CN113817460B - Full-color adjustable long-life room temperature phosphorescent material and preparation method thereof - Google Patents
Full-color adjustable long-life room temperature phosphorescent material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a full-color adjustable long-life room temperature phosphorescent material and a preparation method thereof. The long-life room temperature phosphorescent material is a compound consisting of boron oxide polycrystal and carbon dots, wherein the carbon dots are generated in situ and are uniformly dispersed and embedded in the boron oxide polycrystal, and the boron oxide polycrystal is a blocky polycrystal generated by in-situ dehydration of boric acid molecules. The long-life room temperature phosphorescent material has full-color adjustable long-life room temperature phosphorescent color, the phosphorescent color can be adjusted from blue to red, and the whole visible light area is covered. The long-life room temperature phosphorescent material has the average attenuation life of 113.90-581.76ms in a room temperature air environment, the highest decay life of 1311.07ms in a 77K vacuum environment, the afterglow time recognizable by naked eyes reaches 5-12s in the room temperature air environment, and the phosphorescent material has stable phosphorescence performance and can be stored for a long time.
Description
Technical Field
The invention belongs to the field of phosphorescent materials, and particularly relates to a full-color adjustable long-life room temperature phosphorescent material and a preparation method thereof, in particular to a full-color adjustable carbon dot composite-based long-life room temperature phosphorescent material and a preparation method and application thereof.
Background
The long-life room temperature phosphorescence has important application value in the fields of photoelectricity, photovoltaics, photocatalysis, high-sensitivity biological imaging, information encryption and the like [ adv.Funct.Mater.2018,1802657]. At present, pure organic room temperature phosphorescent materials are promising substitutes for traditional metal doped compounds [ Angew. Chem. Int.Edit.2019,58,7278] due to low consumption and general synthetic strategies (such as crystal engineering, host-guest doping and H-aggregation) [ Angew. Chem. Int.Edit.2019,58,18776]. However, most of the pure organic phosphorescent materials require a relatively complicated synthesis process and it is difficult to control the color of the room temperature phosphorescence in a single system, so that full color room temperature phosphorescence is lacking, which greatly limits their application in the field of photovoltaics.
Recently, carbon Dots (CDs) have attracted great attention in the construction of non-metallic room temperature phosphorescent materials due to their characteristics of easy preparation, high light stability and outstanding biocompatibility. In general, doping of heteroatoms and embedding CDs in a host matrix such as polyvinyl alcohol, silica, inorganic salts, or urea can generate and enhance phosphorescence of CDs. In the prior patent with the application number of CN202011008933, crocin T and sodium hydroxide are used as raw materials to synthesize carbon dots, and then the synthesized carbon dots and boric acid are heated and reacted in a solution to prepare the CDs-based phosphorescent material. In the prior patent with the application number of CN201811314890, six carbon points are synthesized in advance by adopting different raw materials and methods, and then the prepared carbon points and boric acid react in a molten state to prepare the CDs-based phosphorescent material. However, these methods all require multi-step reactions and multiple precursors, require the pre-synthesis of carbon dots, make the preparation process relatively lengthy and uncontrollable, limit its large scale preparation, and limit the room temperature phosphorescent color mainly to a narrow wavelength range and uncontrollable.
Disclosure of Invention
The invention aims to provide a full-color adjustable long-life room temperature phosphorescent material and a preparation method thereof, aiming at the problem that the phosphorescent color is limited in a narrow wavelength range.
The purpose of the invention can be realized by the following scheme:
in a first aspect, the invention provides a full-color adjustable long-life room temperature phosphorescent material, which comprises boron oxide polycrystal and carbon dots; the carbon dots are generated in situ, uniformly dispersed and embedded in the boron oxide polycrystal; the boron oxide polycrystal is a blocky polycrystal generated by in-situ dehydration of boric acid molecules.
In the prior art, carbon dots need to be synthesized firstly, and then the carbon dots react with a matrix to generate new carbon dots which are embedded in the matrix.
As an embodiment of the invention, the particle size of the carbon dots is 2.8-5.3nm, the structure is a graphitization-like structure, and the oxidation degree is 28.16-58.16%.
In one embodiment of the present invention, the long-life room temperature phosphorescent material comprises elements of C, B and O and-OH, C-C/C = C, C-O/C-O-B, C = O, O-C = O, BCO 2 ，B 2 O 3 And a B-O bond.
In a second aspect, the present invention further provides a method for preparing a long-life room temperature phosphorescent material, comprising the following steps:
s1, mixing reactants: completely dissolving citric acid and boric acid in a solvent, heating to completely volatilize the solvent, uniformly mixing the citric acid and the boric acid, and obtaining a mixture of the citric acid and the boric acid;
s2, preparing a phosphorescent material: heating and melting the mixture of the boric acid and the citric acid obtained in the step S1 until the boric acid and the citric acid completely react;
and S3, obtaining the long-life room-temperature phosphorescent material with different phosphorescent colors by changing the proportion of citric acid and boric acid and the heating and melting temperature or time in the step S1.
As an embodiment of the present invention, in step S1, the dosage ratio of the citric acid to the boric acid is 1-1600mg:6g.
As an embodiment of the present invention, in step S1, the solvent is water. The amount of solvent is such that the citric acid and boric acid are completely dissolved.
As an embodiment of the present invention, in step S1, the heating is specifically: placing the solution of boric acid and citric acid in a container and heating the container in an open state; the heating temperature is 70-110 ℃, and the heating time is 7-12h. The solvent does not participate in the reaction and the purpose of heating is to allow the solvent to evaporate sufficiently to avoid bumping of the solvent during the melt reaction. Compared with direct mixing, the boric acid and the citric acid can be fully contacted and reacted, and carbon dots generated by the reaction are uniformly dispersed in the boron oxide polycrystal. In addition, during the open heating process, the solvent generated by the reaction is volatilized, so that a solid product is obtained, and the solid boron oxide polycrystal can limit the molecular rotation of the carbon dots and avoid oxygen quenching in the air.
In the step S1, the heating temperature is 70-110 ℃, the solvent water can be quickly volatilized, the solvent does not participate in the reaction and only has the function of good contact of reactants, in order to avoid the temperature from being too high and the solvent from being quickly volatilized to cause bumping, the solvent is removed before the reaction, and the reactants are melted at 170 ℃ to present a solid-phase reaction. Boric acid can be decomposed into boron oxide at the temperature of more than 170 ℃, and after heating is stopped, the boron oxide is solidified, so that phosphorescence can be realized by limiting the rotation of carbon points. If the reaction is carried out in a liquid state in a reaction vessel, phosphorescence cannot be obtained because of the presence of a large amount of solvent. The temperature for heating the volatilization is not too high to cause the reactants to react, and too low to cause the volatilization too slow. The heating volatilization time depends on whether the solvent is completely volatilized or not, and the bumping in the reaction is avoided.
In one embodiment of the present invention, in step S2, the heating and melting temperature is 170 to 220 ℃, and the heating reaction time is 3 to 6 hours. The heating reaction time is preferably 5 hours. The temperature for heating and melting is higher than the melting point of boric acid, so that boric acid can be decomposed into boron oxide, but not too high, and the melting temperature is too high, so that the generated carbon points are carbonized to a high degree, and the intensity of phosphorescence is reduced. The method mainly adjusts the carbonization degree of the carbon points by adjusting and controlling the reaction temperature and the dosage of the citric acid so as to adjust and control the grain diameter and the oxidation degree of the carbon points. The method for realizing the equivalent effect of the invention by regulating and controlling the reaction time is also within the protection scope of the invention.
As an embodiment of the invention, the phosphorescence color of the long-life room temperature phosphorescent material can be regulated from blue to red in a room temperature air environment, the maximum emission peak range is 466-638nm, and the long-life room temperature phosphorescent material covers the whole visible light region.
As an embodiment of the invention, the average phosphorescence lifetime of the long-life room temperature phosphorescent material can reach 113.90-581.76ms in a room temperature air environment, can reach 1311.07ms at most in a 77K vacuum environment, and can reach 5-12s in a room temperature air environment with afterglow time recognizable to naked eyes.
In a third aspect, the invention also provides application of the long-life room temperature phosphorescent material in multi-dimensional information encryption.
Compared with the prior art, the invention has the advantages that:
1) The full-color adjustable carbon dot composite-based long-life room-temperature phosphorescent material provided by the invention can emit full-color phosphorescence which is distinguishable to naked eyes after the irradiation of an ultraviolet lamp is stopped, the phosphorescence color is from blue to red, the maximum emission peak range is from 466nm to 638nm, the full-color adjustable carbon dot composite-based long-life room-temperature phosphorescent material can cover the whole visible light area, can be adjusted only by changing the mixture ratio of reactants and the reaction temperature, and has the characteristic of excitation dependence. The average decay life of blue-to-red carbon dot composite-based long-life room-temperature phosphorescence can reach 113.90-581.76ms in a room-temperature air environment, can reach 1311.07ms at most in a 77K vacuum environment, can reach 5-12s in a room-temperature air environment with afterglow time recognizable to naked eyes, and has stable phosphorescence luminescence performance and long-time storage;
2) The preparation method of the full-color adjustable carbon dot composite-based long-service-life room temperature phosphorescent material provided by the invention is simple, rapid and high in yield, does not need complex and expensive equipment and harsh operating environment, adopts cheap and easily-obtained raw materials, is low in preparation cost, and is easy to realize industrial production;
3) The full-color adjustable carbon dot composite-based long-life room temperature phosphorescent material provided by the invention has great potential application value in the fields of anti-counterfeiting, photoelectricity, photovoltaics, photocatalysis and the like.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1: schematic diagrams of the phosphor materials in examples 1 to 7 of the present invention;
FIG. 2: transmission electron micrographs of the blue to red phosphorescent carbon dot composites obtained in examples 1-7 of the invention;
FIG. 3: the X-ray diffraction spectra of the blue to red phosphorescent carbon dot composites obtained in examples 1-7 of the present invention;
FIG. 4: phosphorescence emission spectrograms of the blue to red phosphorescence carbon dot compounds obtained in the embodiments 1 to 7 of the invention under different excitation wavelengths;
FIG. 5: fourier transform infrared spectra of blue to red phosphorescent carbon dot composites obtained in examples 1-7 of the invention;
FIGS. 6 to 8: an X-ray photoelectron energy spectrum of the blue to red phosphorescent carbon dot composite obtained in examples 1 to 7 of the invention;
FIG. 9: fourier transform infrared spectrograms of carbon dots in blue to red phosphorescent carbon dot composites obtained in examples 1 to 7 of the invention;
FIG. 10: an X-ray photoelectron energy spectrum of carbon dots in the blue to red phosphorescent carbon dot composite obtained in examples 1 to 7 of the invention;
FIG. 11: phosphorescence attenuation curves of blue to red phosphorescent carbon dot composites obtained in examples 1 to 7 of the present invention;
FIG. 12: the temperature-variable phosphorescence attenuation curve of the yellow phosphorescent carbon dot compound obtained in the embodiment 3 of the invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
The invention prepares the long-life room temperature phosphorescent material by citric acid and boric acid, as shown in figure 1, the citric acid and the boric acid are completely dissolved, the solvent is completely volatilized, and the mixture of the citric acid and the boric acid is obtained; and heating and melting the mixture, and obtaining the long-life room-temperature phosphorescent material with different phosphorescent colors by changing the proportion of the citric acid and the boric acid and the heating and melting temperature or time after the boric acid and the citric acid completely react.
Example 1
6000mg of boric acid and 6mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block in an open manner, heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and heating is continued overnight so that the deionized water is fully volatilized, and a mixture a of the citric acid and the boric acid is obtained.
Heating and melting the mixture a of citric acid and boric acid at 170 ℃, cooling to room temperature after 5h to obtain the blocky blue phosphorescent carbon dot composite
Fig. 2a and 3 are transmission electron micrographs of the blue phosphorescent material obtained in this example, and an X-ray diffraction spectrum thereof shows that the prepared room temperature phosphorescent material is a carbon dot composite, the carbon dots are generated in situ by the reaction of citric acid and boric acid and are uniformly dispersed and embedded in boron oxide polycrystal, the boron oxide polycrystal is a bulk polycrystal generated by in situ dehydration of boric acid molecules, and the particle size of the carbon dots is 2.8nm. FIG. 4a is the phosphorescence spectrum at room temperature of the blue phosphorescent material obtained in this example, and the maximum phosphorescence emission peak is 512nm. FIGS. 9 and 10a are a Fourier transform infrared spectrum and an X-ray photoelectron spectrum of carbon dots in the blue phosphorescent material obtained in this example, and the degree of oxidation of the carbon dots is 28.16%.
Example 2
6000mg of boric acid and 100mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block in an open manner, heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and heating is continued overnight so that the deionized water is fully volatilized, and a mixture b of the citric acid and the boric acid is obtained.
Heating and melting the mixture of citric acid and boric acid at 170 ℃, cooling to room temperature after 5h to obtain the blocky green phosphorescent carbon dot compound
Fig. 2b and fig. 3 are transmission electron micrographs of the green phosphorescent material obtained in this example, respectively, and an X-ray diffraction spectrum thereof shows that the prepared room temperature phosphorescent material is a carbon dot composite, carbon dots are generated in situ by the reaction of citric acid and boric acid and are uniformly dispersed and embedded in boron oxide polycrystal, the boron oxide polycrystal is a block polycrystal generated by in situ dehydration of boric acid molecules, and the particle size of the carbon dots is 3.3nm. FIG. 4b is the phosphorescence spectrum at room temperature of the green phosphorescent material obtained in this example, and the maximum phosphorescence emission peak is 564nm. FIGS. 9 and 10b are a Fourier transform infrared spectrum and an X-ray photoelectron spectrum of carbon dots in the green phosphor material obtained in this example, in which the degree of oxidation of the carbon dots was 32.29%.
Example 3
6000mg of boric acid and 400mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block in an open manner, heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and heating is continued overnight so that the deionized water is fully volatilized, and a mixture c of the citric acid and the boric acid is obtained.
Heating and melting the mixture c of the citric acid and the boric acid at 180 ℃, cooling to room temperature after 5h to obtain the blocky yellow phosphorescent carbon dot compound
Fig. 2c and fig. 3 are transmission electron micrographs of the yellow phosphorescent material obtained in this example, respectively, and an X-ray diffraction spectrum thereof shows that the prepared room temperature phosphorescent material is a carbon dot composite, carbon dots are generated in situ by the reaction of citric acid and boric acid and are uniformly dispersed and embedded in boron oxide polycrystal, the boron oxide polycrystal is a bulk polycrystal generated by in situ dehydration of boric acid molecules, and the particle size of the carbon dots is 4.0nm. FIG. 4c is the phosphorescence spectrum at room temperature of the yellow phosphorescent material obtained in this example, and the maximum phosphorescence emission peak is 570nm. FIGS. 9 and 10c are a Fourier transform infrared spectrum and an X-ray photoelectron spectrum of the carbon dots in the yellow phosphorescent material obtained in the present example, wherein the degree of oxidation of the carbon dots is 36.85%.
Example 4
6000mg of boric acid and 900mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block in an open manner, heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and heating is continued overnight so that the deionized water is fully volatilized, and a mixture d of the citric acid and the boric acid is obtained.
Heating and melting the mixture of citric acid and boric acid at 200 deg.Cd, cooling to room temperature after 5h to obtain a massive orange phosphorescent carbon dot compound
Fig. 2d and fig. 3 are transmission electron micrographs of the orange phosphorescent material obtained in this example, respectively, and an X-ray diffraction spectrum thereof shows that the prepared room temperature phosphorescent material is a carbon dot composite, carbon dots are generated in situ by the reaction of citric acid and boric acid and are uniformly dispersed and embedded in boron oxide polycrystal, the boron oxide polycrystal is a bulk polycrystal generated by in situ dehydration of boric acid molecules, and the particle size of the carbon dots is 4.4nm. FIG. 4d is the phosphorescence spectrum at room temperature of the orange phosphorescent material obtained in the present example, and the maximum phosphorescence emission peak is 592nm. FIGS. 9 and 10d are a Fourier transform infrared spectrum and an X-ray photoelectron spectrum of carbon dots in the orange phosphorescent material obtained in this example, and the degree of oxidation of the carbon dots is 48.61%.
Example 5
6000mg of boric acid and 1000mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block in an open manner, heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and heating is continued overnight so that the deionized water is fully volatilized, and thus a mixture e of the citric acid and the boric acid is obtained.
Heating and melting the mixture e of citric acid and boric acid at 220 ℃, cooling to room temperature after 5h to obtain the blocky red phosphorescent carbon dot compound
Fig. 2e and fig. 3 are transmission electron micrographs of the red phosphorescent material obtained in this example, respectively, and an X-ray diffraction spectrum thereof shows that the prepared room temperature phosphorescent material is a carbon dot composite, carbon dots are generated in situ by the reaction of citric acid and boric acid and are uniformly dispersed and embedded in boron oxide polycrystal, the boron oxide polycrystal is bulk polycrystal generated by in situ dehydration of boric acid molecules, and the particle size of the carbon dots is 4.5nm. FIG. 4e is the phosphorescence spectrum at room temperature of the red phosphorescent material obtained in this example, and the maximum phosphorescence emission peak is 602nm. Fig. 9 and 10e are a fourier transform infrared spectrum and an X-ray photoelectron spectrum of the carbon dots in the red phosphorescent material obtained in this example, and the degree of oxidation of the carbon dots is 50.06%.
Example 6
6000mg of boric acid and 1200mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block in an open manner, heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and heating is continued overnight so that the deionized water is fully volatilized, and a mixture f of the citric acid and the boric acid is obtained.
Heating and melting the mixture f of citric acid and boric acid at 220 ℃, cooling to room temperature after 5h to obtain the blocky red phosphorescent carbon dot compound
Fig. 2f and fig. 3 are transmission electron micrographs of the red phosphorescent material obtained in this example, respectively, and an X-ray diffraction spectrum thereof shows that the prepared room temperature phosphorescent material is a carbon dot composite, carbon dots are generated in situ by the reaction of citric acid and boric acid and are uniformly dispersed and embedded in boron oxide polycrystal, the boron oxide polycrystal is bulk polycrystal generated by in situ dehydration of boric acid molecules, and the particle size of the carbon dots is 4.7nm. FIG. 4f is the room temperature phosphorescence spectrum of the red phosphorescent material obtained in this example, with the maximum phosphorescence emission peak being 621nm. FIGS. 9 and 10f are a Fourier transform infrared spectrum and an X-ray photoelectron spectrum of carbon dots in the red phosphorescent material obtained in this example, and the degree of oxidation of the carbon dots is 54.63%.
Example 7
6000mg of boric acid and 1600mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block in an open manner, heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and heating is continued overnight so that the deionized water is fully volatilized, and a mixture g of the citric acid and the boric acid is obtained.
Heating and melting mixture g of citric acid and boric acid at 220 deg.C, cooling to room temperature after 5 hr to obtain block-shaped red phosphorescent carbon dotComposite material
Fig. 2g and fig. 3 are transmission electron micrographs of the red phosphorescent material obtained in this example, respectively, and an X-ray diffraction spectrum thereof shows that the prepared room temperature phosphorescent material is a carbon dot composite, carbon dots are generated in situ by the reaction of citric acid and boric acid and are uniformly dispersed and embedded in boron oxide polycrystal, the boron oxide polycrystal is bulk polycrystal generated by in situ dehydration of boric acid molecules, and the particle size of the carbon dots is 5.3nm. FIG. 4g is the room temperature phosphorescence spectrum of the red phosphorescent material obtained in this example, with the maximum phosphorescence emission peak being 638nm. FIGS. 9 and 10g are a Fourier transform infrared spectrum and an X-ray photoelectron spectrum of carbon dots in the red phosphorescent material obtained in this example, and the degree of oxidation of the carbon dots is 58.16%.
With the increase of the amount of citric acid and the increase of the reaction temperature, the particle size of the carbon dots is increased, the degree of oxidation is increased, and the phosphorescence color of the carbon dot composite is red-shifted.
Comparative example 1
Adding 6000mg of boric acid and 1800mg of citric acid into a glass bottle filled with 25mL of deionized water, placing the glass bottle in a heating block after initial dissolution, heating the glass bottle on a heating table at 110 ℃ to fully dissolve the boric acid and the citric acid in the water, and continuously heating the glass bottle overnight to fully volatilize the deionized water to obtain a mixture h of the citric acid and the boric acid.
And heating and melting the mixture of the citric acid and the boric acid at 220 ℃ for h, and cooling to room temperature after 5h to obtain the blocky red phosphorescent carbon dot compound.
When the amount of citric acid is too large and boric acid is not enough to restrict the movement of carbon dots, the phosphorescent properties are degraded.
Comparative example 2
6000mg of boric acid and 6mg of citric acid were mixed to obtain a mixture a of citric acid and boric acid.
And heating and melting the mixture a of the citric acid and the boric acid at 170 ℃, cooling to room temperature after 5h, and obtaining the blocky blue phosphorescent carbon dot composite.
The direct mixing effect is poor, and the phosphorescent carbon dots are not uniformly distributed.
Comparative example 3
6000mg of boric acid and 1000mg of citric acid are added into a glass bottle filled with 25mL of deionized water, after initial dissolution, the glass bottle is placed in a heating block with an opening, the heating is carried out on a heating table at 110 ℃ so that the boric acid and the citric acid are fully dissolved in the water, and the heating is continued overnight so that the deionized water is fully volatilized, and a mixture e of the citric acid and the boric acid is obtained.
And heating and melting the mixture e of the citric acid and the boric acid at 240 ℃, cooling to room temperature after 5h, and obtaining the blocky red phosphorescent carbon dot composite.
If the temperature is too high, the carbonization degree of the carbon dots is too high, and the phosphor properties are greatly reduced. And when the temperature is lower than 170 ℃, boric acid cannot be melted to obtain boron oxide and phosphorus is not used.
And (3) application effect verification:
FIGS. 5-8 are the IR spectra and the photoelectron spectra of seven carbon dot composites prepared by the above 7 examples, respectively, and it can be seen that the prepared room temperature phosphorescent materials all contain C, B, O elements and-OH, C-C/C = C, C-O/C-O-B, C = O, O-C = O, BCO 2 ，B 2 O 3 And chemical bonds such as B-O.
FIGS. 11 and 12 are the phosphorescence attenuation curves of the seven carbon dot composites prepared in the above 7 examples and the temperature-variable phosphorescence attenuation curves of example 3, respectively, and FIG. 11 corresponds to FIG. 11 from top to bottom
FIG. 12 corresponds to 77K,100K,150K,200K,250K,300K, respectively, from top to bottom. It can be seen from the figure that the average phosphorescent lifetime of the prepared room temperature phosphorescent material can reach 113.90-581.76ms in a room temperature air environment, and can reach 1311.07ms at most in a 77K vacuum environment.
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (10)
1. The full-color adjustable long-life room temperature phosphorescent material is characterized by comprising boron oxide polycrystal and carbon dots; the carbon dots are generated in situ, uniformly dispersed and embedded in the boron oxide polycrystal; the boron oxide polycrystal is a blocky polycrystal generated by in-situ dehydration of boric acid molecules.
2. The long-life room temperature phosphorescent material as claimed in claim 1, wherein the carbon dots have a particle size of 2.8-5.3nm, a graphitization-like structure, and an oxidation degree of 28.16% -58.16%.
3. The long-life room temperature phosphorescent material of claim 1, wherein the long-life room temperature phosphorescent material comprises C, B, O elements and-OH, C-C/C = C, C-O/C-O-B, C = O, O-C = O, BCO 2 ，B 2 O 3 And a B-O bond.
4. The long-life room temperature phosphorescent material as claimed in claim 1, wherein the phosphorescence color of the long-life room temperature phosphorescent material can be adjusted from blue to red in room temperature air environment, the maximum emission peak range is 466-638nm, and the maximum emission peak range covers the whole visible light region.
5. The long-life room temperature phosphorescent material as claimed in claim 1, wherein the average phosphorescent lifetime of the long-life room temperature phosphorescent material is 113.90-581.76ms in room temperature air environment, the maximum phosphorescent lifetime is 1311.07ms in 77K vacuum environment, and the afterglow time recognizable to naked eyes is 5-12s in room temperature air environment.
6. A method for preparing the long-life room temperature phosphorescent material as claimed in claim 1, comprising the steps of:
s1, mixing reactants: completely dissolving citric acid and boric acid in a solvent, heating to completely volatilize the solvent, uniformly mixing the citric acid and the boric acid, and obtaining a mixture of the citric acid and the boric acid;
s2, preparation of the phosphorescent material: heating and melting the mixture of the boric acid and the citric acid obtained in the step S1 until the boric acid and the citric acid completely react;
and S3, obtaining the long-life room-temperature phosphorescent material with different phosphorescent colors by changing the proportion of citric acid and boric acid and the heating and melting temperature or time in the step S1.
7. The method according to claim 6, wherein in step S1, the citric acid and the boric acid are used in a ratio of 1-1600mg:6g.
8. The method according to claim 6, wherein in step S1, the heating is specifically: placing the solution of boric acid and citric acid in a container and heating the container in an open state; the heating temperature is 70-110 ℃, and the heating time is 7-12h.
9. The preparation method according to claim 6, wherein in the step S2, the heating and melting temperature is 170-220 ℃, and the heating reaction time is 3-6h.
10. Use of the long-lived room temperature phosphorescent material of claim 1 in multi-dimensional information encryption.
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