes, filtering, centrifuging the filtrate (rotating speed is 3000 r/min, centrifuging for 15 minutes), taking the supernatant, dialyzing (the specification of a dialysis bag is 500Da, and the dialysis time is 24 hours), and freeze-drying to obtain the yellow carbon dots.
Adding composite matrix polyacrylamide into a yellow carbon dot solution (30 mL), and stirring at room temperature to form a yellow carbon dot-polyacrylamide composite; the yellow carbon dot-polyacrylamide compound is heated (100 ℃ for 6 hours), cooled and ground to obtain the full-color room temperature phosphorescent carbon dot and the composition (yellow phosphorescence) under the excitation of ultraviolet light. Among them, yellow carbon (1 mg) and polyacrylamide (500 mg).
Example 4
Placing 0.15g of neutral red and 3mL of glacial acetic acid in a sample bottle, adding 7mL of distilled water, and fully stirring and mixing to obtain a precursor solution;
placing a sample bottle filled with the precursor solution into a 25mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an oven, heating the hydrothermal reaction kettle for 4 hours at 140 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after heating to obtain a product;
and (3) dissolving the product obtained in the step (2) by ultrasonic for 15 minutes, filtering, centrifuging the filtrate (rotating speed is 3000 r/min, centrifuging for 15 minutes), taking the supernatant, dialyzing (the specification of a dialysis bag is 500Da, and the dialysis time is 24 hours), and freeze-drying to obtain the red carbon dots.
Adding the composite matrix polyacrylamide into a red carbon dot solution (30 mL), and stirring at room temperature to form a red carbon dot-polyacrylamide composite; heating the red carbon dot-polyacrylamide compound (100 ℃, 6 hours), cooling and grinding to obtain the full-color room temperature phosphorescent carbon dot and the composition (red phosphorescence) under the excitation of ultraviolet light. Among them, red carbon dots (1 mg) and polyacrylamide (500 mg).
Fig. 1 is a fluorescence emission spectrum of a full-color room temperature phosphorescent carbon dot under ultraviolet light excitation prepared in an embodiment of the invention, and fig. 1 (a) is a fluorescence emission spectrum of a blue carbon dot prepared in the embodiment 1 of the invention, wherein the optimal excitation is 320nm, and the optimal emission is 466 nm; FIG. 1 (b) is a graph showing fluorescence emission spectra of green carbon dots prepared in example 2 of the present invention, with optimal excitation at 350nm and optimal emission at 514 nm; FIG. 1 (c) shows the fluorescence emission spectrum of a yellow carbon dot prepared in example 3 of the present invention, with the optimal excitation at 410nm and the optimal emission at 602 nm; FIG. 1 (d) is a fluorescence emission spectrum of a red carbon dot prepared in example 4 of the present invention, with an optimal excitation of 540nm and an optimal emission of 622 nm;
fig. 2 is a blue phosphorescent picture of a full-color room temperature phosphorescent carbon dot under ultraviolet excitation prepared in example 1 of the present invention, wherein: FIG. 2a is a photograph of a 365nm ultraviolet lamp excited with blue fluorescence; FIG. 2b is a photograph of a 365nm UV lamp turned off showing blue phosphorescence, and FIG. 2c is a graph of the phosphorescence spectrum under 365nm UV excitation showing blue phosphorescence emission at 476 nm.
Fig. 3 is a green phosphorescent picture of a full-color room temperature phosphorescent carbon dot under ultraviolet excitation prepared in example 2 of the present invention, wherein: FIG. 3a is a photograph of a 365nm ultraviolet lamp excited with yellowish fluorescence; FIG. 3b is a photograph of a 365nm UV lamp turned off showing green phosphorescence, and FIG. 3c is a graph of the phosphorescence spectrum under 365nm UV excitation showing green phosphorescence emission at 502 nm.
Fig. 4 is a yellow phosphorescent picture of a full-color room temperature phosphorescent carbon dot under ultraviolet light excitation prepared in example 3 of the present invention, wherein: FIG. 4a is a photograph of a photograph taken under 365nm ultraviolet lamp excitation, showing yellow fluorescence; FIG. 4b is a photograph of a 365nm UV lamp turned off showing phosphorescence at yellow, and FIG. 4c is a graph of the phosphorescence spectrum under 365nm UV excitation showing phosphorescence emission at 566 nm.
Fig. 5 is a red phosphorescent picture of a full-color room temperature phosphorescent carbon dot and a composition under ultraviolet light excitation prepared in example 4 of the present invention, wherein: FIG. 5a is a photograph of a 365nm ultraviolet lamp excited with red fluorescence; FIG. 5b is a photograph of a 365nm UV lamp turned off showing red phosphorescence, and FIG. 5c is a graph of the phosphorescence spectrum under 365nm UV excitation showing red phosphorescence emission at 614 nm.
Properties of blue carbon dots: the synthetic raw materials are m-phenylenediamine and citric acid, the optimal excitation is 320nm, the optimal emission is 466nm, the fluorescence lifetime is 5ns, blue phosphorescence is generated after the compound of the m-phenylenediamine and the citric acid and polyacrylamide, and the phosphorescence lifetime is 631 ms.
Green carbon dot properties: the synthetic raw materials are m-phenylenediamine and sodium hydroxide, the optimal excitation is 350nm, the optimal emission is 514nm, the fluorescence lifetime is 4ns, and green phosphorescence is generated after the compound of the m-phenylenediamine and the polyacrylamide, and the phosphorescence lifetime is 560 ms.
Properties of yellow carbon dot: the synthetic raw materials are neutral red and sodium hydroxide, the optimal excitation is 410nm, the optimal emission is 602nm, the fluorescence lifetime is 2.3ns, and the phosphorescence can generate yellow phosphorescence after being compounded with polyacrylamide, and the phosphorescence lifetime is 500 ms.
Properties of red carbon dots: the synthetic raw materials are neutral red and acetic acid, the optimal excitation is 540nm, the optimal emission is 622nm, the fluorescence lifetime is 3.8ns, and the red phosphorescence can be generated after the compound with polyacrylamide, and the phosphorescence lifetime is 460 ms.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. The full-color room temperature phosphorescent carbon dot under ultraviolet excitation is characterized by being formed by compounding a primary color carbon dot and polyacrylamide, wherein the primary color carbon dot is used as a main body, the polyacrylamide is used as a composite matrix, and the primary color carbon dot is uniformly dispersed in the polyacrylamide polymer matrix.
2. The all-color room temperature phosphorescent carbon dot excited by ultraviolet light of claim 1, wherein the primary color carbon dot is selected from one of a blue carbon dot, a green carbon dot, a yellow carbon dot and a red carbon dot; the synthetic raw materials of the blue carbon dots are m-phenylenediamine and citric acid; the synthetic raw materials of the green carbon dots are m-phenylenediamine and sodium hydroxide; the synthetic raw materials of the yellow carbon dots are neutral red and sodium hydroxide; the synthetic raw materials of the red carbon dots are neutral red and acetic acid.
3. The full-color room temperature phosphorescent carbon dot excited by ultraviolet light according to claim 2, wherein the preparation method of the blue carbon dot comprises the following steps: according to the mass ratio of m-phenylenediamine to citric acid to water of 1: 0.3-5: 60-200, placing m-phenylenediamine and citric acid in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
4. The full-color room temperature phosphorescent carbon dot excited by ultraviolet light according to claim 2, wherein the preparation method of the green carbon dot comprises the following steps: according to the mass ratio of m-phenylenediamine to sodium hydroxide to water of 1: 2-10: 50-200, placing m-phenylenediamine and sodium hydroxide in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
5. The full-color room temperature phosphorescent carbon dot excited by ultraviolet light according to claim 2, wherein the preparation method of the yellow carbon dot comprises the following steps: according to the mass ratio of neutral red to sodium hydroxide to water of 1: 2-10: 40-200, placing neutral red and sodium hydroxide in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
6. The full-color room temperature phosphorescent carbon dot excited by ultraviolet light according to claim 2, wherein the preparation method of the red carbon dot comprises the following steps: placing neutral red and glacial acetic acid in a sample bottle, adding distilled water, and fully stirring and mixing to obtain a precursor solution, wherein the final concentration of the neutral red is 0.8-2.4 wt%, and VGlacial acetic acid：VWater (W)= 1: 2-5; placing the sample bottle filled with the precursor solution in a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120-280 ℃ for 2-24 hours, and naturally cooling to room temperature to obtain a crude product; dissolving the crude product with ultrasound, filtering, centrifuging the filtrate, collecting supernatant, dialyzing, and freeze-drying.
7. The full-color room temperature phosphorescent carbon dot excited by the ultraviolet light according to the claim 3, 4, 5 or 6, wherein the ultrasonic time is 5-25 minutes; the centrifugation parameters were: centrifuging for 5-20 minutes at the rotating speed of 1000-10000 rpm; the specification of the dialysis bag is 500 Da-3500 Da, and the dialysis time is 12-96 hours; the freeze drying time is 12-96 hours.
8. The full-color room temperature phosphorescent carbon dot excited by the ultraviolet light as claimed in claim 1 or 2, wherein the mass ratio of the primary color carbon dot to the polyacrylamide is 1: 200 to 5000.
9. A full-color room temperature phosphorescent carbon dot composition under ultraviolet light excitation is characterized by being formed by combining more than two of a blue phosphorescent carbon dot compounded by a blue carbon dot and polyacrylamide, a green phosphorescent carbon dot compounded by a green carbon dot and polyacrylamide, a yellow phosphorescent carbon dot compounded by a yellow carbon dot and polyacrylamide and a red phosphorescent carbon dot compounded by a red carbon dot and polyacrylamide.
10. An application of full-color room temperature phosphorescent carbon dots and a composition thereof as anti-counterfeiting and information encryption and decryption materials under ultraviolet light excitation.
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