CN115448262A - Wide-temperature-range long-life boron nitride phosphor material and preparation method and application thereof - Google Patents
Wide-temperature-range long-life boron nitride phosphor material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a wide-temperature-range long-life boron nitride phosphor material, and a preparation method and application thereof. The preparation method comprises the following steps: dissolving boric acid and a fluorine source in deionized water, adding a nitrogen carbon source, stirring and mixing uniformly, and then reacting; after the reaction is finished, cooling, washing and drying are carried out, so that the wide-temperature-range long-life boron nitride phosphorescent material is obtained. The preparation method disclosed by the invention is simple in preparation process, low in cost, green and environment-friendly, does not need complex post-treatment, can be used for rapidly realizing large-batch preparation, and the obtained wide-temperature-range phosphorescent material is low in toxicity and good in light stability. The wide-temperature-range long-life boron nitride phosphorescent material powder obtained by the invention has blue fluorescence and green phosphorescence, and the phosphorescence emission can cover a high-temperature environment of 150 ℃, so that the wide-temperature-range long-life boron nitride phosphorescent material powder has a wide application prospect.
Description
Technical Field
The invention relates to a wide-temperature-range long-life boron nitride phosphor material, and a preparation method and application thereof, and belongs to the technical field of functional materials.
Background
The Room Temperature Phosphorescence (RTP) material can emit fluorescence under the excitation of a light source, and can emit phosphorescence for eliminating background interference after removing exciting light, and the excellent optical property enables the RTP material to be widely applied to the aspects of information encryption, photoelectricity, photodynamic therapy, biological imaging and the like. The traditional room temperature phosphorescent material such as organic metal complex has the defects of high manufacturing cost and high toxicity; although the pure organic compound solves the above problems, the triplet excitons are likely to be affected by environments such as temperature and humidity, and the like, because the spin-orbit coupling is weak and the nonradiative transition rate constant is large, thereby causing nonradiative transition deactivation. At present, methods for obtaining efficient phosphorescence include promoting intersystem crossing from singlet state to triplet state, such as introduction of heavy atom substituents to increase spin-orbit coupling; inhibit the non-radiative inactivation rate, such as building a rigid environment, and reduce the vibration of molecules.
There are many patent documents on room temperature phosphorescent materials. For example: chinese patent document CN108440603A reports a preparation method of an organometallic complex phosphorescent material, wherein a ligand containing a pyridine unit is introduced into an organometallic complex of cyclometalated iridium to obtain a heterocomplex phosphorescent material of iridium, but the material contains toxic metal elements, pollutes the environment and limits the application range of the material. Chinese patent document CN113717151a reports a preparation method of a pure organic room temperature phosphorescent compound, which takes potassium tert-butoxide, carbazole, and 2-cyano-6-fluoropyridine as raw materials, and N, N-Dimethylformamide (DMF) as a solvent, and the pure organic room temperature phosphorescent compound is prepared by stirring and heating. Chinese patent document CN113817460A provides a full-color adjustable long-life room temperature phosphorescent material, which is a compound composed of boron oxide polycrystal and carbon dots, wherein the carbon dots are generated in situ, uniformly dispersed and embedded in the boron oxide polycrystal, and the boron oxide polycrystal is a block polycrystal generated by in-situ dehydration of boric acid molecules. Although this method achieves a tunable phosphorescence wavelength, the longest phosphorescence lifetime at room temperature is 581ms, and involves embedding the phosphorescent material in a specific matrix, which limits its application range. At present, room temperature phosphorescent materials are often serious in non-radiative transition under high temperature conditions, the phosphorescent efficiency is greatly reduced, and materials which still maintain phosphorescent emission under high temperature conditions are explored, so that the research value is greater.
Many current phosphorescent materials require loading into a matrix to block contact with oxygen and water and reduce molecular vibration to exhibit their properties. The room temperature phosphorescent material without the matrix and with good thermal stability and chemical stability has greater application potential. Therefore, it is urgent to prepare a wide temperature range phosphorescent material which has long service life, low toxicity and low cost and is easy to produce in a large scale.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a wide-temperature-range long-life boron nitride phosphor material, and a preparation method and application thereof. The invention takes boric acid, a fluorine source and a nitrogen-carbon source as raw materials, and prepares the non-matrix fluorine-carbon-oxygen doped boron nitride phosphorescent material after the boric acid, the fluorine source and the nitrogen-carbon source are dissolved in water and calcined. The phosphorescent material prepared by the invention has long phosphorescence service life, low toxicity, good thermal stability and chemical stability, and still has phosphorescence at 150 ℃, thereby realizing wide-temperature-range phosphorescence emission. The preparation method has simple steps and low cost, and is easy for large-scale production.
The technical scheme of the invention is as follows:
a preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
dissolving boric acid and a fluorine source in deionized water, adding a nitrogen carbon source, stirring and mixing uniformly, and then reacting; after the reaction is finished, cooling, washing and drying are carried out, so that the wide-temperature-range long-life boron nitride phosphorescent material is obtained.
According to the present invention, the ratio of the number of moles of the boric acid to the volume of the deionized water is 0.0001 to 0.001mol, and is more preferably 0.0003 to 0.0005 mol.
Preferably according to the invention, the fluorine source is ammonium fluoride and/or ammonium fluoroborate; the molar ratio of the fluorine source to boric acid is 0.02 to 0.3, and more preferably 0.1 to 0.2.
According to the invention, the nitrogen carbon source is preferably one or a combination of more than two of ethylenediamine, diethylamine, propylenediamine, butylenediamine, oleylamine and ethanolamine, and is more preferably ethylenediamine; the molar ratio of the nitrogen carbon source to boric acid is 0.3 to 3:1, more preferably 0.5 to 1.5.
According to the invention, the reaction temperature is preferably 200-400 ℃, and more preferably 250-300 ℃; the reaction time is 10 to 90min, and more preferably 20 to 30min, and the reaction is performed under an open heating condition, for example, the reaction may be performed in a muffle furnace under an open heating condition.
According to the invention, the cooling is natural cooling to room temperature, wherein the room temperature is 25 +/-5 ℃.
According to the invention, the washing is to disperse the solid obtained by the reaction in ethanol for centrifugation, wherein the centrifugation speed is 5000-10000 rmp, and is further preferably 7000-8000 rmp; centrifuging for 5-15min, preferably 10min, removing supernatant, and repeating for 5-8 times.
According to the invention, the drying is preferably carried out at 40-90 ℃ for 8-15 h, more preferably at 50-60 ℃ for 10-12 h.
The wide-temperature-range long-life boron nitride phosphorescent material is prepared by the preparation method.
According to the invention, the wide-temperature-range long-life boron nitride phosphorescent material is applied to information encryption or cell imaging.
The invention has the following technical characteristics and beneficial effects:
1. according to the invention, the fluorine-carbon-oxygen defect is introduced into the boron nitride, and the existence of the carbon-oxygen defect can effectively reduce the optical band gap of the boron nitride, so that blue fluorescence emission and green phosphorescence emission of the boron nitride are realized; the surface of a sample obtained by reacting in the form of aqueous solution contains rich functional groups and has good water solubility, the existence of hydroxyl, amino and fluorine substituents on the surface of the obtained material can enhance the interaction of hydrogen bonds among molecules, inhibit the vibration and rotation of the molecules, reduce the quenching of water and oxygen to phosphorescence, realize the phosphorescence service life as long as 1.17s, and observe the phosphorescence lasting for 10s under naked eyes; meanwhile, after fluorine doping, the material has high-temperature phosphorescence property, phosphorescence can be still observed at the high temperature of 150 ℃, and the boron nitride phosphorescence material has the phosphorescence property in a wider temperature range.
2. The preparation method disclosed by the invention is simple in preparation process, low in cost, green and environment-friendly, does not need complex post-treatment, and can be used for quickly realizing large-batch preparation. The obtained product has low toxicity, good light stability and huge application prospect.
Drawings
FIG. 1 is an optical photograph of the wide temperature range long-life boron nitride phosphorescent material powder prepared in example 1 in daylight (a), under a 405nm ultraviolet lamp (b) and after the 405nm ultraviolet lamp is turned off (c).
FIG. 2 is an atomic force micrograph and profile height profile (inset) of a wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 3 is a fluorescence emission spectrum of a wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 4 is a phosphorescence emission spectrum of a wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 5 is a time-resolved spectrum of a wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 6 is an X-ray diffraction pattern of the wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 7 is a Fourier transform infrared spectrum of a wide temperature range long life boron nitride phosphorescent material prepared in example 1.
FIG. 8 is an X-ray photoelectron spectroscopy analysis chart of the wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 9 is a graph showing the phosphorescence effect of the wide temperature range long-life boron nitride phosphorescent material prepared in example 1 under different temperature conditions and the carbon-oxygen doped boron nitride room temperature phosphorescent material prepared in comparative example 1 after being irradiated with a 405nm UV lamp at 150 ℃ and turned off.
FIG. 10 is a temperature-varying phosphorescence emission spectrum of the wide temperature range long-life boron nitride phosphorescent material prepared in example 1.
FIG. 11 is a graph showing the effect of the pen-written numbers of the wide-temperature-range long-life boron nitride phosphorescent anti-counterfeiting ink prepared in example 1 under the irradiation of a 405nm ultraviolet lamp (a) and after the ultraviolet lamp (b) is turned off.
Fig. 12 is a phosphorescence image of chinese characters under irradiation of uv lamps at room temperature (a) and at a high temperature of 150 ℃ (b) and turned off, drawn together by the wide temperature range long-life boron nitride phosphorescent material prepared in example 1 and the carbon-oxygen doped boron nitride room temperature phosphorescent material prepared in comparative example 1.
Detailed Description
The invention is further illustrated by the following specific examples, which are provided for the understanding of the invention only and are not intended to be limiting.
The methods described in the examples are conventional methods unless otherwise specified; the reagents used are commercially available without specific indication.
Example 1
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 50mg of ammonium fluoroborate are dissolved in 10mL of deionized water, 202mg of ethylenediamine is added after 30min of magnetic stirring, and the magnetic stirring is continued for 20min to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace and heated open to the atmosphere, reacted at 300 ℃ for 25min, and then taken out and cooled naturally to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, and the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) drying the centrifuged sample in an oven at 60 ℃ for 12h, and then grinding to obtain the wide-temperature-range long-life boron nitride phosphorescent material.
The optical photographs of the wide temperature range long-life boron nitride phosphor powder prepared in this example under sunlight (a), under a 405nm ultraviolet lamp (b) and after the 405nm ultraviolet lamp is turned off (c) are shown in fig. 1. As can be seen from FIG. 1, the obtained product is light yellow under sunlight, and emits blue fluorescence under the irradiation of an ultraviolet lamp, and emits green phosphorescence after the ultraviolet light source is turned off.
The atomic force microscopic image and the profile height distribution of the wide-temperature-range long-life boron nitride phosphorescent material prepared in the embodiment are shown in fig. 2. As can be seen from FIG. 2, the prepared boron nitride phosphorescent material is uniformly distributed nanoparticles, and the profile height is 2-3 nm.
The fluorescence emission spectrum of the wide temperature range long-life boron nitride phosphorescent material prepared in this example is shown in fig. 3. As can be seen from FIG. 3, the optimal excitation wavelength is 340nm and the optimal emission wavelength is 410nm.
The phosphorescence emission spectrum of the wide-temperature range long-life boron nitride phosphorescent material prepared in this example is shown in fig. 4. As can be seen from FIG. 4, the optimal excitation wavelength is 360nm and the optimal emission wavelength is 525nm.
The time-resolved spectrum of the wide-temperature-range long-life boron nitride phosphorescent material prepared in the example is shown in fig. 5, and the data fitting result shows that the phosphorescence decay life is 1.17 seconds.
The X-ray diffraction pattern of the wide temperature range long-life boron nitride phosphorescent material prepared in this example is shown in FIG. 6. As can be seen from fig. 6, the broad diffraction peak in the vicinity of 23 degrees corresponds to the (002) crystal plane of hexagonal boron nitride, and the diffraction peak in the vicinity of 43 degrees corresponds to the (100) crystal plane. The diffraction peak is shifted to a small angle compared to pure hexagonal boron nitride, which is caused by the enlargement of the interplanar spacing due to the incorporation of the heteroatom.
The Fourier transform infrared spectrum of the wide temperature range long-life boron nitride phosphorescent material prepared in the example is shown in FIG. 7. From FIG. 7, it can be seen that the light source is located at 1337cm -1 And 761cm -1 The absorption peaks correspond to the stretching and bending vibration of B-N respectively; is located at 1043cm -1 And 708cm -1 The absorption peaks correspond to the stretching and bending vibration of B-O respectively; is located at 3210cm -1 And 3120cm -1 Absorption peaks at (A) correspond to-OH and-NH, respectively 2 Vibration of (2); at 1606cm -1 The absorption peak at (b) corresponds to the vibration of C = N.
An X-ray photoelectron spectroscopy analysis chart of the wide-temperature-range long-life boron nitride phosphorescent material prepared in this example is shown in fig. 8. As can be seen in fig. 8, in addition to boron and nitrogen, the elements carbon, oxygen, and fluorine are also present, indicating successful incorporation of the elements carbon, oxygen, and fluorine.
The effect of the wide temperature range long-life boron nitride phosphor powder prepared in this example at different temperatures and the carbon-oxygen doped boron nitride room temperature phosphor prepared in comparative example 1 after irradiation and shutdown with a 405nm uv lamp at 150 ℃ is shown in fig. 9. It can be seen from the figure that the phosphorescence time of the material of the embodiment is gradually shortened along with the increase of the temperature, but the material still has phosphorescence emission at 150 ℃, which shows that the boron nitride phosphorescence material prepared by the invention has phosphorescence properties in a wider temperature range, while the material of the comparison example to the material of the comparison example 1 has no phosphorescence at 150 ℃.
The temperature-variable phosphorescence emission spectrum of the wide-temperature-range long-life boron nitride phosphorescent material prepared in the embodiment is shown in fig. 10. It can be seen from the graph that the phosphorescence intensity gradually decreases with increasing temperature, but the phosphorescence emission is still strong at 150 ℃.
The wide-temperature-range long-life boron nitride phosphorescent material prepared by the embodiment is dissolved in deionized water, and the concentration is 50mg/mL, so that the anti-counterfeiting ink is obtained. As shown in FIG. 11, "101010" was written with a pen on cellulose paper using the prepared forgery preventive ink, and the graphs of the effects thereof during irradiation of an ultraviolet lamp at 405nm and after turning off are shown in FIG. 11 (a) and FIG. 11 (b), respectively.
The wide temperature range long-life boron nitride phosphorescent material prepared in the embodiment and the carbon-oxygen doped boron nitride room temperature phosphorescent material prepared in the comparative example 1 are dissolved in deionized water, the concentrations of the materials are both 50mg/mL, ink is obtained, and Chinese character 'learning' is drawn together, namely, the ink prepared from the phosphorescent material in the embodiment 1 is used for drawing a 'son' word part, and the ink prepared from the phosphorescent material in the comparative example 1 is used for drawing the rest part. As shown in FIG. 12, the phosphorescence image after irradiation with a 405nm UV lamp at room temperature and turning off is shown in FIG. 12 (a), and the phosphorescence image after heating at 150 ℃ for 5min on a hot stage and irradiation with a 405nm UV lamp and turning off is shown in FIG. 12 (b). It can be seen from fig. 12 that the material shows a complete "learning" character at room temperature, and only the "son" character drawn by the material of example 1 can show after being heated at high temperature, which indicates that the material has high-temperature phosphorescence property after fluorine doping, can resist high temperature, and can be applied to higher-level anti-counterfeiting.
Example 2
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 50mg of ammonium fluoroborate are dissolved in 10mL of deionized water, 249mg of propane diamine is added after magnetic stirring is carried out for 30min, and magnetic stirring is continued for 20min to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace and heated open to the atmosphere, reacted at 300 ℃ for 25min, and then taken out and cooled naturally to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, and the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) drying the centrifuged sample in an oven at 60 ℃ for 12h, and then grinding to obtain the wide-temperature-range long-life boron nitride phosphorescent material.
Example 3
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 20mg of ammonium fluoride are dissolved in 10mL of deionized water, 202mg of ethylenediamine is added after 30min of magnetic stirring, and the magnetic stirring is continued for 20min to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace and heated open to the atmosphere, reacted at 300 ℃ for 25min, and then taken out and cooled naturally to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, and the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) drying the centrifuged sample in an oven at 60 ℃ for 12h, and then grinding to obtain the wide-temperature-range long-life boron nitride phosphorescent material.
Example 4
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 10mg of ammonium fluoroborate are dissolved in 10mL of deionized water, 202mg of ethylenediamine is added after 30min of magnetic stirring, and the magnetic stirring is continued for 20min to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace and heated open to the atmosphere, reacted at 300 ℃ for 25min, and then taken out and cooled naturally to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, and the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) drying the centrifuged sample in an oven at 60 ℃ for 12h, and then grinding to obtain the wide-temperature-range long-life boron nitride phosphorescent material.
Example 5
A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
206mg of boric acid and 50mg of ammonium fluoroborate are dissolved in 10mL of deionized water, 303mg of ethylenediamine is added after 30min of magnetic stirring, and the magnetic stirring is continued for 20min to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace and heated open to the atmosphere, reacted at 300 ℃ for 25min, and then taken out and cooled naturally to room temperature. The resulting product was dispersed in 30ml ethanol and centrifuged at 8000rmp for 10min, and the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) drying the centrifuged sample in an oven at 60 ℃ for 12h, and then grinding to obtain the wide-temperature-range long-life boron nitride phosphorescent material.
Example 6
A wide temperature range long life boron nitride phosphorescent material is prepared as described in example 1, except that: the reaction time was 50min.
Example 7
A wide temperature range long life boron nitride phosphorescent material was prepared as described in example 1, except that the reaction temperature was 350 ℃.
Comparative example 1
A preparation method of a carbon-oxygen doped boron nitride room temperature phosphorescent material comprises the following steps:
206mg of boric acid is dissolved in 10mL of deionized water, 202mg of ethylenediamine is added after 30min of magnetic stirring, and the magnetic stirring is continued for 20min to obtain a uniformly mixed solution. The solution was transferred to a muffle furnace and heated open to the atmosphere, reacted at 300 ℃ for 25min, and then taken out and cooled naturally to room temperature. The resulting product was dispersed in 30mL of ethanol and centrifuged at 8000rmp for 10min, and the pellet was taken and centrifuged 5 times with ethanol repeatedly. And (3) drying the centrifuged sample in an oven at 60 ℃ for 12h, and then grinding to obtain the carbon-oxygen doped boron nitride room temperature phosphorescent material.
The phosphor decay life time of the room temperature phosphor material of boron nitride doped with carbon and oxygen prepared by the comparative example is 0.89 second, which is lower than that of the example 1 of the present invention, and it can be seen from fig. 9 and 12 that it does not have the property of high temperature phosphor.
Claims (10)
1. A preparation method of a wide-temperature-range long-life boron nitride phosphorescent material comprises the following steps:
dissolving boric acid and a fluorine source in deionized water, adding a nitrogen carbon source, stirring and mixing uniformly, and then reacting; after the reaction is finished, cooling, washing and drying are carried out to obtain the boron nitride phosphorescent material with wide temperature range and long service life.
2. The preparation method of the wide-temperature-range long-life boron nitride phosphorescent material as claimed in claim 1, wherein the ratio of the number of moles of the boric acid to the volume of the deionized water is 0.0001 to 0.001mol, 1mL, preferably 0.0003 to 0.0005 mol.
3. The method for preparing a wide temperature range long life boron nitride phosphorescent material as claimed in claim 1, wherein the fluorine source is ammonium fluoride and/or ammonium fluoroborate; the molar ratio of the fluorine source to the boric acid is 0.02 to 0.3, preferably 0.1 to 0.2.
4. The method for preparing the wide-temperature-range long-life boron nitride phosphorescent material according to claim 1, wherein the nitrogen carbon source is one or a combination of more than two of ethylenediamine, diethylamine, propylenediamine, butylenediamine, oleylamine and ethanolamine, preferably ethylenediamine.
5. The preparation method of the wide-temperature-range long-life boron nitride phosphorescent material as claimed in claim 1, wherein the molar ratio of the nitrogen carbon source to the boric acid is 0.3-3:1, preferably 0.5-1.5.
6. The preparation method of the wide-temperature-range long-life boron nitride phosphorescent material as claimed in claim 1, wherein the reaction temperature is 200-400 ℃, preferably 250-300 ℃; the reaction time is 10 to 90min, preferably 20 to 30min.
7. The method for preparing the wide-temperature-range long-life boron nitride phosphorescent material according to claim 1, wherein the cooling is natural cooling to room temperature; the washing is to disperse the solid obtained by the reaction in ethanol for centrifugation, wherein the centrifugal rotation speed is 5000-10000 rmp, and is preferably 7000-8000 rmp; centrifuging for 5-15min, preferably 10min, removing supernatant, and repeating for 5-8 times.
8. The method for preparing the wide-temperature-range long-life boron nitride phosphorescent material as claimed in claim 1, wherein the drying is performed at 40-90 ℃ for 8-15 h, preferably at 50-60 ℃ for 10-12 h.
9. A wide-temperature-range long-life boron nitride phosphorescent material, which is characterized by being prepared by the preparation method of claim 1.
10. Use of the wide temperature range long life boron nitride phosphorescent material of claim 9 for information encryption or cellular imaging.
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