CN114316966B - Preparation method and application of nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot - Google Patents
Preparation method and application of nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot, wherein the carbon dot is prepared by utilizing solvothermal method, has fluorescent emission of ultraviolet/blue/green three wavelengths under ultraviolet excitation, and the proportion of three fluorescent peaks can be controllably adjusted. Under the excitation of light with the same wavelength, fluorescence with different colors can be obtained, so that fluorescence coding can be realized to a certain extent, and the fluorescent dye has wide application prospects in the fields of color display, anti-counterfeiting, information encryption and the like.
Description
Technical Field
The invention relates to the field of carbon dot preparation, in particular to a preparation method and application of nitrogen-sulfur co-doped ultraviolet/blue/green three-wavelength fluorescent carbon dots.
Background
Fluorescent carbon dots have excellent optical properties, low toxicity and good biocompatibility and are widely used in many fields, such as biology and environmental monitoring. In recent years, researchers regulate and control fluorescence properties of carbon dots by structural changes caused by heteroatom doping, wherein the most studied carbon dots are doped with nitrogen, phosphorus, sulfur and other elements. However, most of the double doped fluorescent carbon dots emit only a single wavelength, and synthesis methods of dual-wavelength or even three-wavelength fluorescent carbon dots are rarely reported.
In addition, the conventional fluorescent coding is to assemble and compound single fluorescent materials with different colors into microspheres, the proportion of the materials is regulated to control and realize fluorescent coding signals, and the assembled composite fluorescent materials are generally large in size and easy to gather, so that the light stability of the probe is affected.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot, which aims to solve the defects that most of the existing double-doped fluorescent carbon dots only emit at a single wavelength, the assembled composite fluorescent material is large in size and easy to gather and the light stability of a probe is affected.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of a nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot, which comprises the following steps:
1) Adding citric acid, urea and diaminobenzenesulfonic acid into the mixed solvent, and fully stirring to obtain a mixed solution;
2) And (3) placing the mixed solution obtained in the step (1) into a reaction kettle, heating the mixed solution to perform hydrothermal reaction, cooling the mixed solution after the reaction, centrifuging the mixed solution, and dialyzing the cooled mixed solution to obtain the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dots.
According to the invention, citric acid, urea and diaminobenzenesulfonic acid are used as raw materials, water and alcohol are used as mixed solvent environments, and the nitrogen-sulfur co-doped fluorescent carbon dots can be obtained by heating in a reaction kettle for a short time (one-step hydrothermal method), so that the raw materials are easy to obtain, the cost is low, the preparation method is simple, the time is short, the danger is low, and the mass production is easy to realize.
As a preferable scheme of the invention, in the step 1), the mixed solvent comprises water and alcohol, and the volume ratio of the water to the alcohol is 1:0.2-2.
As a preferred embodiment of the present invention, the alcohol is at least one of methanol, ethanol, and propanol.
As a preferable scheme of the invention, the molar ratio of the citric acid, the urea and the diaminobenzene sulfonic acid is 1:1.0-3.5:0.2-1.4.
As a preferred embodiment of the present invention, the diaminobenzenesulfonic acid includes at least one of 2, 4-diaminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid, 3, 4-diaminobenzenesulfonic acid, 2, 4-diaminobenzenesulfonic acid salt, 2, 5-diaminobenzenesulfonic acid salt, and 3, 4-diaminobenzenesulfonic acid salt.
In a preferred embodiment of the present invention, in step 2), the hydrothermal reaction conditions are: the reaction temperature is 160-200 ℃ and the reaction time is 4-6h.
In a preferred embodiment of the present invention, in step 2), the centrifugation conditions are: the rotating speed is 8000r/min, and the centrifugation is carried out for 15min; dialysis is carried out for 24 hours by using a dialysis bag with the molecular weight cut-off of 500-1000 Da.
The second aspect of the invention provides the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot prepared by the preparation method.
The third aspect of the invention provides an application of the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot in the optical field.
As a preferable scheme of the invention, the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot is applied to fluorescent coding.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, citric acid, urea and diaminobenzenesulfonic acid are used as raw materials, water and alcohol are used as mixed solvent environments, and nitrogen-sulfur co-doped fluorescent carbon dots can be obtained by heating in a reaction kettle for a short time (one-step hydrothermal method), so that the raw materials are easy to obtain, the cost is low, the preparation method is simple, the time is short, the danger is low, and batch production is easy to realize;
2) The nitrogen-sulfur co-doped fluorescent carbon dot obtained by the invention has three-wavelength emission of ultraviolet/blue/green, and the fluorescence intensity proportion of the three wavelengths can be adjusted, so that the fluorescent quality is excellent. Under the excitation of light with the same wavelength, fluorescence with different colors can be obtained, so that fluorescence coding can be realized to a certain extent, and the fluorescent dye has wide application prospects in the fields of color display, anti-counterfeiting, information encryption and the like.
Drawings
FIG. 1 shows carbon dot fluorescence spectra obtained in examples 1 to 3 and comparative example 1.
FIG. 2 shows carbon dot fluorescence spectra obtained in examples 4 to 6 and comparative example 2.
FIG. 3 shows carbon dot fluorescence spectra obtained in examples 7 to 9 and comparative example 3.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot, which comprises the following steps:
(1) Adding 100mg of citric acid, 50mg of urea and 100mg of 2, 4-diaminobenzenesulfonic acid into the mixed solvent, and fully stirring to obtain a mixed solution; the mixed solution is prepared by the following method: mixing water and ethanol to obtain the water-ethanol composite material, wherein the volume ratio of water to ethanol is 1:2 (30 mL total).
(2) And (3) heating the mixed solution in a reaction kettle to perform hydrothermal reaction, wherein the reaction temperature is 160 ℃, the reaction time is 6 hours, cooling is performed after the reaction, the rotation speed is 8000r/min, centrifuging is performed for 15min, and dialysis is performed for 24 hours by adopting a dialysis bag with the molecular weight cut-off of 1000Da, so that the nitrogen-sulfur co-doped ultraviolet/blue/green three-wavelength fluorescent carbon dots are obtained, and the fluorescence spectrum of the obtained carbon dots is shown in figure 1.
Example 2
This example differs from example 1 in that the volume ratio of water to ethanol is 1:1 (30 mL total), the rest is exactly the same as in example 1, and the obtained carbon dot fluorescence spectrum is shown in FIG. 1.
Example 3
This example differs from example 1 in that the volume ratio of water to ethanol is 2:1 (30 mL total), the rest is exactly the same as in example 1, and the obtained carbon dot fluorescence spectrum is shown in FIG. 1.
Comparative example 1
This comparative example differs from example 1 in that the volume ratio of water to ethanol is 1:0 (30 mL total), i.e., all water, the resulting carbon point fluorescence spectrum is shown in FIG. 1.
As can be seen from fig. 1, the mixed solvent environment with different water-alcohol ratios can adjust the ratio of the intensity of the three wavelengths of the fluorescent carbon dots, while the carbon dots prepared by the pure water solvent environment only have ultraviolet/blue dual-wavelength emission.
Example 4
The embodiment provides a preparation method of a nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot, which comprises the following steps:
(1) 100mg of citric acid, 50mg of urea and 2, 5-diaminobenzenesulfonic acid are added into the mixed solvent, wherein the molar ratio of the citric acid to the 2, 5-diaminobenzenesulfonic acid is 1:0.51, fully stirring to obtain a mixed solution; the mixed solution is prepared by the following method: mixing water and methanol to obtain the water-alcohol composite material, wherein the volume ratio of water to alcohol is 1:1 (30 mL total);
(2) The mixed solution is placed in a reaction kettle to be heated for hydrothermal reaction, the reaction temperature is 160 ℃, the reaction time is 4 hours, the reaction is cooled, the rotation speed is 8000r/min, the centrifugation is carried out for 15 minutes, the dialysis bag with the molecular weight cut-off of 800Da is adopted for dialysis for 24 hours, and the nitrogen-sulfur co-doped ultraviolet/blue/green three-wavelength fluorescent carbon dots are obtained, and the fluorescence spectrum of the obtained carbon dots is shown in figure 2.
Example 5
This example differs from example 4 in that the molar ratio of citric acid to 2, 5-diaminobenzenesulfonic acid is 1:0.77, the rest is exactly the same as in example 1, and the obtained carbon dot fluorescence spectrum is shown in FIG. 2.
Example 6
This example differs from example 4 in that the molar ratio of citric acid to 2, 5-diaminobenzenesulfonic acid is 1:1.02, the rest is exactly the same as in example 1, and the obtained carbon dot fluorescence spectrum is shown in FIG. 2.
Comparative example 2
This comparative example differs from example 4 in that the molar ratio of citric acid to 2, 5-diaminobenzenesulfonic acid is 1:1.53, the rest is exactly the same as in example 1, and the obtained carbon dot fluorescence spectrum is shown in FIG. 2.
As can be seen from fig. 2, as the content of diaminobenzenesulfonic acid increases, the intensity of the blue light peak gradually decreases, and when diaminobenzenesulfonic acid is excessive, only ultraviolet/green dual-wavelength emission is exhibited.
Example 7
The embodiment provides a preparation method of a nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot, which comprises the following steps:
(1) 100mg of citric acid, urea and 100mg of 2, 4-diaminobenzenesulfonic acid are added into the mixed solvent, wherein the molar ratio of the citric acid to the urea is 1:1.60, fully stirring to obtain a mixed solution; the mixed solution is prepared by the following method: mixing water and ethanol to obtain the water-ethanol composite material, wherein the volume ratio of water to ethanol is 1:1 (30 mL total);
(2) The mixed solution is placed in a reaction kettle to be heated for hydrothermal reaction, the reaction temperature is 180 ℃, the reaction time is 4 hours, the reaction is cooled, the rotation speed is 8000r/min, the centrifugation is carried out for 15 minutes, the dialysis is carried out for 24 hours by adopting a dialysis bag with the molecular weight cut-off of 800Da, and the nitrogen-sulfur co-doped ultraviolet/blue/green three-wavelength fluorescent carbon dots are obtained, and the fluorescence spectrum of the obtained carbon dots is shown in figure 3.
Example 8
This example differs from example 7 in that the molar ratio of citric acid to urea is 1:2.24, the rest being exactly the same as in example 7, the carbon point fluorescence spectrum obtained is shown in FIG. 3.
Example 9
This example differs from example 7 in that the molar ratio of citric acid to urea is 1:3.2, the rest is exactly the same as in example 7, and the obtained carbon dot fluorescence spectrum is shown in FIG. 3.
Comparative example 3
This comparative example differs from example 7 in that urea was not added and the carbon point fluorescence spectrum obtained is shown in fig. 3.
As can be seen from fig. 3, the carbon dots prepared without urea addition have only uv/green emission; as the urea content increases, the intensity of the blue light peak increases gradually.
The nitrogen-sulfur co-doped fluorescent carbon dot obtained by the invention has three-wavelength emission of ultraviolet/blue/green, and the fluorescence intensity proportion of the three wavelengths can be adjusted, so that the fluorescent quality is excellent. Under the excitation of light with the same wavelength, fluorescence with different colors can be obtained, so that fluorescence coding can be realized to a certain extent, and the fluorescent dye has wide application prospects in the fields of color display, anti-counterfeiting, information encryption and the like.
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various modifications and additions may be made without departing from the scope of the invention. Equivalent embodiments of the present invention will be apparent to those skilled in the art having the benefit of the teachings disclosed herein, when considered in the light of the foregoing disclosure, and without departing from the spirit and scope of the invention; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot is characterized by comprising the following steps of:
1) Adding citric acid, urea and diaminobenzenesulfonic acid into the mixed solvent, and fully stirring to obtain a mixed solution; the mixed solvent comprises water and alcohol, and the volume ratio of the water to the alcohol is 1:0.2-2; the mol ratio of the citric acid, the urea and the diaminobenzene sulfonic acid is 1:1.0-3.5:0.2-1.4;
2) And (3) placing the mixed solution obtained in the step (1) into a reaction kettle, heating the mixed solution to perform hydrothermal reaction, cooling the mixed solution after the reaction, centrifuging the mixed solution, and dialyzing the cooled mixed solution to obtain the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dots.
2. The method for preparing the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dots according to claim 1, wherein the alcohol is at least one of methanol, ethanol and propanol.
3. The method for preparing the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot according to claim 1, wherein the diaminobenzenesulfonic acid comprises at least one of 2, 4-diaminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid and 3, 4-diaminobenzenesulfonic acid.
4. The method for preparing the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dots according to claim 1, wherein in the step 2), hydrothermal reaction conditions are as follows: the reaction temperature is 160-200 ℃ and the reaction time is 4-6h.
5. The method for preparing the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dots according to claim 1, wherein in the step 2), the centrifugation condition is as follows: the rotating speed is 8000r/min, and the centrifugation is carried out for 15min; dialysis is carried out for 24 hours by using a dialysis bag with the molecular weight cut-off of 500-1000 Da.
6. The nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot prepared by the preparation method of any one of claims 1-5.
7. The use of the nitrogen-sulfur co-doped three-wavelength fluorescent carbon dot of claim 6 in the optical field, wherein fluorescent light of different colors is obtained under the excitation of light of the same wavelength.
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