CN117165289B - Waterproof carbon quantum dot matrix composite phosphorescence material and preparation method thereof - Google Patents
Waterproof carbon quantum dot matrix composite phosphorescence material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a water-resistant carbon quantum dot matrix composite phosphorescent material and a preparation method thereof, and belongs to the technical field of phosphorescent luminescent materials. The preparation method comprises the following steps: and mixing a carbon source with urea, performing hydrothermal reaction, and collecting solids after the reaction is finished to obtain the water-resistant carbon quantum dot matrix composite phosphorescence material. The carbon source is a compound obtained by substituting at least one hydrogen atom on a benzene ring with a boric acid group and a chromophoric group, and is preferably 3-aminophenylboric acid. The water-resistant carbon quantum dot matrix composite phosphorescence material prepared by the method can generate blue phosphorescence which lasts for about 40s after being irradiated by ultraviolet light of 275nm, the service life can reach more than 2s, cyanuric acid crystals are formed on the surface of a carbon dot material, molecular vibration of carbon dots can be restrained, quenching of dissolved oxygen in water is effectively isolated, and therefore good phosphorescence performance can be maintained in water.
Description
Technical Field
The invention belongs to the technical field of phosphorescent luminescent materials, and particularly relates to a water-resistant carbon quantum dot matrix composite phosphorescent material and a preparation method thereof.
Background
The room temperature phosphorescent material has special optical properties of long afterglow after excitation and stopping, so that the room temperature phosphorescent material has unique advantages when being applied to the application fields of biological imaging, anti-counterfeiting, information encryption, luminescent devices and the like. However, most of the conventional room temperature phosphorescent materials are pure organic matters or doped with heavy metal atoms, so that the defects of toxicity, complex preparation process, high cost and the like always exist, in addition, most of the phosphorescent materials are easily quenched by dissolved oxygen and solvent auxiliary relaxation in water in aqueous solution, and most of RTP materials can only play a phosphorescent role under the anhydrous solid state condition.
Compared with the traditional room temperature phosphorescence material, the carbon dot has the characteristics of high biocompatibility, low toxicity, easy preparation, low cost and the like, and has excellent optical performance, so the carbon dot is an ideal material for room temperature phosphorescence research. Carbon dots refer to zero-dimensional carbon nanomaterials of less than 10nm in size, mostly having a skeletal structure of sp 2 hybridized carbon, the lattice spacing of which is consistent with that of graphite or amorphous carbon. The surface of the carbon dot contains rich surface state, and can display bright and visible fluorescence and afterglow under the excitation of light with specific wavelength. The carbon dot has the advantages of good chemical stability, controllable luminescent color, high fluorescence quantum yield, light bleaching resistance and the like, and simultaneously has the characteristics of low toxicity, environment friendliness, wide carbon source, low preparation cost and the like. However, the existing phosphorescent carbon dot material has the problems of short service life, phosphorescence quenching in water environment and the like, which hinders further research and application of the room-temperature phosphorescent material.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a water-resistant carbon quantum dot matrix composite phosphorescent material and a preparation method thereof, and the preparation method is simple in steps, and can prepare the composite phosphorescent material with longer phosphorescent service life and good water-resistant effect, so that the problems of shorter service life, phosphorescent quenching under water environment and the like of the conventional phosphorescent material are solved.
In order to achieve the above object, the present invention provides the following technical solutions:
A preparation method of a water-resistant carbon quantum dot matrix composite phosphor material comprises the following steps: and mixing a carbon source with urea, performing hydrothermal reaction, and collecting solids after the reaction is finished to obtain the water-resistant carbon quantum dot matrix composite phosphorescence material.
Preferably, the carbon source is a compound containing a benzene ring, and at least 1 hydrogen atom on the benzene ring is substituted with a boric acid group.
Preferably, the carbon source is a compound containing a benzene ring, and 1 to 2 hydrogen atoms on the benzene ring are substituted with a boric acid group.
Preferably, the carbon source is a compound containing a benzene ring, and 2 to 4 hydrogen atoms on the benzene ring are independently substituted with an amino group or a carboxyl group.
Preferably, the mixed solution of the carbon source and urea is placed in heating equipment to react for 3-5 hours at 190-220 ℃.
Preferably, the carbon source includes at least one of 3-aminophenylboronic acid, phenylboronic acid, 1, 3-phenyldiboronic acid, 2-aminophenylboronic acid, 4-aminophenylboronic acid and 4-carboxyphenylboronic acid.
Preferably, the mixed solution of the carbon source and urea is poured into an open container, then the container mouth is covered with a metal foil, and the container is placed in a heating apparatus to react.
Preferably, the mass ratio of the carbon source to urea is (0.020-0.100): 3.
Preferably, the mass ratio of the carbon source to urea is 0.025:3 and the reaction time is 3 hours.
The invention also provides a water-resistant carbon quantum dot matrix composite phosphorescent material, which is prepared by adopting any one of the methods.
The beneficial effects are that:
(1) The phosphorescence carbon quantum dot based composite material is a solid carbon quantum dot based composite material, can keep phosphorescence performance in an aqueous environment, does not contain metal elements, has low toxicity and simple preparation process.
(2) The initial product of the solid carbon quantum dot matrix composite material prepared by the invention is crystalline solid, white powder is obtained after grinding, and under the irradiation of 275nm excitation light, the emission peak position of the product is positioned near 448nm, blue phosphorescence can be emitted, and the phosphorescence life can reach more than 2 s.
(3) The preparation of the solid carbon quantum dot matrix composite material is carried out under normal-pressure hydrothermal conditions, the reaction time is short, the reaction conditions are easy to be achieved, and the preparation process is simple.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Wherein:
FIG. 1 is a photograph of the u-CDs provided in example 1 of the present invention under irradiation of a fluorescent lamp, a 365nm ultraviolet lamp and a 365nm ultraviolet lamp.
FIG. 2 shows the phosphorescence emission spectra of u-CDs provided in example 1 of the present invention at different excitation wavelengths.
FIG. 3 shows fluorescence emission spectra of u-CDs according to example 1 of the present invention at different excitation wavelengths.
FIG. 4 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 1 of the present invention.
FIG. 5 is an XRD spectrum for u-CDs provided in example 1 of the present invention.
FIG. 6 is a photograph showing the phosphorescence emission of u-CDs according to example 1 of the present invention after excitation by 254nm and 365nm excitation light in a submerged state.
FIG. 7 is a FT-IR spectrum of u-CDs provided in example 1 of the invention.
FIG. 8 is a phosphorescence emission spectrum of u-CDs provided in example 2 of the present invention at an optimal excitation wavelength.
FIG. 9 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 2 of the present invention.
FIG. 10 is a phosphorescence emission spectrum of u-CDs provided in example 3 of the present invention at an optimal excitation wavelength.
FIG. 11 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 3 of the present invention.
FIG. 12 is a phosphorescent emission spectrum of u-CDs according to example 4 of the present invention at an optimal excitation wavelength.
FIG. 13 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 4 of the present invention.
FIG. 14 is a phosphorescence emission spectrum of u-CDs provided in example 5 of the present invention at an optimal excitation wavelength.
FIG. 15 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 5 of the present invention.
FIG. 16 is a graph showing the phosphorescence emission spectrum of u-CDs of example 6 of the present invention at an optimal excitation wavelength.
FIG. 17 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 6 of the present invention.
FIG. 18 is a phosphorescent emission spectrum of u-CDs according to example 7 of the present invention at an optimal excitation wavelength.
FIG. 19 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 7 of the present invention.
FIG. 20 is a graph showing the phosphorescence emission spectrum of u-CDs according to example 8 of the present invention at an optimal excitation wavelength.
FIG. 21 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 8 of the present invention.
FIG. 22 is a graph showing the phosphorescence emission spectrum of u-CDs according to example 9 of the present invention at an optimal excitation wavelength.
FIG. 23 is a graph showing the room temperature phosphorescence attenuation spectrum of u-CDs provided in example 9 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Aiming at the problems of shorter phosphorescence service life and no water resistance of the existing phosphorescence material, the invention provides a water-resistant carbon quantum dot matrix composite phosphorescence material which has the advantages of simple preparation method, easy popularization, longer phosphorescence service life and better water resistance, and can normally emit phosphorescence in an underwater environment.
The preparation method of the water-resistant carbon quantum dot matrix composite phosphorescent material comprises the following steps: and mixing a carbon source with urea, performing hydrothermal reaction, and collecting solids after the reaction is finished to obtain the water-resistant carbon quantum dot matrix composite phosphorescence material.
In a preferred embodiment of the invention, the carbon source is a compound comprising a benzene ring, and at least 1 (e.g., 2,3,4, 5, 6) hydrogen atoms on the benzene ring are replaced with a boronic acid group.
In a preferred embodiment of the present invention, the carbon source is a compound containing a benzene ring, and 1 to 2 hydrogen atoms on the benzene ring are substituted with a boric acid group.
In a preferred embodiment of the present invention, the carbon source is a compound containing a benzene ring, and 2 to 4 hydrogen atoms on the benzene ring are independently substituted with an amino group or a carboxyl group.
In a preferred embodiment of the present invention, the mixed solution of the carbon source and urea is placed in a heating apparatus and reacted at 190 to 220 ℃ (e.g., 191 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 219 ℃) for 3 to 5 hours (e.g., 3.5 hours, 4.0 hours, 4.5 hours).
In a preferred embodiment of the present invention, the carbon source includes at least one of 3-aminophenylboronic acid, phenylboronic acid, 1, 3-phenyldiboronic acid, 2-aminophenylboronic acid, 4-aminophenylboronic acid and 4-carboxyphenylboronic acid.
In a preferred embodiment of the invention, the mixed solution of carbon source and urea is poured into an open container, then the container mouth is covered with a metal foil, and the container is placed in a heating device for reaction.
In a preferred embodiment of the invention, the mass ratio of carbon source to urea is (0.020-0.100): 3, e.g. 0.021:3, 0.025:3, 0.030:3, 0.040:3, 0.050:3, 0.060:3, 0.070:3, 0.080:3, 0.090:3, 0.099:3.
In a preferred embodiment of the invention, the mass ratio of the carbon source to urea is 0.025:3 and the reaction time is 3 hours.
The invention also provides a water-resistant carbon quantum dot matrix composite phosphorescent material, which is prepared by adopting any one of the methods.
The water-resistant carbon quantum dot matrix composite phosphor material and the preparation method thereof are described in detail by specific examples.
The sources of the individual raw materials in the following examples are as follows:
3-aminophenylboronic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
urea: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
2-aminophenylboronic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
4-aminophenylboronic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
3-carboxyphenylboronic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
4-carboxyphenylboronic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
phenylboronic acid: analytically pure, purchased from Shanghai Taitan technologies Co., ltd;
1, 3-phenyldiboronic acid: analytically pure, purchased from Shanghai Taitan technologies Co.
In the following examples, the phosphorescent lifetime of u-CDs is calculated by the formula:
Wherein, tau avg is the phosphorescence lifetime of u-CDs, alpha i is an exponential factor, tau i is lifetime, alpha i、τi is obtained by fitting a lifetime curve through room temperature phosphorescence attenuation spectrum of a sample, and related fitting process is carried out by using Origin software, and other software with the same function can be used for processing.
Example 1
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 25mg of 3-aminophenylboronic acid was added to 3g of urea, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction at 200 ℃ for 3 hours.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
As shown in FIG. 1, the u-CDs powder prepared in this example was irradiated with a fluorescent lamp and a 365nm ultraviolet lamp, respectively, and it was found that the u-CDs powder was white solid powder under the irradiation of sunlight (left side of the figure), and the u-CDs powder emitted bright blue fluorescence under the irradiation of 365nm ultraviolet lamp (right side of the figure), and the u-CDs powder emitted bright cyan phosphorescence after the 365nm ultraviolet lamp was turned off.
FIG. 2 shows the phosphorescence emission spectra of the u-CDs powder prepared in this example at different excitation wavelengths, where the u-CDs phosphorescence emission has an optimal excitation wavelength of 275nm and a corresponding emission peak position of 448nm, and may generate blue phosphorescence.
FIG. 3 shows fluorescence emission spectra of the u-CDs powder prepared in this example at different excitation wavelengths, wherein the optimal excitation wavelength of the u-CDs fluorescence prepared in this example is 260nm, and the corresponding emission peak position is 340nm.
FIG. 4 shows the phosphorescence attenuation spectrum of the u-CDs powder prepared in this example, and shows that the remaining afterglow time reaches about 40s, and after fitting by a three-exponential function, the phosphorescence lifetime of the u-CDs is calculated to be 2.351s according to the formula τ avg＝Σαiτi 2/αiτi.
FIG. 5 is an XRD diffraction pattern of u-CDs and cyanuric acid prepared in this example, where cyanuric acid crystals are present in the u-CDs powder material prepared in this example, and the crystal rigid network formed by cyanuric acid can not only effectively inhibit molecular vibration of carbon dots and reduce non-radiative transition, but also effectively isolate quenching of dissolved oxygen in water by carbon dots under the coating of cyanuric acid, so that u-CDs can maintain their phosphorescent properties in an aqueous environment.
The u-CDs powder prepared in this example was mixed with water in a test tube and excited with excitation light having a wavelength of 254nm and 365nm, respectively, and after immersing the u-CDs powder prepared in this example in water, excitation was performed with excitation light having a wavelength of 254nm to generate blue phosphorescence, excitation was performed with excitation light having a wavelength of 365nm to generate cyan phosphorescence, as shown in FIG. 6, which proves that the u-CDs powder prepared in this example was excellent in water resistance.
In addition, different solutions with pH values of 0-14 are used for respectively replacing water for soaking, and when the solution is soaked for more than one week, the solution is excited by using excitation light with wavelength of 254nm and 365nm, and good phosphorescence performance can be maintained.
FIG. 7 is a FT-IR spectrum of u-CDs powder prepared in the present example, showing that the FT-IR spectrum of u-CDs powder shows distinct peaks at wave numbers of 3000-3200, 1722, 1463, 1398cm -1, corresponding to functional groups of N-H, C = O, C-N, C =N, respectively.
Example 2
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 50mg of 3-aminophenylboronic acid is added to 3g of urea, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction at 200 ℃ for 3 hours.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 8 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, where the u-CDs prepared in this example has an emission peak position of 447nm, which can produce blue phosphorescence.
FIG. 9 shows the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining afterglow time is more than 35s, and the phosphorescence lifetime of u-CDs is calculated to be 2.276s according to the formula τ avg＝Σαiτi 2/αiτi after fitting with a three-exponential function.
Example 3
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 100mg of 3-aminophenylboronic acid is added to 3g of urea, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction at 200 ℃ for 3 hours.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 10 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, where the u-CDs prepared in this example has an emission peak position of 447nm, which can produce blue phosphorescence.
FIG. 11 is a graph showing the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining afterglow time is more than 35s, and the phosphorescence lifetime of u-CDs is calculated to be 2.187s according to the formula τ avg＝Σαiτi 2/αiτi after fitting by a three-exponential function.
As can be seen from the phosphorescence emission spectra and the phosphorescence lifetime decay spectra of comparative examples 1 to 3, the phosphorescent intensity and the phosphorescent lifetime of the u-CDs samples both show a decreasing trend with increasing doping amount of the carbon source.
Example 4
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 25mg of 3-aminophenylboronic acid was added to 3g of urea, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction at 190 ℃ for 4 hours.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 12 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, where the u-CDs prepared in this example has an emission peak position of 448nm, which can produce blue phosphorescence.
FIG. 13 is a graph showing the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining afterglow time length reaches about 40s, and the phosphorescence lifetime of u-CDs is calculated to be 2.364s according to the formula τ avg＝Σαiτi 2/αiτi after fitting by a three-exponential function.
Example 5
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 100mg of 3-aminophenylboronic acid is added to 3g of urea respectively, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction at 190 ℃ for 4 hours.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 14 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, as shown in the figure, the emission peak position of u-CDs prepared in this example is 449nm.
FIG. 15 shows the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining luminescence duration is approximately 40s, and the phosphorescence lifetime of u-CDs is calculated to be 2.259s according to formula τ avg＝Σαiτi 2/αiτi after three-exponential function fitting.
Example 6
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 25mg of 3-aminophenylboronic acid is added to 3g of urea respectively, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction at 210 ℃ for 3 hours.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 16 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, as shown in the figure, the u-CDs prepared in this example has an emission peak position of 447nm.
FIG. 17 is a graph showing the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining afterglow time is more than 35s, and the phosphorescence lifetime of u-CDs is calculated to be 2.229s according to the formula τ avg＝Σαiτi 2/αiτi after fitting by a three-exponential function.
Example 7
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 25mg of 3-aminophenylboronic acid was added to 3g of urea, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction for 3h at 220 ℃.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 18 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, as shown in the figure, the emission peak position of u-CDs prepared in this example is 448nm.
FIG. 19 is a graph showing the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining afterglow time length reaches 40s, and the phosphorescence lifetime of u-CDs is calculated to be 2.307s according to the formula τ avg＝Σαiτi 2/αiτi after fitting by a three-exponential function.
Example 8
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 25mg of 3-aminophenylboronic acid was added to 3g of urea, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction for 4h at 200 ℃.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 20 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, as shown in the figure, the emission peak position of u-CDs prepared in this example is 448nm.
FIG. 21 is a graph showing the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining afterglow time length reaches 40s, and the phosphorescence lifetime of u-CDs is calculated to be 2.300s according to the formula τ avg＝Σαiτi 2/αiτi after fitting by a three-exponential function.
Example 9
The embodiment provides a water-resistant carbon quantum dot matrix composite phosphor material, which is prepared by the following steps:
(1) 25mg of 3-aminophenylboronic acid was added to 3g of urea, and dissolved and uniformly mixed with 20mL of deionized water to obtain a mixed solution of 3-aminophenylboronic acid and urea.
(2) The mixed solution is placed in a 100mL beaker, covered with tinfoil paper to prevent the solution from evaporating too fast, placed in an oven and subjected to hydrothermal reaction at 200 ℃ for 5 hours.
(3) After the reaction is finished, cooling to room temperature, taking out the solid in the beaker, and grinding the solid into powder by using a mortar to obtain the water-resistant carbon quantum dot matrix composite phosphorescent material, namely u-CDs for short.
FIG. 22 is a phosphorescence emission spectrum of u-CDs prepared in this example at an excitation wavelength of 275nm, as shown in the figure, the emission peak position of u-CDs prepared in this example is 448nm.
FIG. 23 shows the phosphorescence attenuation spectrum of u-CDs prepared in this example, wherein the remaining luminescence duration is approximately 40s, and the phosphorescence lifetime of u-CDs is calculated to be 2.241s according to formula τ avg＝Σαiτi 2/αiτi after three-exponential function fitting.
Examples 10 to 14
On the basis of example 1, u-CDs were prepared using phenylboronic acid, 2-aminophenylboronic acid, 4-aminophenylboronic acid, 1, 3-phenyldiboronic acid, 4-carboxyphenylboronic acid instead of 3-aminophenylboronic acid, with the other conditions unchanged, and analyzed for the optimal excitation wavelength, emission peak position as follows:
| examples | Carbon source | Optimal excitation wavelength/nm | Emission peak position/nm |
| 10 | Phenylboronic acid | 270 | 408 |
| 11 | 2-Aminophenylboronic acid | 260 | 431 |
| 12 | 4-Aminophenylboronic acid | 280 | 465 |
| 13 | 1, 3-Benzodiboronic acid | 260 | 444 |
| 14 | 4-Carboxyphenylboronic acid | 260 | 423 |
Under the excitation condition, phenylboronic acid, 2-aminophenylboronic acid, 4-aminophenylboronic acid and 1, 3-phenyldiboronic acid can emit phosphorescence visible to naked eyes, but the duration is shorter, and the calculated phosphorescence life is shorter than that of 3-aminophenylboronic acid.
Comparative example 1
Based on the example 1, the tinfoil paper placed at the beaker mouth is canceled, other conditions are unchanged, u-CDs are prepared, and moisture is quickly evaporated in half an hour in the reaction process, so that a target product cannot be prepared.
Comparative example 2
Based on example 1, the amount of 3-aminophenylboronic acid was adjusted to 10mg, and the other conditions were unchanged, to prepare u-CDs having an optimum excitation wavelength of 275nm, an emission peak position of 447nm, and a phosphorescence lifetime of 2.259s.
Comparative example 3
Based on example 1, the amount of 3-aminophenylboronic acid was adjusted to 150mg, and the other conditions were unchanged, to prepare u-CDs having an optimum excitation wavelength of 275nm, an emission peak position of 445nm, and a phosphorescence lifetime of 2.017s.
In summary, the phosphorescent carbon quantum dot-based composite material prepared by the method can realize blue phosphorescence emission, has very stable material performance under different preparation conditions and carbon source doping amounts, has stable emission wavelength and phosphorescence service life, and has simple preparation conditions, and the preparation conditions are easy to achieve the condition of mass production.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The preparation method of the water-resistant carbon quantum dot matrix composite phosphorescent material is characterized by comprising the following steps of: mixing a carbon source with urea, performing a hydrothermal reaction, and collecting solids after the reaction is finished to obtain the water-resistant carbon quantum dot matrix composite phosphorescence material;
the carbon source is at least one of 3-aminophenylboric acid, phenylboric acid, 1, 3-phenyldiboronic acid, 2-aminophenylboric acid, 4-aminophenylboric acid and 4-carboxyphenylboric acid;
The temperature of the hydrothermal reaction is 190-220 ℃, and the reaction time is 3-5 h.
2. The method for preparing a water-resistant carbon quantum dot matrix composite phosphor material according to claim 1, wherein a mixed solution of a carbon source and urea is poured into an open container, then a metal foil is used to cover the mouth of the container, and the container is placed in a heating device for reaction.
3. The method for preparing the water-resistant carbon quantum dot matrix composite phosphor material according to claim 2, wherein the mass ratio of the carbon source to urea is (0.020-0.100): 3.
4. The method for preparing the water-resistant carbon quantum dot matrix composite phosphor material according to claim 3, wherein the mass ratio of the carbon source to the urea is 0.025:3, and the reaction time is 3h.
5. The water-resistant carbon quantum dot matrix composite phosphor material is characterized by being prepared by the method according to any one of claims 1-4.
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