CN110669516B - Solid fluorescent carbon dot and preparation method and application thereof - Google Patents

Solid fluorescent carbon dot and preparation method and application thereof Download PDF

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CN110669516B
CN110669516B CN201911080599.3A CN201911080599A CN110669516B CN 110669516 B CN110669516 B CN 110669516B CN 201911080599 A CN201911080599 A CN 201911080599A CN 110669516 B CN110669516 B CN 110669516B
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fluorescent carbon
solid fluorescent
carbon dots
resin acid
rosin
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CN110669516A (en
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韩世岩
葛敏
韩有奇
李淑君
陈志俊
于海鹏
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Northeast Forestry University
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    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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    • 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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    • H01L33/502—Wavelength conversion materials
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Abstract

The invention belongs to the technical field of carbon dots, and particularly relates to a solid fluorescent carbon dot and a preparation method and application thereof. According to the invention, a natural biomass resource, namely rosin resin acid with a tricyclic phenanthrene skeleton structure is used as a raw material, and the prepared solid fluorescent carbon dots are not easy to dissolve in water, have adjustable fluorescence and emit yellow (or yellow-green) fluorescence; the invention adopts a one-step hydrothermal synthesis method, does not need complex synthesis and separation and purification, and has simple method and high yield; the prepared solid fluorescent carbon dots can be successfully used for manufacturing White Light Emitting Diodes (WLEDs) emitting warm white, pure white and cold white light, and can also be applied to the fields of waterproof ink printing and cell imaging.

Description

Solid fluorescent carbon dot and preparation method and application thereof
Technical Field
The invention relates to the technical field of carbon dots, in particular to a solid fluorescent carbon dot and a preparation method and application thereof.
Background
Phosphor-based White Light Emitting Diodes (WLEDs) are widely used due to their advantages of low energy consumption, long lifetime, green and environmental protection. In recent years, solid fluorescent carbon dots (SF-CDs) have attracted much attention in the field of white light emitting diodes due to their advantages such as low cost, fluorescence tunability, and environmental friendliness. Currently, most of the solid fluorescent carbon dots prepared by the existing method are fluorescence emission of three primary colors (blue, green and red), while the research for directly obtaining yellow or yellow-green solid fluorescence emission is relatively less, and particularly, the solid fluorescent carbon dots with water resistance are relatively less. And the preparation and purification methods are complicated (such as multiple synthesis, secondary surface structure modification, multiple centrifugal dialysis and the like).
Disclosure of Invention
The invention aims to provide a preparation method of a solid fluorescent carbon dot, and the prepared solid fluorescent carbon dot can emit yellow or yellow-green fluorescence in a solid state.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a solid fluorescent carbon dot, which comprises the following steps:
mixing rosin resin acid, water and ethylenediamine, and carrying out hydrothermal reaction to obtain the solid fluorescent carbon dots.
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 0.1-2 g: 70-80 mL.
Preferably, the dosage ratio of the rosin resin acid to the ethylenediamine is 1g: 0.1-10 mL.
Preferably, the temperature of the hydrothermal reaction is 110-240 ℃ and the time is 1-24 h.
Preferably, after the hydrothermal reaction is completed, the method further comprises: naturally cooling the obtained materials to room temperature, separating, freeze-drying the obtained liquid, dissolving a crude product obtained by freeze-drying in absolute ethyl alcohol, filtering, and sequentially concentrating and vacuum-drying the obtained filtrate to obtain the solid fluorescent carbon dots.
Preferably, the filtration mode is suction filtration, and the pore diameter of the organic microporous filter membrane used in the suction filtration is 0.22 μm or 0.45 μm.
The invention provides the solid fluorescent carbon dots prepared by the preparation method in the technical scheme.
The invention provides application of the solid fluorescent carbon dots in the technical scheme in WLED (white light emitting diode) manufacturing, cell imaging and waterproof ink printing.
The invention provides a preparation method of a solid fluorescent carbon dot, which comprises the following steps:
mixing rosin resin acid, water and ethylenediamine, and carrying out hydrothermal reaction to obtain the solid fluorescent carbon dots.
The invention uses natural biomass resource-rosin resin acid with tricyclic phenanthrene skeleton structure as raw material, which has rich raw material, low cost and green resource.
The invention adopts a one-step hydrothermal synthesis method, does not need complex synthesis and separation and purification, and has simple method and high yield; most of the existing methods are one-step or two-step synthesis treatment, and purification and separation are carried out by adopting methods such as multiple separation or dialysis, and the synthesis and purification methods are relatively complex.
The invention utilizes the unique structural characteristics of the rosin resin acid raw material, and the prepared solid fluorescent carbon dots are not easy to dissolve in water, have adjustable fluorescence and emit yellow (or yellow green) fluorescence in a solid state.
The solid fluorescent carbon dots prepared by the invention can be directly used as a color conversion layer material of a WLED (white light emitting diode), other color series fluorescent powder does not need to be doped and prepared, a 450nm blue light emitting semiconductor chip is used as an excitation source for packaging, a White Light Emitting Diode (WLED) emitting warm white light, pure white light and cold white light can be successfully manufactured, the CIE1931 coordinate of the WLED can reach (0.33 ), the CRI (color rendering index) is more than 80, and the pure white light LED can be successfully realized. The existing three-primary-color (blue, green and red) solid fluorescent carbon dots need to be prepared into WLED on 365nm purple light or 450nm blue light semiconductor chips by adjusting the proportion of fluorescent carbon dot materials of various colors and packaging, and the preparation steps are complicated.
The solid fluorescent carbon dots prepared by the method can also be applied to waterproof ink printing and cell imaging.
Drawings
FIG. 1 is an infrared spectrum of a rosin (abietic acid) raw material, water-soluble carbon dots (product I) and solid fluorescent carbon dots (product II) in example 1;
FIG. 2 is an XPS spectrum (a) of a solid fluorescent carbon dot and a high power XPS spectrum (b) of an N element in example 1;
FIG. 3 is a TEM image of the solid fluorescent carbon dot of example 1;
FIG. 4 is a photograph of solid fluorescent carbon dots prepared in examples 1 and 2 under sunlight (a) and ultraviolet light (b, 365 nm);
FIG. 5 is a fluorescence emission spectrum of the solid fluorescent carbon dot prepared in example 1 at different excitation wavelengths;
FIG. 6 is a photograph showing the water-repellent effect of two kinds of solid fluorescent carbon dots prepared in example 1 (top) and example 2 (bottom);
FIG. 7 is a photograph of an image of Human Umbilical Vein Endothelial Cells (HUVEC) of solid fluorescent carbon dots prepared in example 1;
FIG. 8 is a photograph of a White Light Emitting Diode (WLED) fabricated with solid fluorescent carbon dots prepared in example 1;
FIG. 9 shows the fluorescence emission spectrum of an aqueous solution of water-soluble carbon dots (product I) prepared in example 1.
FIG. 10 is a normalized spectrum of fluorescence emission at 365nm for ethanol solutions of different concentrations of solid fluorescent carbon dots prepared in example 1.
Detailed Description
The invention provides a preparation method of a solid fluorescent carbon dot, which comprises the following steps:
mixing rosin resin acid, water and ethylenediamine, and carrying out hydrothermal reaction to obtain the solid fluorescent carbon dots.
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 BDA0002263833280000031
Figure BDA0002263833280000041
in the present invention, the pimaric type resin acid has the following structural formula:
Figure BDA0002263833280000042
in the present invention, the formula of the isopimaric acid-type resin acid is as follows:
Figure BDA0002263833280000051
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 0.1-2 g/70-80 mL, more preferably 0.2-1.6 g/70-80 mL, and most preferably 0.2-1 g/70-80 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 solid fluorescent carbon dots by controlling the using amount of water.
In the present invention, the amount ratio of the rosin-based resin acid to ethylenediamine is preferably 1 g/0.1 to 10mL, more preferably 1 g/1 to 8mL, and most preferably 1 g/1.5 to 5 mL. The invention uses ethylene diamine as passivation and reaction reagent, and because rosin is insoluble in water, the rosin can be dissolved in water in alkaline aqueous solution after ethylene diamine is added.
In the present invention, the passivation effect of ethylenediamine is mainly to passivate rosin-based resin acids, and N is doped in the carbon core (i.e., pyridine nitrogen, pyrrole nitrogen, or graphite nitrogen exists), and ethylenediamine mainly reacts with carboxyl groups on the rosin-based resin acids to dope N on the surface of the carbon core, i.e., to form amide (O ═ C — NH).
In the invention, the temperature of the hydrothermal reaction is preferably 110-240 ℃, more preferably 150-220 ℃, most preferably 180-200 ℃, and the time is preferably 1-24 hours, more preferably 3-12 hours, and most preferably 4-8 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 is subjected to chemical reaction and carbonization reaction, namely chemical reaction such as decarboxylation and amidation can be carried out, and carbonization reaction is simultaneously carried out along with the chemical reaction, so that the solid fluorescent carbon dots with the resin acid tricyclic phenanthrene structures on the surfaces of the carbon cores are prepared.
In the present invention, after the completion of the hydrothermal reaction, it is preferable to further include: naturally cooling the obtained materials to room temperature, separating, freeze-drying the obtained liquid, dissolving a crude product obtained by freeze-drying in absolute ethyl alcohol, filtering, and sequentially concentrating and vacuum-drying the obtained filtrate to obtain the solid fluorescent carbon dots.
In the present invention, the separation is preferably performed by centrifugation or filtration, and insoluble materials in the hydrothermal reaction product are separated and removed. In the present invention, it is preferable to select a method for removing insoluble matter depending on the viscosity of the product (the material obtained by the hydrothermal reaction), to perform centrifugation if the viscosity of the hydrothermal solution is too high to facilitate filtration, and to perform suction filtration using a microporous filter membrane, which is preferably an aqueous filter membrane, and which has a pore diameter of preferably 0.22 μm or 0.45 μm.
The freeze-drying is preferably performed in a freeze-dryer, and the freeze-drying process is not particularly limited, and may be performed by a process known to those skilled in the art.
When the crude product is dissolved in absolute ethyl alcohol, the dosage of the ethyl alcohol is not particularly limited, and the crude product can be completely dissolved. The method adopts the ethanol solvent for dissolution and separation, and has the advantages of simple method, easy operation and high yield.
In the present invention, the filtration is preferably suction filtration, the medium for suction filtration is preferably filter paper or a filter membrane, the filter membrane is preferably an organic filter membrane, and the pore size of the filter membrane is preferably 0.22 μm or 0.45 μm. The invention adopts a filtration method for separation, and the separation method is simple.
In the invention, the solid insoluble substance obtained by filtering can be directly a dried substance, and can also be further dried by an oven drying or vacuum drying method to obtain a by-product, namely a water-soluble carbon dot. In the invention, the obtained water-soluble carbon dots are mainly carbonized products obtained by the reaction of carboxyl removed from rosin resin acid at high temperature and ethylenediamine, are easily soluble in water and have fluorescence emission property in water solution, and the aqueous solution of the water-soluble carbon dots is blue fluorescence emission under the irradiation of a 365nm ultraviolet lamp and can be used for cell imaging.
The concentration and vacuum drying process is not particularly limited in the present invention, and may be a process known to those skilled in the art.
The invention provides the solid fluorescent carbon dots prepared by the preparation method in the technical scheme. In the invention, the particle size of the solid fluorescent carbon dots is less than 20 nm. The solid fluorescent carbon dots prepared by a hydrothermal method show yellow or yellow-green fluorescence under the irradiation of a 365nm ultraviolet lamp, mainly because the solid fluorescent carbon dots are composed of graphitized carbon cores and molecular structures on the surfaces of the carbon cores, the molecular structures on the surfaces of the carbon cores can be mainly an amidated tricyclic phenanthrene molecular structure and a decarboxylated tricyclic phenanthrene molecular structure, and the solid non-planar steric hindrance effect of the tricyclic phenanthrene framework structure hinders pi-pi interaction between the carbon cores and resists the occurrence of fluorescence self-quenching of the carbon cores in a solid state, so that the solid fluorescent carbon dots can emit fluorescence in the solid state. The solid fluorescent carbon dot prepared by the invention is not easy to dissolve in water, has adjustable fluorescence and is yellow (or yellow green) fluorescence emission.
The invention provides application of the solid fluorescent carbon dots in the technical scheme in preparation of WLED, cell imaging and waterproof ink printing.
When the solid fluorescent carbon dots are used for manufacturing a WLED, the solid carbon dots and a curing adhesive are mixed in a proper proportion, other color series fluorescent materials are not required to be mixed and mixed, the mixture is directly packaged on a 450nm blue light emitting semiconductor chip, a White Light Emitting Diode (WLED) emitting warm white light, pure white light and cold white light can be manufactured, the CIE1931 coordinate can reach (0.33 ) pure white light, and the color rendering index is more than 80. In the present invention, the glue preferably includes one of epoxy glue, a/B glue, PDMS glue, and uv-curable glue. In the packaging process, the glue consumption is mainly used for obtaining the white light emitting diode, and the proportion of the glue and the powder can influence the color rendering index, CIE1931 coordinate and color temperature of the WLED lamp due to the shape and the thickness of the chip packaged in the packaging process.
In the present invention, the steps of making the WLED lamp are preferably: grinding the solid fluorescent carbon dots, stirring and mixing the ground solid fluorescent carbon dots with glue uniformly, if bubbles exist in the mixture, defoaming by adopting ultrasonic (or centrifugation or vacuumizing), then covering the obtained mixture on a 450nm blue-light semiconductor chip (the chip cannot be leaked, namely air cannot be leaked), and drying the semiconductor chip in an oven at 80 ℃ for 2-3 h (or naturally drying at room temperature) (according to the curing condition of the used glue), thereby obtaining the WLED. The specific conditions for the stirring and ultrasound are not particularly limited in the present invention, and a process known to those skilled in the art may be selected.
In the invention, the carbon dot fluorescent powder is not easy to dissolve in water but easy to dissolve in an absolute ethyl alcohol solvent, and solid fluorescent carbon dot solutions with different concentrations are prepared by using the ethyl alcohol solvent, so that multicolor fluorescence emitted by different fluorescence can be obtained, and therefore, the solid fluorescent carbon dots can be used in multicolor waterproof fluorescent ink. The method for applying the solid fluorescent carbon dots to the printing of the waterproof ink is not particularly limited, and a method known to those skilled in the art can be used.
The method for using the solid fluorescent carbon dot in cell imaging is not particularly limited in the present invention, and a method well known to those skilled in the art may be selected.
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
Uniformly mixing and dispersing 0.4g of rosin (abietic acid) and 70mL of deionized water, pouring into a 100mL hydrothermal reaction kettle, adding 1mL of ethylenediamine, uniformly mixing, carrying out hydrothermal reaction at 200 ℃ for 5 hours, naturally cooling the obtained material to room temperature, centrifuging, and freeze-drying the obtained solution to obtain a crude product; adding absolute ethyl alcohol into the crude product to dissolve the crude product, filtering and separating out insoluble substances, and drying the insoluble substances in an oven to obtain water-soluble carbon dots (product I); the filtrate was concentrated and filtered, and dried under vacuum to obtain solid fluorescent carbon dots (product II).
The solid fluorescent carbon dots (product II) were determined to have yellow fluorescence under 365nm UV light, and the aqueous solution of water-soluble carbon dots (product I) exhibited blue fluorescence emission under 365nm UV light.
FIG. 1 is an infrared spectrum of a rosin starting material, water-soluble carbon dots (product I) and solid fluorescent carbon dots (product II) of example 1; as can be seen from the analysis of the figure, the solid fluorescent carbon dots and the water-soluble carbon dots are 1640cm-1an-C ═ O stretching vibration absorption peak on amide appears in the vicinity of the solid fluorescent carbon dots, an N-H bending vibration absorption peak and a C-N stretching vibration absorption peak also appear in the structure of the solid fluorescent carbon dots, and the solid fluorescent carbon dots mainly take amidation reaction between rosin and ethylenediamine, namely the solid fluorescent carbon dots (product II) take surface N-doping reaction.
FIG. 2 is an XPS spectrum (a) of a solid fluorescent carbon dot (product II) and a high power XPS spectrum (b) of an N element in example 1; according to analysis of (a), the prepared solid fluorescent carbon dot mainly consists of C, O, N elements, which indicates the successful introduction of N element; from the analysis of (b), the existence mode of the N element in the solid fluorescent carbon dots mainly comprises the following steps: the existence of pyridine N, N-H (N on amide), pyrrole N, and graphite N in a combined manner shows that the N element exists in two manners of internal graphitizing N doping and surface N doping.
FIG. 3 is a transmission electron micrograph of a solid fluorescent carbon dot (product II) in example 1; as can be seen from the graph analysis, the solid fluorescent carbon dots prepared in example 1 mainly have a particle size distribution of 2 to 13nm and are carbon dot materials.
FIG. 5 is a fluorescence emission spectrum of the solid fluorescent carbon dot prepared in example 1 at different excitation wavelengths; as can be seen from graph analysis, the solid fluorescent carbon dot prepared by using rosin as a raw material has the characteristic that the corresponding strongest fluorescence emission peak position is subjected to red shift along with the increase of the excitation wavelength in the solid state, so that the solid fluorescent carbon dot has fluorescence excitation dependency and the strongest emission peak position is in a green light region. (Note: the fluorescence spectroscopy test data used in the present invention was LS55 type fluorescence spectrometer).
FIG. 7 is a photograph of an image of solid fluorescent carbon dots prepared in example 1 on Human Umbilical Vein Endothelial Cells (HUVEC), wherein (a) is a photograph in a bright field, (b) is a cell stained with DAPI (4', 6-diamidino-2-phenylindole), (c) is a cell stained with a solid fluorescent carbon dot, and (d) is the coincidence of the graphs of (b) and (c); the solid fluorescent carbon dots and the DAPI are respectively used for staining human umbilical vein vascular endothelial cells (HUVEC), and from the staining effect, the prepared solid fluorescent carbon dots have the same staining capability with the DAPI, can be completely coincided and are used for staining cell nuclei, so that the solid fluorescent carbon dots prepared by the method can be further used for cell imaging. In addition, imaging experiments were performed on cells of "human immortalized epidermal cells (Hacat) and human osteosarcoma cells (MG 63)" using the solid fluorescent carbon dots prepared in example 1, and the results showed that the prepared solid fluorescent carbon dots can be used for cell imaging and staining cell nuclei.
FIG. 8 is a photograph of a White Light Emitting Diode (WLED) fabricated with solid fluorescent carbon dots prepared in example 1;
the steps for preparing the white light-emitting diode are as follows: grinding the solid fluorescent carbon dots, mixing the ground solid fluorescent carbon dots with epoxy resin glue (powder: glue is 1:13), carrying out ultrasonic treatment, then covering the obtained mixture on a 450nm blue-light semiconductor chip, and drying the blue-light semiconductor chip in an oven at 80 ℃ for 2 hours to obtain a WLED (white light emitting diode), wherein the WLED is an LED with white light emission and has CIE1931 coordinates (0.33 ). By adjusting the dosage of the solid fluorescent carbon dot powder and the glue, the WELD capable of emitting warm white light, pure white light and cold white light can be respectively obtained, and the color rendering index is more than 80.
FIG. 9 is a fluorescence emission spectrum of an aqueous solution of water-soluble carbon dots (product I) prepared in example 1; as can be seen from the graph analysis, the resultant product I has blue fluorescence emission in aqueous solution, and the emission peak position is red-shifted with the increase of the excitation wavelength, indicating that the fluorescence emission has excitation wavelength dependence.
FIG. 10 is a normalized spectrum of fluorescence emission of 365nm excited by ethanol solutions of solid fluorescent carbon dots prepared in example 1 at different concentrations (from left to right, in order, 1, 5, 10, 15, 20, 25, 30, 35 mg/mL); as can be seen from the graph analysis, the strongest fluorescence emission peak position of the solid fluorescent carbon dot ethanol solution is red-shifted along with the increase of the concentration, which shows that the solid fluorescent carbon dot has multicolor fluorescence adjustability along with the difference of the concentration.
Example 2
Mixing and dispersing 0.4g of dehydroabietic acid (dehydroabietic acid) and 70mL of deionized water uniformly, pouring the mixture into a 100mL hydrothermal reaction kettle, adding 1mL of ethylenediamine, mixing uniformly, carrying out hydrothermal reaction at 200 ℃ for 5h, naturally cooling the obtained material to room temperature, centrifuging, freeze-drying the obtained solution to obtain a crude product, adding absolute ethyl alcohol into the crude product to dissolve the crude product, filtering and separating out insoluble substances, and vacuum-drying the obtained insoluble substances to obtain water-soluble carbon dots (product I); the filtrate was concentrated and filtered, and dried under vacuum to obtain solid fluorescent carbon dots (product II).
The solid fluorescent carbon dots (product II) have yellow green fluorescence under the irradiation of a 365nm ultraviolet lamp, and the water solution of the water-soluble carbon dots (product I) has blue fluorescence emission under the irradiation of the 365nm ultraviolet lamp.
FIG. 4 is a photograph of solid fluorescent carbon dots (product II) prepared in examples 1 and 2 under sunlight (a) and ultraviolet light (b, 365 nm); wherein (a) the left side is the solid fluorescent carbon dot prepared in example 1, which is a dark yellow solid in sunlight, (b) the left side is the solid fluorescent carbon dot prepared in example 1, which shows yellow fluorescence under an ultraviolet lamp (365 nm); (a) the right is the solid fluorescent carbon dot prepared in example 2 as a pale yellow solid in daylight, (b) the right is the solid fluorescent carbon dot prepared in example 2, exhibiting yellow-green fluorescence under an ultraviolet lamp (365 nm).
FIG. 6 is a photograph showing the water repellent effect of two solid fluorescent carbon dots prepared in example 1 (top) and example 2 (bottom); as can be seen from the figure, after two solid fluorescent carbon dots prepared by using rosin and dehydrogenated rosin as raw materials are washed by cold water for 60min after being dissolved in absolute ethyl alcohol, the written NEFU font still has the fluorescent color under the irradiation of an ultraviolet lamp of 365nm, which indicates that the fluorescent powder has the waterproof effect and can be used in waterproof fluorescent ink.
Imaging experiments of the solid fluorescent carbon dots prepared in example 2 on cells of Human Umbilical Vein Endothelial Cells (HUVEC), human immortalized epidermal cells (Hacat) and human osteosarcoma cells (MG63) show that the prepared solid fluorescent carbon dots can be used for cell imaging and staining cell nuclei.
Example 3
Mixing and dispersing 0.4g of hydrogenated rosin (hydrogenated abietic acid) and 70mL of deionized water uniformly, pouring the mixture into a 100mL hydrothermal synthesis reaction kettle, adding 1mL of ethylenediamine, mixing uniformly, carrying out hydrothermal reaction at 200 ℃ for 5h, naturally cooling the obtained material to room temperature, centrifuging, freeze-drying the obtained solution to obtain a crude product, adding absolute ethyl alcohol into the crude product to dissolve the crude product, filtering and separating out insoluble substances, and carrying out cold vacuum drying on the obtained insoluble substances to obtain water-soluble carbon dots (product I); the filtrate was concentrated and filtered, and dried under vacuum to obtain solid fluorescent carbon dots (product II).
The solid fluorescent carbon dots (product II) were determined to have yellow fluorescence under 365nm UV light, and the aqueous solution of water-soluble carbon dots (product I) was determined to have blue fluorescence emission under 365nm UV light.
Example 4
Uniformly mixing and dispersing 2g of rosin (abietic acid) and 80mL of deionized water, pouring the mixture into a 100mL hydrothermal synthesis reaction kettle, adding 0.5mL of ethylenediamine, uniformly mixing, carrying out hydrothermal reaction at 200 ℃ for 5h, naturally cooling the obtained material to room temperature, centrifuging, freeze-drying the obtained solution to obtain a crude product, adding absolute ethyl alcohol into the crude product to dissolve the crude product, filtering to separate out insoluble substances, and drying the obtained insoluble substances in an oven to obtain water-soluble carbon dots (product I); the filtrate was concentrated and filtered, and dried under vacuum to obtain solid fluorescent carbon dots (product II).
The solid fluorescent carbon dots (product II) were determined to have yellow fluorescence under 365nm UV light, and the aqueous solution of water-soluble carbon dots (product I) was determined to have blue fluorescence emission under 365nm UV light.
Example 5
Uniformly mixing and dispersing 0.5g of rosin (abietic acid) and 70mL of deionized water, pouring the mixture into a 100mL hydrothermal synthesis reaction kettle, adding 1mL of ethylenediamine, uniformly mixing, carrying out hydrothermal reaction at 120 ℃ for 24 hours, naturally cooling the obtained material, centrifuging, freeze-drying the obtained solution to obtain a crude product, adding absolute ethyl alcohol into the crude product to dissolve the crude product, filtering to separate out insoluble substances, and vacuum-drying the obtained insoluble substances to obtain water-soluble carbon dots (product I); the filtrate was concentrated and filtered, and dried under vacuum to obtain solid fluorescent carbon dots (product II).
The solid fluorescent carbon dots (product II) have yellow green fluorescence under the irradiation of a 365nm ultraviolet lamp, and the water solution of the water-soluble carbon dots (product I) has blue fluorescence emission under the irradiation of the 365nm ultraviolet lamp.
Example 6
Uniformly mixing and dispersing 2g of rosin (abietic acid) and 70mL of deionized water, pouring the mixture into a 100mL hydrothermal synthesis reaction kettle, adding 10mL of ethylenediamine, uniformly mixing, carrying out hydrothermal reaction at 240 ℃ for 3h, naturally cooling the obtained material, carrying out freeze drying to obtain a crude product, adding absolute ethyl alcohol into the crude product to dissolve the crude product, filtering to separate out insoluble substances, and drying the insoluble substances in an oven to obtain water-soluble carbon dots (product I); the filtrate was concentrated and filtered, and dried under vacuum to obtain solid fluorescent carbon dots (product II).
The solid fluorescent carbon dots (product II) have yellow green fluorescence under the irradiation of a 365nm ultraviolet lamp, and the water solution of the water-soluble carbon dots (product I) has blue fluorescence emission under the irradiation of the 365nm ultraviolet lamp.
The performance test of the carbon dot phosphors prepared in examples 3 to 6 was carried out according to the methods of examples 1 and 2, and the results show that the solid fluorescent carbon dots prepared in examples 3 to 6 have the performance similar to that of the solid fluorescent carbon dots prepared in examples 1 and 2, and can be used for manufacturing WLED, cell imaging and waterproof ink printing.
From the above embodiments, the invention provides a solid fluorescent carbon dot, and a preparation method and an application thereof. The solid fluorescent carbon dots prepared by taking natural biomass resources, namely rosin resin acids, as raw materials can emit yellow or yellow-green fluorescence in a solid state; the solid fluorescent carbon dots prepared by the method can be used for manufacturing WLED, cell imaging and waterproof ink printing.
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 (9)

1. A preparation method of a solid fluorescent carbon dot is characterized by comprising the following steps:
mixing rosin resin acid, water and ethylenediamine, and carrying out hydrothermal reaction to obtain solid fluorescent carbon dots;
the temperature of the hydrothermal reaction is 110-240 ℃, and the time is 1-24 h.
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 2g:70 to 80 mL.
5. The method according to claim 1 or 4, wherein the rosin-based resin acid and ethylenediamine are used in an amount of 1g:0.1 to 10 mL.
6. The method according to claim 1, further comprising, after the hydrothermal reaction is completed: naturally cooling the obtained materials to room temperature, separating, freeze-drying the obtained liquid, dissolving a crude product obtained by freeze-drying in absolute ethyl alcohol, filtering, and sequentially concentrating and vacuum-drying the obtained filtrate to obtain the solid fluorescent carbon dots.
7. The method according to claim 6, wherein the filtration is performed by suction filtration, and the pore size of the organic microporous membrane used in the suction filtration is 0.22 μm or 0.45 μm.
8. A solid fluorescent carbon dot prepared by the preparation method of any one of claims 1 to 7.
9. Use of the solid fluorescent carbon dot of claim 8 in WLED fabrication, cell imaging and water-repellent ink printing.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542764A (en) * 2016-01-29 2016-05-04 兰州大学 Yellow fluorescence carbon dots with high quantum yield and preparation method thereof
CN109054821A (en) * 2018-07-13 2018-12-21 山西大学 A kind of fluorescent carbon point and its preparation method and application
CN109988571A (en) * 2019-04-06 2019-07-09 天津大学 A kind of preparation of solid state fluorescence carbon quantum dot material and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542764A (en) * 2016-01-29 2016-05-04 兰州大学 Yellow fluorescence carbon dots with high quantum yield and preparation method thereof
CN109054821A (en) * 2018-07-13 2018-12-21 山西大学 A kind of fluorescent carbon point and its preparation method and application
CN109988571A (en) * 2019-04-06 2019-07-09 天津大学 A kind of preparation of solid state fluorescence carbon quantum dot material and application

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