CN111647402B - Carbon quantum dot, preparation method thereof and tracer - Google Patents
Carbon quantum dot, preparation method thereof and tracer Download PDFInfo
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- CN111647402B CN111647402B CN202010660569.6A CN202010660569A CN111647402B CN 111647402 B CN111647402 B CN 111647402B CN 202010660569 A CN202010660569 A CN 202010660569A CN 111647402 B CN111647402 B CN 111647402B
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
Abstract
The application provides a carbon quantum dot and a preparation method thereof, and a tracer, wherein the preparation method comprises the following steps: s1, carrying out first heating treatment on a first mixed solution containing a first compound, a second compound, a third compound and a protic solvent to form a first reactant; s2, carrying out second heating treatment on a second mixed solution of the first reactant, the protic solvent and the polyalcohol compound to form carbon quantum dots; wherein the first compound is an aromatic compound containing two or more amino groups; the second compound is polycarboxylic acid with amino; the third compound is inorganic acid, and the prepared carbon quantum dot has high light efficiency, narrow half-peak width and strong adsorption resistance, and can be widely applied to the fields of tracing, lighting, displaying and the like.
Description
Technical Field
The application belongs to the field of nano materials, and particularly relates to a carbon quantum dot, a preparation method thereof and a tracer.
Background
The carbon quantum dot is a carbon nano material with three-dimensional sizes within 10nm, and the main constituent elements of the carbon quantum dot comprise carbon, hydrogen, oxygen and the like. The fluorescent material has attracted more and more attention due to its unique advantages of excellent luminescent properties, non-toxicity, excellent biocompatibility, etc. The fluorescent carbon quantum dots are widely applied to the fields of photoelectricity, biological labeling and the like.
The half-peak width of the carbon quantum dots prepared by the conventional technology is large, usually larger than 65nm, and further application of the carbon quantum dots is limited. In addition, due to the variability of raw materials, the complexity of the reaction process, the complexity of later purification and the like, the synthesis reproducibility of the carbon quantum dots is poor, and the size distribution, the surface oxidation degree and the like of the carbon quantum dots are affected, so that the light-emitting characteristics of the carbon quantum dots, such as the light-emitting efficiency, the half-height peak width, the fluorescence emission peak position and the like, are affected finally.
Therefore, the development and preparation of the fluorescent carbon quantum dots with narrow half-peak width and high efficiency are of great significance to the development of the fluorescent carbon quantum dots.
Disclosure of Invention
In order to solve the technical problems, the application provides a preparation method of the fluorescent carbon quantum dot, and the prepared fluorescent carbon quantum dot is small in half-peak width and easy to adjust the position of an emission peak.
According to an aspect of the present application, there is provided a method of preparing a carbon quantum dot, including the steps of:
s1, performing first heating treatment on a first mixed solution containing a first compound, a second compound, a third compound and a protic solvent to form a first reactant;
s2, carrying out second heating treatment on a second mixed solution of the first reactant, the protic solvent and the polyalcohol compound to form carbon quantum dots;
wherein the first compound is an aromatic compound containing two or more amino groups;
the second compound is polycarboxylic acid with amino;
the third compound is an inorganic acid.
In the step S1, the protic solvent is used to dissolve the first compound and the second compound, the first compound and the second compound may be dissolved in the protic solvent respectively and then mixed, or may be added to the protic solvent simultaneously to be dissolved and mixed, and the third compound is used as a catalyst, which can accelerate the chemical reaction and control the selectivity of the first reactant; in the step S2, the protic solvent is used to dissolve the first reactant, and the polyol substance can modify the surface of the carbon quantum dot after being heated to react with the first reactant, thereby increasing the solubility of the carbon quantum dot in the polar solvent and effectively enhancing the anti-adsorption property to impurities (such as clay) in the solution, so as to obtain the carbon quantum dot with excellent optical properties. The protic solvent in the step S1 and the protic solvent in the step S2 may be the same or different, and may be selected according to actual needs. This application adopts two steps of heat treatment methods to prepare carbon quantum dot, and the carbon quantum dot that obtains can realize that multiple colour is luminous, luminous efficacy is high, half peak width is narrow, anti adsorptivity reinforcing, is applicable to the scene that requires height, anti adsorptivity strong to quantum dot luminous efficiency, half peak width, is favorable to strengthening carbon quantum dot's use flexibility, is expected to realize its wide application in fields such as hydrology monitoring, biological multi-target's mark, demonstration and illumination.
Further, the first compound is phenylenediamine and a derivative thereof;
preferably, the first compound is selected from at least one of o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and benzenetriamine.
Further, the second compound is dicarboxylic acid with amino;
preferably, the second compound is at least one selected from the group consisting of 2-aminoglutaric acid, 3-aminoglutaric acid, 2-aminoadipic acid, 3-aminoadipic acid, 2-aminopimelic acid, 3-aminopimelic acid, and 4-aminopimelic acid.
Further, the molar concentration of the inorganic acid in the first mixed solution is between 0.025mol/L and 10 mol/L;
preferably, the inorganic acid is nitric acid or sulfuric acid.
The inorganic acid provides an acidic environment for the first mixed solution, and facilitates and accelerates the generation of the first reactant.
Further, the molar ratio of the first compound to the second compound in the first mixed solution is between 0.25 and 3. The first compound and the second compound are caused to react sufficiently during the first heat treatment to form a first reactant.
Further, the protic solvent includes at least one of water and an alcohol solvent, and the alcohol solvent includes, but is not limited to, at least one of ethanol, methanol, propanol and butanol, so as to effectively dissolve the first compound and the second compound.
Further, the polyalcohol compounds comprise at least one of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000 and polyvinyl alcohol with the viscosity value lower than 1000 cP. The applicant finds that by using at least one of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000 and polyvinyl alcohol with a viscosity value lower than 1000cP as a first reactant, the prepared carbon quantum dots can have high light efficiency, narrow half-peak width and enhanced adsorption resistance, and simultaneously, the carbon quantum dots can be effectively separated after the second heat treatment.
Preferably, the mass-to-volume ratio of the first reactant to the polyalcohol compound is 1g (0.5-1) L, when the mass ratio of the first reactant to the polyalcohol compound is too low, the surface of the first reactant cannot be fully optimized, the particle size of the carbon quantum dots is not uniform enough, and when the mass ratio of the first reactant to the polyalcohol compound is too high, the surface of the carbon dots is excessively modified, so that the fluorescence quantum yield of the carbon quantum dots is reduced.
Further, the temperature of the first heating treatment is between 160 ℃ and 240 ℃, and in the temperature range, the first compound and the second compound effectively generate the first reactant under the catalysis of the third compound.
Preferably, the first heat treatment is carried out for a period of time between 6 hours and 24 hours, so that the first reactant is sufficiently generated.
In the first heat treatment of the present application, the first compound, the second compound, the third compound, and the protic solvent are sufficiently reacted, and the obtained first reactant contains the carbon quantum dot precursor.
Further, S1 comprises the steps of:
s11, obtaining a first reaction solution through the first heating treatment;
s12, separating the first reaction liquid to obtain a first reactant;
preferably, S2 comprises the steps of:
s21, obtaining a carbon quantum dot solution through the second heating treatment;
s22, separating the carbon quantum dot solution to obtain the carbon quantum dots.
The separation method of the present application is, for example, vacuum drying or vacuum freeze drying, and the first reaction solution and the first reactant are efficiently separated.
Further, the temperature of the second heating treatment is 120-160 ℃, and in the temperature range, the first reactant and the polyalcohol compounds effectively react to generate the carbon quantum dots.
Preferably, the time of the second heat treatment is between 3 hours and 6 hours, and carbon quantum dots are sufficiently generated.
According to another aspect of the application, the carbon quantum dot is prepared by adopting the method, has rich luminescent color, narrow half-peak width and high luminescent efficiency, and can be widely applied to the fields of hydrological monitoring, biological multi-target marking, display, illumination and the like.
Preferably, the half-peak width of the carbon quantum dot is less than 40nm, so that the luminous purity of the carbon quantum dot is higher, and the carbon quantum dot is favorably applied to the fields of biology, display, illumination and the like.
Preferably, the excitation wavelength of the carbon quantum dots is 300-700 nm;
preferably, the fluorescence emission peak of the carbon quantum dot is 500 nm-800 nm.
According to another aspect of the present application, there is provided a tracer comprising a carbon quantum dot as described above. When the tracer of this application was applied to the common mark of multiobjective, for example aspects such as biomarker, oil tracer, paddy field tracer, because the half-peak width of carbon quantum dot is narrow, effectively avoid detecting the spectrum peak stack problem between the different markers in the appearance for the tracer detects more accurately.
Has the advantages that:
(1) The carbon quantum dots prepared in the application have high luminous efficiency, narrow half-peak width and strong adsorbability resistance;
(2) The preparation process of the carbon quantum dots is simple and easy to implement, low in cost, good in repeatability and beneficial to large-scale preparation;
(3) The application of the tracer can be used for aspects such as biomarkers, petroleum tracing and paddy field tracing, and the half-peak width of the carbon quantum dots is narrow, so that the problem of spectral peaks among different markers in a detection sample is effectively avoided, and tracing detection is more accurate.
Drawings
FIG. 1 is a spectrum of an emission spectrum of carbon quantum dots in example 1 of the present application;
FIG. 2 is a transmission electron micrograph of carbon quantum dots in example 1 of the present application;
FIG. 3 is a spectrum of an emission spectrum of carbon quantum dots in example 2 of the present application;
FIG. 4 is a graph showing an emission spectrum of carbon quantum dots in example 3 of the present application;
FIG. 5 is a graph showing an emission spectrum of carbon quantum dots in example 4 of the present application;
FIG. 6 is an absorption spectrum of carbon quantum dots in example 4 of the present application;
FIG. 7 is a spectrum of an emission spectrum of carbon quantum dots in example 5 of the present application;
FIG. 8 is a spectrum of an emission spectrum of carbon quantum dots in example 6 of the present application;
fig. 9 is a graph showing a comparison of the adsorption resistance effect of the carbon quantum dots in comparative example 1, example 8, and example 9.
In the drawings like parts are provided with the same reference numerals. The figures show embodiments of the application only schematically.
Detailed Description
The following describes technical solutions in the examples of the present application in detail with reference to the embodiments of the present application. It should be noted that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. Unless otherwise defined, all terms (including technical and scientific terms) in the specification may be defined as commonly understood by one of ordinary skill in the art. Terms defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and may not be interpreted in an idealized or overly formal sense unless expressly so defined. Furthermore, unless expressly stated to the contrary, the terms "comprises" and "comprising," when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof. Thus, the above wording will be understood to mean that the stated elements are included, but not to exclude any other elements.
It will be understood that, although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the present embodiments.
The following definitions apply to aspects described in relation to some embodiments of the invention, and these definitions may be extended herein as well.
As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Unless the context clearly dictates otherwise, reference to an object may include multiple objects.
As used herein, the term "adjacent" refers to being proximate or contiguous. The adjacent objects may be spaced apart from each other, or may be in actual or direct contact with each other. In some cases, adjacent objects may be connected to each other, or may be integrally formed with each other.
As used herein, the term "connected" refers to an operative coupling or link. The linked objects may be directly coupled to each other or may be indirectly coupled to each other via another set of objects.
As used herein, "above" is meant to include the present numbers, e.g., two or more, including two; polyethylene glycol followed by a number is the molecular weight of polyethylene glycol, e.g., polyethylene glycol 400 is a polyethylene glycol having a molecular weight of 400; the polyalcohol substances refer to polymers of alcohols; the aromatic compound having two or more amino groups includes a compound having at least two amino groups connected to a benzene ring, and polyethylene glycol may be abbreviated as PEG in this application.
As used herein, relative terms such as "inside," "interior," "exterior," "top," "bottom," "front," "back," "upper," "lower," "vertical," "transverse," "above … …," and "below … …" refer to the orientation of a set of objects to one another first, for example, according to the drawings, but do not require a particular orientation of the objects during manufacture or use.
The basic raw materials used in the invention, such as polyethylene glycol, o-phenylenediamine, 2-aminoglutaric acid, concentrated nitric acid, concentrated sulfuric acid, ethanol, polyvinyl alcohol and the like, can be purchased in various large chemical raw materials at home and abroad.
Example 1
Adding 1mmol of o-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of distilled water and 60 muL of concentrated nitric acid (the molar concentration in the mixed solution is 0.0435 mol/L) to form a mixed solution, carrying out a solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 12 h), cooling to room temperature, filtering to obtain a purified first reaction solution, carrying out freeze-drying on the first reaction solution to obtain a first reactant powder, dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 1mL of PEG600 into the first reaction solution, carrying out a solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with the half-peak width of 35nm, wherein the luminous efficiency is 30%, as shown in figure 1, the emission spectrogram of the carbon quantum dot is shown, and as shown in figure 2, the scanning electron microscope image of the carbon quantum dot can show that the particle size of the carbon quantum dot is about 4nm.
Example 2
Adding 1mmol of o-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of distilled water and 120 mu L of concentrated nitric acid (the molar concentration in the mixed solution is 0.087 mol/L) to form a mixed solution, carrying out a solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 12 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain first reactant powder, dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 0.5mL of PEG600 into the first reaction solution, carrying out a solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with the half-peak width of 32nm, wherein the luminous efficiency is 24%, and a light emission spectrogram of the carbon quantum dot is shown in figure 3.
Example 3:
adding 1mmol of o-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of distilled water and 3.2mL of concentrated sulfuric acid (the molar concentration in the mixed solution is 3 mol/L) to form a mixed solution, carrying out a solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 12 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain a first reactant powder, dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 0.8mL of PEG600 into the first reaction solution, carrying out the solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with a half-peak width of 34nm, wherein the luminous efficiency is 25%, and a light emission spectrogram of the carbon quantum dot is shown in figure 4.
Example 4:
adding 1mmol of o-phenylenediamine and 1mmol of 3-aminoglutaric acid into 20mL of distilled water and 60 mu L of concentrated nitric acid (the molar concentration in the mixed solution is 0.0435 mol/L) to form a mixed solution, carrying out a solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 12 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain a first reactant powder, dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 0.7mL of PEG600 into the first reaction solution, carrying out the solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with the half-peak width of 37nm, wherein the luminous efficiency is 24%, the emission spectrogram of the carbon quantum dot is shown in figure 5, and the absorption spectrogram of the carbon quantum dot is shown in figure 6.
Example 5:
adding 1mmol of o-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of ethanol and 60 mu L of concentrated nitric acid (the molar concentration in the mixed solution is 0.0435 mol/L) to form a mixed solution, carrying out a solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 12 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain first reactant powder, dispersing 1mg of the first reactant powder into 20mL of ethanol, adding 1mL of PEG600 into the first reaction solution, carrying out the solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with the half-peak width of 35nm, wherein the luminous efficiency is 21%, and a light emission spectrogram of the carbon quantum dot is shown in figure 7.
Example 6:
adding 1mmol of p-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of distilled water and 60 mu L of concentrated nitric acid (the molar concentration in the mixed solution is 0.0435 mol/L) to form a mixed solution, carrying out a solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 12 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain a first reactant powder, dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 0.6mL of PEG600 into the first reaction solution, carrying out the solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with the half-peak width of 55nm, wherein the luminous efficiency is 48%, and a light emission spectrogram of the carbon quantum dot is shown in figure 8.
Example 7
Adding 1mmol of o-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of distilled water and 60 mu L of concentrated nitric acid (the molar concentration in the mixed solution is 0.0435 mol/L) to form a mixed solution, carrying out solvothermal reaction (the reaction temperature is 180 ℃, the reaction time is 12 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain first reactant powder, dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 0.8mL of polyvinyl alcohol with the polymerization degree of 600 into the first reaction solution, carrying out the solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining the carbon quantum dot with the luminous efficiency of 31%.
Example 8
Adding 1mmol of o-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of distilled water and 60 mu L of concentrated nitric acid (the molar concentration in the mixed solution is 0.0435 mol/L) to form a mixed solution, carrying out solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 8 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain first reactant powder, dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 1mL of PEG400 into the first reaction solution, carrying out solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with the luminous efficiency of 28%.
Example 9
Adding 1mmol of o-phenylenediamine and 1mmol of 2-aminoglutaric acid into 20mL of distilled water and 60 mu L of concentrated nitric acid (the molar concentration in the mixed solution is 0.0435 mol/L) to form a mixed solution, carrying out a solvothermal reaction (the reaction temperature is 200 ℃, the reaction time is 10 h), cooling to room temperature, filtering to obtain a purified first reaction solution, freezing and draining the first reaction solution to obtain first reactant powder, re-dispersing 1mg of the first reactant powder into 20mL of distilled water, adding 0.75mL of PEG1000 into the first reaction solution, carrying out a solvothermal reaction again (the reaction temperature is 120 ℃, the reaction time is 4 h), and finally obtaining a carbon quantum dot with the luminous efficiency of 25%.
Comparative example 1
Dissolving 20mg of 4-aminophenol and 60mg of potassium periodate in 10mL of absolute ethyl alcohol, transferring the mixed reaction liquid to a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting at 195 ℃ for 1h, then naturally cooling, and carrying out rotary evaporation on the cooled reaction liquid to obtain carbon quantum dot powder, wherein the emission wavelength of the obtained quantum dot is 620nm, and the half-height peak width is about 80nm.
The initial intensity of fluorescence I was measured by preparing the carbon quantum dots of example 8, example 9, and comparative example 1 as aqueous solutions of a certain concentration, respectively 1 Then 5g of soil is added, after shaking uniformly, standing and adsorbing for 3 days, and the fluorescence intensity value I is measured 2 Adding 5g of soil again, shaking uniformly, standing for 3 days for adsorption, and measuring fluorescence intensity value I 3 As can be seen from the comparison of fluorescence intensities shown in fig. 9, the carbon quantum dots prepared according to the present invention have excellent anti-adsorption performance, and can effectively avoid the influence of impurities on the accuracy of the optical property measurement result during labeling.
Although the present disclosure has been described and illustrated in greater detail by the inventors, it should be understood that modifications and/or alterations to the above-described embodiments, or equivalent substitutions, will be apparent to those skilled in the art without departing from the spirit of the disclosure, and that no limitations to the present disclosure are intended or should be inferred therefrom.
Claims (16)
1. A method for preparing a carbon quantum dot is characterized by comprising the following steps:
s1, performing first heating treatment on a first mixed solution containing a first compound, a second compound, a third compound and a protic solvent to form a first reactant;
s2, carrying out second heating treatment on a second mixed solution of the first reactant, the protic solvent and the polyalcohol compound to form carbon quantum dots;
wherein the first compound is selected from at least one of o-phenylenediamine and p-phenylenediamine;
the second compound is selected from 2-aminoglutaric acid;
the third compound is an inorganic acid.
2. The method according to claim 1, wherein the molar concentration of the inorganic acid in the first mixed solution is between 0.025mol/L and 10 mol/L.
3. The method according to claim 2, wherein the inorganic acid is nitric acid or sulfuric acid.
4. The method according to claim 1, wherein a molar ratio of the first compound to the second compound in the first mixed solution is 0.25 to 3.
5. The method according to claim 1, wherein the protic solvent comprises at least one of water and an alcohol solvent.
6. The method of claim 1, wherein the polyol compound comprises at least one of polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, and polyvinyl alcohol having a viscosity value of less than 1000 cP.
7. The preparation method according to claim 6, wherein the mass-to-volume ratio of the first reactant to the polyalcohol compound is 1g (0.5 to 1) L.
8. The method according to claim 1, wherein the temperature of the first heat treatment is between 160 ℃ and 240 ℃.
9. The method of claim 8, wherein the first heat treatment is performed for a period of time between 6 hours and 24 hours.
10. The method of claim 1, wherein S1 comprises the steps of:
s11, obtaining a first reaction solution through the first heating treatment;
s12, separating the first reaction liquid to obtain a first reactant.
11. The method of claim 10, wherein S2 comprises the steps of:
s21, obtaining a carbon quantum dot solution through the second heating treatment;
s22, separating the carbon quantum dot solution to obtain the carbon quantum dots.
12. The method of claim 11, wherein the second heat treatment is at a temperature between 120 degrees celsius and 160 degrees celsius.
13. The method according to claim 12, wherein the time of the second heat treatment is between 3 hours and 6 hours.
14. A carbon quantum dot produced by the method according to any one of claims 1 to 13.
15. The carbon quantum dot of claim 14, wherein the carbon quantum dot has a half-peak width of less than 40 nm.
16. A tracer comprising the carbon quantum dot of claim 14 or 15.
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| CN106978169A (en) * | 2017-04-17 | 2017-07-25 | 大连理工大学 | A kind of high-fluorescence quantum yield N, the preparation method of S doped carbons point |
| CN108659833A (en) * | 2018-05-25 | 2018-10-16 | 山西大学 | A kind of yellow fluorescence carbon dots and its preparation method and application |
| CN110184050A (en) * | 2019-06-06 | 2019-08-30 | 武汉工程大学 | A kind of controllable synthesis method of nearly full spectral emissions carbon quantum dot |
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| CN108659833A (en) * | 2018-05-25 | 2018-10-16 | 山西大学 | A kind of yellow fluorescence carbon dots and its preparation method and application |
| CN110184050A (en) * | 2019-06-06 | 2019-08-30 | 武汉工程大学 | A kind of controllable synthesis method of nearly full spectral emissions carbon quantum dot |
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| 用于LED的单一基质碳量子点荧光粉的合成与发光性能;冯晓婷;《中国博士学位论文全文数据库》;20160815;全文 * |
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