CN111748344A - Synthesis method of full-color fluorescent carbon dots, and product and application thereof - Google Patents
Synthesis method of full-color fluorescent carbon dots, and product and application thereof Download PDFInfo
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- CN111748344A CN111748344A CN202010698172.6A CN202010698172A CN111748344A CN 111748344 A CN111748344 A CN 111748344A CN 202010698172 A CN202010698172 A CN 202010698172A CN 111748344 A CN111748344 A CN 111748344A
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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Abstract
The invention discloses a synthesis method of full-color fluorescent carbon dots, a product and an application thereof, wherein the synthesis method is characterized in that indole or methyl substituted indole is used as a raw material, the full-color fluorescent carbon dots are prepared by a one-pot hydrothermal reaction in an ethanol solution of acid and an oxidant, 10 fluorescent carbon dots with independent laser properties can be separated, the emission wavelengths of the fluorescent carbon dots are 333nm, 380nm, 416nm, 437nm, 475nm, 508nm, 543nm, 571nm, 587nm and 608nm respectively, the fluorescent carbon dots cover the ultraviolet to near-infrared emission regions, and the fluorescent carbon dots have the characteristic of strong photobleaching resistance and can be applied to multi-color LEDs.
Description
Technical Field
The invention relates to the field of carbon dots, in particular to a synthesis method of a full-color fluorescent carbon dot, and also relates to a product prepared by the method and application of the product.
Background
Since 2004, Carbon Dots (CDs) were first prepared by purifying fluorescent single-walled carbon nanotube fragments, researchers have developed carbon dots with different sizes, microstructures, morphologies, and fluorescence properties. Compared with the traditional semiconductor quantum dots and aromatic fluorescent dyes, the carbon dots have more excellent characteristics including low toxicity or no toxicity, high chemical inertness, good biocompatibility, strong photobleaching resistance, excellent photoelectric property, easy surface modification and the like, and show huge potential in the fields of biological imaging, chemical/biological sensing, drug/gene delivery, photoelectric devices and the like. In recent years, carbon dots with multicolor fluorescence have attracted more research interest because they overcome the shortwave emission of carbon dots, are suitable for multicolor cell labeling, multi-mode fluorescence imaging and full-color LED illumination, and broaden the application fields of carbon dots. However, most of the carbon dots reported can emit only a single blue-green light, greatly limiting the application fields thereof. Therefore, it is necessary to develop a method for synthesizing multicolor quantum dots.
At present, the synthesis strategies of multicolor fluorescent carbon dots mainly comprise the following three strategies: (1) under the same reaction conditions, by using different materials as precursors. For example, Jiang and the like take three phenylenediamine isomers as raw materials, and synthesize blue, green and red three-color fluorescent products through the same hydrothermal reaction; (2) the same raw material is processed by different reaction conditions and methods, including changing reaction types (hydrothermal reaction, microwave reaction, acid-base corrosion, laser ablation and the like), solvent types, pH values of reaction liquid, reaction time, reaction temperature and the like. Rogach et al use urea and citric acid as raw materials to perform a solvothermal reaction, synthesize a series of carbon dots with emission wavelengths of 448-638 nm by using different types of solvents (water, glycerol, DMF), and regard the solvent effect as the most critical factor of dehydration and carbonization in the formation process of the carbon dots; by adjusting the treatment temperature of strong acid, Lee and the like destroy the complete structure of the carbon fiber, and a blue to deep red (460-805 nm) luminescent product is obtained. (3) Simultaneously, the precursor and the synthesis method are changed. The Yang subject group selects different mixtures of diaminonaphthalene and citric acid as precursors, and finally obtains blue, green, yellow, orange and red five-color fluorescent carbon dots by adjusting the pH value of reaction liquid and controlling the melting and carbonization of raw materials through reaction time. Although these methods have strong advantages in the synthesis of multicolor fluorescent carbon dots, the synthesis process is relatively complex, and the introduction of more variables may affect the reproducibility of the experiment and is also not beneficial to research on the fluorescence mechanism. Therefore, a strategy for synthesizing full-color fluorescent carbon dots from a single precursor under the same reaction conditions is urgently needed.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for synthesizing a full-color fluorescent carbon dot; the second purpose of the invention is to provide a full-color fluorescent carbon dot synthesized by the synthesis method; the invention also aims to provide application of the full-color fluorescent carbon dot in preparation of an LED illuminating lamp.
In order to achieve the purpose, the invention provides the following technical scheme:
1. the synthesis method of the full-color fluorescent carbon dot comprises the following steps: indole or methyl substituted indole is used as a raw material, and a one-pot hydrothermal reaction is carried out in an ethanol solution of acid and an oxidant, wherein the methyl substituted indole is 3-methylindole, 4-methylindole, 5-methylindole or 6-methylindole.
As the preferable technical scheme of the invention, the acid is strong/medium-strong organic acid or inorganic acid; the oxidant is an organic oxidant or an inorganic oxidant. The acid is hydrochloric acid, sulfuric acid, trifluoroacetic acid or phosphoric acid; the oxidant is hydrogen peroxide, potassium periodate, periodic acid, di-tert-butyl peroxide, dilauroyl peroxide or dibenzoyl peroxide.
In the invention, the preparation method comprises the following steps: dissolving indole or methyl substituted indole in ethanol under the action of ultrasound, adding acid and oxidant, stirring and mixing uniformly, and carrying out hydrothermal reaction to obtain dark brown red liquid.
Preferably, the hydrothermal reaction is carried out for 0.5-2.0 h at 160-180 ℃.
Preferably, the mol ratio of indole or methyl substituted indole to acid to hydrogen peroxide in the synthesis process is 3.4: 0.2-1.5: 0.4 to 2.00.
Preferably, the indole or methyl-substituted indole, the acid and H2O2In a molar ratio of 3.4: 0.74: 1.59.
preferably, the addition amount of the ethanol is 0.34-3.40 mmol/ml according to the concentration of the added indole or methyl substituted indole.
2. The full-color fluorescent carbon dots synthesized by the synthesis method.
Preferably, the full-color fluorescent carbon dots are eluted in a silica gel column by using a mixed solution of ethanol and ethyl acetate as an eluent to obtain 10 kinds of fluorescent carbon dots, the color of the fluorescent carbon dots changes from blue to red, and the emission wavelengths of the fluorescent carbon dots are 333nm, 380nm, 416nm, 437nm, 475nm, 508nm, 543nm, 571nm, 587nm and 608nm respectively.
3. The full-color fluorescent carbon dot is applied to preparation of fluorescent powder or LED illuminating lamps.
The invention has the beneficial effects that: the invention discloses a synthesis method of a full-color fluorescent carbon dot, which comprises the steps of taking single indole or methyl substituted indole as a raw material, carrying out one-pot hydrothermal reaction in an ethanol solution of acid and an oxidant, and then separating 10 fluorescent carbon dots which do not depend on laser properties by utilizing a silica gel column chromatography, wherein the emission wavelengths of the fluorescent carbon dots are 333, 380, 416, 437, 475, 508, 543, 571, 587 and 608nm respectively, and the fluorescent carbon dots cover an ultraviolet to near-infrared emission region. The synthesized carbon dot and starch composite material is used as fluorescent powder, epoxy resin is mixed, and the LED lamp is assembled, so that multi-color light emitting can be realized.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 shows the synthesis and effect of panchromatic fluorescent carbon dots prepared from indole (a: panchromatic fluorescent carbon dots prepared from indole; b: carbon dot distribution in silica gel column (365 nm ultraviolet irradiation with Ethyl Acetate (EAC) and Ethanol (EA) as eluent), c: carbon dot ethanol dispersion in visible light (top) and ultraviolet (bottom)).
FIG. 2 shows the effect of reaction temperature and time on the product (a: reaction at 160 ℃ for 0.5/1.0/1.5/2.0h, b: reaction at 180 ℃ for 0.5/1.0/1.5/2.0h, c: reaction at 200 ℃ for 0.5/1.0/1.5/2.0h, respectively).
FIG. 3 shows HCl and H2O2Effect of dose on the product (a: 0.4g indole and 0.16mL H2O2After the solution is prepared, 0/0.02/0.04/0.06/0.08/0.10mL of HCl is added respectively; b: 0.4g indole and 0.06mL HCl are prepared into solution and then0/0.04/0.08/0.12/0.16/0.20mL of H was added separately2O2(ii) a c: 0.4g of indole was directly dissolved in ethanol and reacted).
FIG. 4 shows the distribution of carbon dots synthesized from different raw materials in a chromatographic column (from left to right, the raw materials are indoline, 1-methylindole, 2-methylindole, 3-methylindole, 4-methylindole, 5-methylindole and 6-methylindole in sequence).
FIG. 5 shows the excitation spectra (blue) corresponding to the UV-visible absorption spectrum (black), emission spectrum (red), and optimal fluorescence emission for each carbon spot (a: 1-CD; b: 2-CD; c: 3-CD; d: 4-CD; e: 5-CD; f: 6-CD; g: 7-CD; h: 8-CD; i: 9-CD; j: 10-CD).
FIG. 6 shows the variation trend of UV-visible absorption, fluorescence excitation spectrum, fluorescence emission spectrum peak and Stokes shift value.
FIG. 7 shows the fluorescence intensity of the five ethanol solutions as a function of the illumination time.
FIG. 8 shows the fluorescent pictures of the multi-color carbon dot/starch phosphor in the 365nm UV lamp, the fluorescent pictures of five starch/carbon dot composite phosphors in the visible light (upper) and under different excitation lights (lower) under the inverted fluorescence microscope (a-Por and b-Por are excited by UV, c-and d-Por are excited by blue light, and e-Por is excited by green light), and d is five LED effects when direct current with voltage of 3V (supplied by a battery) is applied.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1 Synthesis of panchromatic fluorescent carbon dots
0.4g of indole (3.4mmol) was dissolved in 10mL of ethanol under sonication, 0.06mL of 38% HCl (0.74 mmol) and 0.16mL of 30% H were added2O2(1.59mmol) and stirred rapidly. The light yellow clear solution was quickly transferred to a 20mL Teflon linerIn a high-pressure reaction kettle, the deep brown red liquid is obtained after the reaction is carried out for 1.5h at 180 ℃ in an oven (figure 1, a). Removing excessive solvent by rotary evaporation, eluting in silica gel column with mixed solution of ethanol and ethyl acetate as eluent, and distributing the components in the silica gel column under 365nm ultraviolet irradiation (figure 1, b), which shows that from bottom to top, the fluorescence color changes from blue to red as the polarity of the carbon dot component increases, and the components are respectively marked as 1-CD and 2-CD … 10-CD.
And (3) storing one part of the separated solid in a constant-temperature sample storage cabinet, quantitatively dissolving the other part of the solid in ethanol to prepare a carbon point concentrated solution, storing the carbon point concentrated solution in a refrigerator at 4 ℃, preparing solutions with different concentrations according to experimental needs, and observing the solutions by ultraviolet, wherein the result is shown as c in figure 1. The results showed that 10 fluorescent carbon spots were isolated and obtained by stepwise column chromatography.
Optimizing synthesis reaction conditions: to optimize the reaction conditions, a series of comparative experiments were performed:
(1) orthogonal test: 0.4g indole, 0.06mL HCl and 0.16mL H2O2The solution is placed at 160 ℃ and reacts for 0.5h, 1.0h, 1.5h and 2.0h respectively; reacting at 180 deg.C for 0.5h, 1.0h, 1.5h, and 2.0h, respectively; the reaction is carried out for 0.5h, 1.0h, 1.5h and 2.0h at 200 ℃, and the synthetic result is shown in figure 2. The result shows that the full-color fluorescent carbon dots can be synthesized at the reaction temperature of 160-180 ℃ for 0.5-2.0 h, wherein the effects are the best when the reaction temperature and the reaction time are respectively 180 ℃ and 1.5 h.
(2) The reaction was carried out at 180 ℃ for 1.5h with varying concentrations of the components: 0.4g of indole and 0.16mL of H2O2After the solution is prepared, 0mL, 0.02mL, 0.04mL, 0.06mL, 0.08mL and 0.10mL of HCl are respectively added; preparing 0.4g indole and 0.06mL HCl into solution, and adding 0mL, 0.04mL, 0.08mL, 0.12mL, 0.16mL, 0.20mL H2O2(ii) a Only 0.4g indole was made into solution without addition of H2O2And HCl. The dark brown liquid obtained above was diluted ten times with ethanol to prepare a diluted solution, which was placed under a 365nm ultraviolet lamp, and the results are shown in fig. 3. The results show that HCl and H2O2The dosage of the fluorescent carbon can synthesize full-color fluorescent carbon under 0.02-0.10 ml and 0.04-0.20 ml respectivelyPoint, but HCl and H2O2The effect is best when the dosage is 0.06mL and 0.16m respectively; certain amount of HCl and H are not added into the reaction liquid2O2Multicolor fluorescent products could not be obtained, indicating HCl and H2O2Both participate in the reaction.
Example 2 Synthesis of carbon dots starting with methyl-substituted indole or indoline
The synthesis method is consistent with the method: 0.06mL of HCl and 0.16mL of H were added to 0.4g (3.4mmol) of indoline or 0.45g (3.4mmol) of methyl-substituted indole (1-methylindole, 2-methylindole, 3-methylindole, 4-methylindole, 5-methylindole, 6-methylindole)2O2And 10mL of ethanol, and carrying out solvothermal reaction at 180 ℃ for 1.5 h. Concentrating the obtained crude product by rotary evaporation, and performing column chromatography by using a mixed solution of ethyl acetate and ethanol (the ratio is 10:1) as an eluent. Slightly separated, the chromatographic column was switched off and placed under a 365nm ultraviolet lamp to observe the distribution of each component, and the results are shown in FIG. 4.
The results show that the following phenomena can be observed from the upper graph:
(1) when raw materials (3-methylindole, 4-methylindole, 5-methylindole and 6-methylindole) with methyl on a benzene ring are used, similar multicolor carbon points can be obtained, which indicates that the synthesis of the carbon points is not greatly related to the benzene ring;
(2) when starting materials with methyl groups at the 2 or 3 position of the pyrrole ring (1-methylindole and 2-methylindole) are used, no analogous carbon points are obtained, probably because the steric hindrance provided by the methyl group hinders the reaction of the C ═ C bond of the pyrrole ring;
(3) when the raw material (1-methylindole) with methyl at the substitution position of pyrrole ring 1 is used, the phenomenon of fluorescence stratification is not obvious, and pyrrole ring N may participate in carbon point formation;
(4) when indoline without a C ═ C bond is used as a raw material, a large amount of non-fluorescent components remain at the upper end of the chromatographic column, and only a blue light product with extremely low yield can be obtained.
The above phenomena indicate that the pyrrole ring C ═ C bond is critical for carbon point formation, while for 1-methylindole, its 1-H is substituted, inhibiting protonation of the pyrrole ring under acidic conditions. It is presumed that during the formation of the carbon dots, oxidation of indole and acidic cationic polymerization occur.
Example 3 optical Properties of full color fluorescent carbon dots
The UV-VIS absorption spectra of ten carbon spots were measured, and the results are shown in FIG. 5. The results show that, in addition to 1-CDs, other carbon dots have two distinct absorption peaks. This is probably because the first and second absorption peaks are too close to coincide on the Abs spectrum of 1-CDs. From 2-CDs to 10-CDs, the absorption peak with longer wavelength (namely the second peak of 330-565 nm) corresponds to n-pi transition caused by the surface functional group of the carbon dot; similarly, the absorption peak with shorter wavelength (i.e. the first peak of 283-372 nm) corresponds to the pi-pi transition of C-C on the carbon core where the conjugated structure is dominant; as the fluorescence of the carbon dots is red-shifted, the two groups of absorption peaks also gradually move towards the long wavelength direction. The excitation spectrum (blue line, Ex) corresponding to the optimal emission wavelength of each carbon spot in fig. 5 also shows two excitation peaks, one in front of the other very close to the corresponding two absorption peaks, which means that these carbon spots have two energy absorption centers related to the generation of fluorescence, i.e. the carbon core and the carbon spot surface absorb the energy for the emission of fluorescence together. As described above, there is a one-to-one correspondence between Abs, Ex, and Em, which are shown in table 1 and fig. 6 for convenience of comparison, and Stokes shifts (Stokes-shifts, i.e., differences between Em wavelengths and corresponding Abs peaks) are calculated. The results show that the fluorescence emission peak (Em) is red-shifted from 1-CDs to 10-CDs with increasing Abs peak, 333, 380, 416, 437, 475, 508, 543, 571, 587 and 608nm, respectively. These wavelengths covered the ultraviolet to near infrared emission region with an average difference of 8, indicating that the components were evenly distributed on the silica gel column, which is advantageous for separation and purification. More notably, from 2-CDs to 6-CDs, the optimal excitation wavelength is the first excitation peak corresponding to the first Abs absorption peak; whereas for 7-CDs to 10-CDs, the optimal excitation wavelength is the second excitation peak corresponding to the second Abs absorption peak, where the fluorescence emission intensity is highest (but not necessarily the quantum yield is highest). It can be seen from the table that the stokes shift between the first Abs absorption peak and the fluorescence emission peak Em from 6-CDs to 10-CDs is even more than 200nm, which helps to eliminate other fluorescence interference during sensing and improves the specificity and sensitivity of measurement.
TABLE 1 UV-VISIBLE ABSORPTION, FLUORESCENCE EXCITATION SPECTRUM, FLUORESCENCE EMISSION SPECTRUM PEAK VALUES, Stokes' SHIFT VALUES
(Note: the excitation peak of red marker is the optimum excitation wavelength of each carbon spot, at which the fluorescence emission intensity is highest)
EXAMPLE 4 Synthesis of multicolor carbon dot/starch phosphor and LED Assembly
Selecting four representative carbon spots (2-CDs, 6-CDs, 7-CDs and 8-CDs) with higher yield as samples, renaming as a-CDs, b-CDs, c-CDs and d-CDs, adding red light carbon spots (10-CDs, renaming as e-CDs), observing the light stability of the samples, and continuously irradiating ethanol solutions of the five carbon spots by using a 365nm ultraviolet lamp. The results in FIG. 7 show that after 240min of continuous irradiation, the fluorescence of the carbon dots still maintains more than 80% of the original intensity, and the strong photobleaching resistance of the carbon dots is proved.
Mixing the selected carbon dot sample with starch (mass ratio is 1:40) to prepare fluorescent powder, and dispersing the fluorescent powder in chloroform to prepare concentrated emulsion (0.5 g/mL). Respectively taking 0.5mL of the liquid and 1.0mL of organic silicon resin, mixing, mechanically stirring for 15min, filling the viscous mixed liquid into a 5.0mL syringe, slowly dripping the viscous mixed liquid into a semi-finished product LED, and ensuring that each chip is uniformly covered with 0.08mL of glue solution; and finally, placing the 5730 type LED lamp beads with the glue in a 60 ℃ oven for curing, and respectively naming the type LED lamp beads as a-LED, b-LED, c-LED, d-LED and e-LED. When the LED is turned on by direct current at 3V, the glare light can be seen in the colors blue white, green, yellow, orange, pink (fig. 8). Therefore, the carbon dots have great application value in the field of multicolor LED illumination.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The method for synthesizing the full-color fluorescent carbon dots is characterized by comprising the following steps of: indole or methyl substituted indole is used as a raw material, and a one-pot hydrothermal reaction is carried out in an ethanol solution of acid and an oxidant, wherein the methyl substituted indole is 3-methylindole, 4-methylindole, 5-methylindole or 6-methylindole.
2. The method of synthesis according to claim 1, characterized in that: the acid is strong/medium-strong organic acid or inorganic acid; the oxidant is an organic oxidant or an inorganic oxidant.
3. The synthesis method according to claim 1 or 2, characterized in that it is prepared as follows: dissolving indole or methyl substituted indole in ethanol under the action of ultrasound, adding acid and oxidant, stirring and mixing uniformly, and carrying out hydrothermal reaction to obtain dark brown red liquid.
4. The method of synthesis according to claim 1, characterized in that: the hydrothermal reaction is carried out for 0.5-2.0 h at 160-180 ℃.
5. The method of synthesis according to claim 1, characterized in that: in the synthesis process, the mol ratio of indole or methyl substituted indole to acid to oxidant is 3.4: 0.2-1.5: 0.4 to 2.00.
6. The method of synthesis according to claim 5, characterized in that: the mol ratio of the indole or methyl substituted indole to the acid to the oxidant is 3.4: 0.74: 1.59.
7. the method of synthesis according to claim 3, characterized in that: the addition amount of the ethanol is 0.34-3.40 mmol/ml according to the concentration of the added indole or methyl substituted indole.
8. A panchromatic fluorescent carbon dot synthesized by the synthesis method according to any one of claims 1 to 7.
9. The full-color fluorescent carbon dot of claim 8, wherein: the panchromatic fluorescent carbon dots are eluted in a silica gel column by using a mixed solution of ethanol and ethyl acetate as an eluent to obtain 10 kinds of fluorescent carbon dots, the color of the fluorescent carbon dots is changed from blue to red, and the emission wavelengths of the fluorescent carbon dots are 333nm, 380nm, 416nm, 437nm, 475nm, 508nm, 543nm, 571nm, 587nm and 608nm respectively.
10. Use of the full color fluorescent carbon dot of claim 8 or 9 for the preparation of phosphors or LED lighting lamps.
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