CN110724528A - Rosin-based carbon dot material and preparation method and application thereof - Google Patents

Rosin-based carbon dot material and preparation method and application thereof Download PDF

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CN110724528A
CN110724528A CN201911080606.XA CN201911080606A CN110724528A CN 110724528 A CN110724528 A CN 110724528A CN 201911080606 A CN201911080606 A CN 201911080606A CN 110724528 A CN110724528 A CN 110724528A
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韩世岩
葛敏
倪佳馨
周军丹
李淑君
姜贵全
庞久寅
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Northeast Forestry University
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Abstract

The invention belongs to the technical field of carbon dot materials, and particularly relates to a rosin-based carbon dot material and a preparation method and application thereof. The invention mixes rosin resin acid with water to carry out hydrothermal reaction to obtain the rosin-based carbon dot material. The invention takes natural biomass resource-rosin resin acid as raw material, the raw material is rich and low in price, the prepared rosin-based carbon dot material has fluorescence emission property in solid and liquid states, and has special characteristics incomparable with CDs prepared from other biomass raw materialsSex; the invention adopts a one-step hydrothermal synthesis method to prepare CDs materials, the preparation method is simple and easy to operate, and the rosin-based carbon dot material prepared by the invention can be used for cell imaging and metal Fe3+Detection of ions, in the solid state, can be used to fabricate White Light Emitting Diodes (WLEDs).

Description

Rosin-based carbon dot material and preparation method and application thereof
Technical Field
The invention relates to the technical field of carbon dot materials, in particular to a rosin-based carbon dot material and a preparation method and application thereof.
Background
Carbon Dots (CDs) refer to carbon particles having fluorescent properties with a size of less than 20 nm. The biomass raw materials for preparing the Carbon Dots (CDs) are more, such as corn, oat, various fruits, rice hulls, catkin, walnut shells and the like, and the raw materials can be prepared into the carbon dots with good fluorescence properties by hydrothermal, microwave and other methods. However, most of the carbon dots prepared by using biomass raw materials are complicated in preparation methods, such as high-temperature calcination, deep carbonization using strong acid and strong base, or extraction using organic solvents, and the purification and separation process takes a long time (such as dialysis), and the yield of the prepared CDs is low. In addition, the carbon dots made of biomass material only have fluorescence in solution and no fluorescence in solid state.
Disclosure of Invention
The invention aims to provide a preparation method of a rosin-based carbon dot material, and the prepared rosin-based carbon dot material has fluorescence emission properties in both solid and solution (water or ethanol).
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a rosin-based carbon dot material, which comprises the following steps:
mixing rosin resin acid with water, and carrying out hydrothermal reaction to obtain the rosin-based carbon dot material.
Preferably, the rosin-based resin acid is a resin acid having a tricyclic phenanthrene skeleton structure.
Preferably, the rosin-based resin acid is one or more of abietic acid-type resin acid, pimaric acid-type resin acid and isopimaric acid-type resin acid.
Preferably, the dosage ratio of the rosin resin acid to water is 0.1-1 g: 70-80 mL.
Preferably, the temperature of the hydrothermal reaction is 150-240 ℃ and the time is 5-24 h.
Preferably, after the hydrothermal reaction is completed, the method further comprises: and naturally cooling the obtained material to room temperature, filtering, and freeze-drying the obtained filtrate to obtain the rosin-based carbon dot material.
Preferably, the filtration mode is suction filtration, and the pore diameter of the water-based microporous filter membrane used for the suction filtration is 0.22 μm or 0.45 μm.
The invention provides the rosin-based carbon dot material prepared by the preparation method in the technical scheme.
The invention provides application of the rosin-based carbon dot material in the technical scheme in manufacturing WLED.
The invention provides the technical scheme that the rosin-based carbon dot material is used for cell imaging and Fe detection3+The use of (1).
The invention provides a preparation method of a rosin-based carbon dot material, which comprises the following steps: mixing rosin resin acid with water, and carrying out hydrothermal reaction to obtain the rosin-based carbon dot material.
The invention takes natural biomass resource-rosin resin acid as raw material, the raw material is rich and low in price, and the prepared rosin-based carbon dot material has fluorescence emission property when being dissolved in solid (powder) and liquid (water or ethanol) and has incomparable characteristics with CDs prepared from other biomass raw materials;
the invention adopts a one-step hydrothermal synthesis method to prepare the CDs material, and the preparation method is simple and easy to operate;
the raw materials of the rosin resin acid, the solvent water and the hydro-thermal synthesis method adopted by the invention are green and environment-friendly, and the whole preparation process has no complex operation steps and is green and environment-friendly;
the invention has high utilization rate of raw materials, and the filter residue filtered in the preparation process can be subjected to carbon point synthesis by using the same method and secondary hydrothermal treatment.
The invention provides application of the rosin-based carbon dot material, and the rosin-based carbon dot material prepared by the invention can be used for cell imaging and metal Fe3+And (3) detecting ions, wherein the solid (powder) can be used for manufacturing a WLED (white light emitting diode).
Drawings
FIG. 1 is an infrared spectrum of CDs and hydrogenated rosin feedstock prepared in example 1;
FIG. 2 is a high magnification transmission electron micrograph (HRTEM) of CDs prepared in example 1;
FIG. 3 is a fluorescence emission spectrum of an aqueous solution (concentration: 125. mu.g/mL) of CDs prepared in example 1 at different excitation wavelengths and a fluorescence color photograph under a 365nm UV lamp;
FIG. 4 is a fluorescent emission spectrum of CDs solid prepared in example 1 under different excitation wavelengths and a fluorescent color photograph of powder under 365nm UV light;
FIG. 5 is a photograph of imaging Human Umbilical Vein Endothelial Cells (HUVEC) with CDs prepared in example 1;
FIG. 6 is a graph showing the effect of different metal ions on the fluorescence intensity of an aqueous solution (concentration: 20. mu.g/mL) of CDs prepared in example 1.
Detailed Description
The invention provides a preparation method of a rosin-based carbon dot material, which comprises the following steps:
mixing rosin resin acid with water, and carrying out hydrothermal reaction to obtain the rosin-based carbon dot material.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
In the present invention, the rosin-based resin acid is preferably a resin acid having a tricyclic phenanthrene skeleton structure, and more preferably one or more of abietic acid-based resin acid, pimaric acid-based resin acid, and isopimaric acid-based resin acid.
In the present invention, the structural formula of the abietic acid-type resin acid is preferably:
Figure BDA0002263834530000031
in the present invention, the pimaric type resin acid has the following structural formula:
Figure BDA0002263834530000042
in the present invention, the formula of the isopimaric acid-type resin acid is as follows:
Figure BDA0002263834530000043
in the present invention, the structural formulas of the rosin-based resin acids listed above are specific structural formulas of different types of resin acids, and when the rosin-based resin acids are used as raw materials in examples, the dehydrorosin (i.e., dehydroabietic acid) is a pure product, and both the rosin and the hydrogenated rosin are a mixture, wherein the main component of the rosin (i.e., abietic acid) is abietic acid, and the main component of the hydrogenated rosin (i.e., hydrogenated abietic acid) is dihydroabietic acid and tetrahydroabietic acid. In the present invention, the ratio of the rosin-based resin acid to water is preferably 0.1 to 1 g/70 to 80mL, more preferably 0.3 to 0.8 g/70 to 80mL, and most preferably 0.5 to 0.7 g/70 to 80 mL. In the present invention, the water is preferably deionized water or distilled water, which serves as a dispersion solvent. The invention further ensures the smooth synthesis of the carbonized product (namely the rosin-based carbon dots) by controlling the consumption of water.
In the invention, the temperature of the hydrothermal reaction is preferably 150-240 ℃, more preferably 160-220 ℃, most preferably 180-200 ℃, and the time is preferably 5-24 hours, more preferably 8-20 hours, and most preferably 10-15 hours. In the invention, the hydrothermal reaction is preferably carried out in a hydrothermal kettle, and the dosage of the rosin resin acid is preferably adjusted according to the volume of the hydrothermal kettle; the amount of the water is preferably up to 70-80% of the filling degree of the hydrothermal kettle. In the hydrothermal reaction process, the rosin resin acid generates carbonization reaction to obtain the carbon dot material consisting of carbon cores and carbon core surface molecule functional groups.
In the present invention, after the completion of the hydrothermal reaction, it is preferable to further include: and naturally cooling the obtained material to room temperature, filtering, and freeze-drying the obtained filtrate to obtain the rosin-based carbon dot material. In the present invention, the filtration is preferably performed by suction filtration, and the pore diameter of the water-based microporous filter membrane used for suction filtration is preferably 0.22 μm or 0.45 μm. The freeze-drying is preferably carried out in a vacuum freeze-dryer, and the freeze-drying process is not particularly limited in the present invention, and may be a process well known to those skilled in the art. The invention adopts a filtration method for separation, and the separation method is simple. In the invention, the filter residue obtained by filtering can be subjected to hydrothermal synthesis reaction again by using the same method, and the utilization rate of raw materials is high.
The invention provides the rosin-based carbon dot material prepared by the preparation method in the technical scheme. In the present invention, the particle size of the rosin-based carbon dot material is 5nm or less. The invention adopts biomass resource rosin resin acid as raw material, and the carbon dot material prepared by the hydrothermal synthesis method has fluorescence emission property in solid (powder) and solution (dissolved by water or ethanol).
The invention provides application of the rosin-based carbon dot material in the technical scheme in manufacturing WLED. In the present invention, when the rosin-based carbon dot material is used for manufacturing a WLED, the rosin-based carbon dot material is preferably a solid. The method for preparing the WLED from the rosin-based carbon dot material has no special requirement, and the method known by the person skilled in the art can be adopted.
The invention provides the technical scheme that the rosin-based carbon dot material is used for cell imaging and Fe detection3+The use of (1). In the invention, the rosin-based carbon dot material is used for cell imaging and Fe detection3+The method is not particularly limited, and a method known to those skilled in the art may be used.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Putting 0.7g of hydrogenated rosin (hydrogenated abietic acid) into a 100mL hydrothermal synthesis reaction kettle, then pouring 70mL of deionized water into the hydrothermal synthesis reaction kettle, uniformly mixing, carrying out hydrothermal reaction at 180 ℃ for 12h, naturally cooling to room temperature, carrying out suction filtration by using a water-based microporous filter membrane with the aperture of 0.22 mu m, separating filtrate, and carrying out freeze drying on the filtrate to obtain rosin-based CDs solid, namely the rosin-based carbon dot material.
FIG. 1 is an infrared spectrum of the CDs solid prepared in example 1 and a hydrogenated rosin feedstock, from which analysis it can be seen that the functional group structure of the CDs is substantially identical to that of the feedstock, indicating that the carbon core surface may retain the basic structural units of the tricyclic phenanthrene resin acids of the feedstock; moreover, because the basic functional group on the surface of the carbon core is formed by the tricyclic phenanthrene skeleton structure of the raw material, the non-planar steric hindrance effect of the basic functional group can block pi-pi interaction between the carbon cores, so that the occurrence of fluorescence quenching caused by aggregation between the carbon cores is resisted, and the solid CDs material with fluorescence emission property is obtained.
Fig. 2 is an HRTEM photograph of the CDs prepared in example 1, and it is found that the CDs prepared in example 1 mainly consist of nanoparticles having a particle size of 5nm or less, and the particles have good dispersibility.
FIG. 3 is a fluorescence emission spectrum of an aqueous solution (concentration: 125. mu.g/mL) of CDs prepared in example 1 at different excitation wavelengths and a fluorescence color photograph under a 365nm UV lamp; as can be seen from the graph analysis, the strongest peak position of the fluorescence emission of the carbon dot aqueous solution is red-shifted with the increase of the excitation wavelength, which indicates that the CDs aqueous solution has fluorescence excitation dependence. The CDs water solution is irradiated by a 365nm ultraviolet lamp to show blue fluorescence color.
FIG. 4 is a fluorescent emission spectrum of CDs solid prepared in example 1 under different excitation wavelengths and a fluorescent color photograph of powder under 365nm UV light; as can be seen from the graph analysis, the strongest emission peak position of the CDs solid is red-shifted with the increase of the excitation wavelength, which indicates that the prepared CDs solid has the excitation wavelength dependence. The CDs powder is irradiated by a 365nm ultraviolet lamp to show yellow fluorescence emission. According to the optimal excitation wavelength of the emission spectrum, a 450nm blue light semiconductor chip is selected as an excitation source, and the yellow fluorescent CDs are used as a color conversion layer to manufacture a White Light Emitting Diode (WLED).
FIG. 5 is a photograph of Human Umbilical Vein Endothelial Cells (HUVEC) imaged with CDs prepared in example 1, wherein (a) is a photograph in bright field, (b) is a cell after DAPI staining, (c) is a cell after carbon dot fluorescent powder staining, and (d) is a coincidence of (b) and (c); the cells are stained by CDs and DAPI respectively, and from the staining effect, the prepared carbon dot fluorescent powder has the same staining capability with DAPI, can be completely coincided and is used for staining cell nucleuses, so that the CDs prepared by the method can be further used for cell imaging. In addition, imaging experiments of human osteosarcoma cells (MG63) were performed using the CDs prepared in example 1, and as a result, it was found that the carbon dots were useful for cell imaging thereof, and all were stained for cell nucleus. Therefore, the CDs prepared by the invention can be used for cell imaging.
Description of the drawings: the fluorescence spectra were measured using a model LS55 fluorescence spectrometer from Perkinelmer.
FIG. 6 is a graph showing the effect of different metal ions on the fluorescence intensity of an aqueous solution of CDs (20. mu.g/mL) prepared in example 1; wherein, after the metal ions are added into the CDs aqueous solution, the concentration of the metal ions reaches 50 mu M. From the analysis of the graph, Fe3+Since there is a significant quenching effect on the fluorescence intensity of an aqueous CDs solution, Fe is used3+The fluorescence quenching effect on CDs solution can be used for metallic Fe3+Detection of (3).
Example 2
Putting 0.1g of hydrogenated rosin (hydrogenated abietic acid) into a 100mL hydrothermal synthesis reaction kettle, then pouring 70mL of deionized water into the hydrothermal synthesis reaction kettle, uniformly mixing, carrying out hydrothermal reaction at 240 ℃ for 5h, naturally cooling to room temperature, carrying out suction filtration by using a water-based microporous filter membrane with the aperture of 0.22 mu m, separating filtrate, and carrying out freeze drying on the filtrate to obtain rosin-based CDs solid, namely the rosin-based carbon dot material.
Example 3
Putting 0.5g of hydrogenated rosin (hydrogenated abietic acid) into a 100mL hydrothermal synthesis reaction kettle, then pouring 80mL of deionized water into the hydrothermal synthesis reaction kettle, uniformly mixing, carrying out hydrothermal reaction at 160 ℃ for 15h, naturally cooling to room temperature, carrying out suction filtration by using a water-based microporous filter membrane with the aperture of 0.22 mu m, separating filtrate, and carrying out freeze drying on the filtrate to obtain rosin-based CDs solid, namely the rosin-based carbon dot material.
Example 4
Putting 0.3g of rosin (abietic acid) into a 100mL hydrothermal synthesis reaction kettle, then pouring 70mL of deionized water into the hydrothermal synthesis reaction kettle, uniformly mixing, carrying out hydrothermal reaction at 220 ℃ for 8h, naturally cooling to room temperature, carrying out suction filtration by using a water-based microporous filter membrane with the aperture of 0.22 mu m, separating a filtrate, and carrying out freeze drying on the filtrate to obtain the rosin-based CDs solid, namely the rosin-based carbon dot material.
Example 5
Putting 1.0g of rosin (abietic acid) into a 100mL hydrothermal synthesis reaction kettle, then pouring 80mL of deionized water into the hydrothermal synthesis reaction kettle, uniformly mixing, carrying out hydrothermal reaction at 150 ℃ for 18h, naturally cooling to room temperature, carrying out suction filtration by using a water-based microporous filter membrane with the aperture of 0.22 mu m, separating a filtrate, and carrying out freeze drying on the filtrate to obtain the rosin-based CDs solid, namely the rosin-based carbon dot material.
Example 6
Putting 0.5g of dehydrorosin (dehydroabietic acid) into a 100mL hydrothermal synthesis reaction kettle, then pouring 80mL of deionized water into the hydrothermal synthesis reaction kettle, uniformly mixing, carrying out hydrothermal reaction at 180 ℃ for 10h, naturally cooling to room temperature, carrying out suction filtration by using a water-based microporous filter membrane with the aperture of 0.22 mu m, separating filtrate, and freeze-drying the filtrate to obtain the rosin-based CDs solid, namely the rosin-based carbon dot material.
Example 7
Putting 0.8g of dehydrorosin (dehydroabietic acid) into a 100mL hydrothermal synthesis reaction kettle, then pouring 80mL of deionized water into the hydrothermal synthesis reaction kettle, uniformly mixing, carrying out hydrothermal reaction at 120 ℃ for 24h, naturally cooling to room temperature, carrying out suction filtration by using a water-based microporous filter membrane with the aperture of 0.22 mu m, separating filtrate, and freeze-drying the filtrate to obtain rosin-based CDs solid powder, namely the rosin-based carbon dot material.
According to the method in the embodiment 1, the performance test is performed on the rosin-based carbon dot materials prepared in the embodiments 2 to 7, and the result shows that the rosin-based carbon dot materials prepared in the embodiments 2 to 7 can have fluorescence emission properties in solid and solution (dissolved in water or ethanol) and have similar performance to the rosin-based carbon dot material prepared in the embodiment 1.
From the above embodiments, the invention provides a rosin-based carbon dot material, and a preparation method and an application thereof. The rosin-based carbon dot material solid and the solution (water or ethanol solution) prepared by taking the natural biomass resource-rosin resin acid as the raw material both have fluorescence emission properties and have incomparable characteristics with CDs prepared by other biomass raw materials; the rosin-based carbon dot material prepared by the invention can be used for cell imaging and metal Fe3+Detection of ions, solids can be used to make WLEDs.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the rosin-based carbon dot material is characterized by comprising the following steps of:
mixing rosin resin acid with water, and carrying out hydrothermal reaction to obtain the rosin-based carbon dot material.
2. The production method according to claim 1, wherein the rosin-based resin acid is a resin acid having a tricyclic phenanthrene skeleton structure.
3. The method according to claim 2, wherein the rosin-based resin acid is one or more of abietic acid-based resin acid, pimaric acid-based resin acid, and isopimaric acid-based resin acid.
4. The method according to claim 1, wherein the amount of the rosin-based resin acid to water is 0.1 to 1 g/70 to 80 mL.
5. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 150 to 240 ℃ for 5 to 24 hours.
6. The method according to claim 1, further comprising, after the hydrothermal reaction is completed: and naturally cooling the obtained material to room temperature, filtering, and freeze-drying the obtained filtrate to obtain the rosin-based carbon dot material.
7. The method according to claim 6, wherein the filtration is suction filtration, and the pore size of the water-based microporous filter membrane used for the suction filtration is 0.22 μm or 0.45 μm.
8. The rosin-based carbon dot material prepared by the preparation method of any one of claims 1 to 7.
9. Use of the rosin-based carbon dot material of claim 8 in the manufacture of a WLED.
10. Imaging cells or detecting Fe in the rosin-based carbon dot material of claim 83+The use of (1).
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