CN116283052B - Method for rapidly preparing multicolor carbon material based on solvent effect, obtained product and application - Google Patents
Method for rapidly preparing multicolor carbon material based on solvent effect, obtained product and application Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 77
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- 238000002360 preparation method Methods 0.000 claims abstract description 11
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
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- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
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- WIHHVKUARKTSBU-UHFFFAOYSA-N 4-bromobenzene-1,2-diamine Chemical compound NC1=CC=C(Br)C=C1N WIHHVKUARKTSBU-UHFFFAOYSA-N 0.000 claims description 10
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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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Abstract
The invention belongs to the field of functional material preparation, and particularly relates to a method for rapidly preparing a multicolor carbon material based on a solvent effect, an obtained product and application. The method is realized by the following steps: (1) synthesizing a fluorescent carbon material; (2) preparing a white light model. The preparation method provided by the invention can adjust the synthesis process by changing the polarity and the boiling point, adjust the dehydration and carbonization degree, has strong process controllability, and is safe and efficient. According to the invention, the white fluorescent carbon material is mixed with the PVA solution to prepare the solid model capable of emitting bright white fluorescence under ultraviolet excitation, and the prepared material has larger Stokes displacement and higher quantum yield, has excellent optical performance, has great application potential in a solid phase state and has wide market prospect.
Description
Technical Field
The invention belongs to the field of functional material preparation, and particularly relates to a method for rapidly preparing a multicolor carbon material based on a solvent effect, an obtained product and application.
Background
Carbon Materials (CMs), including carbon dot and large-sized fluorescent materials, have attracted considerable attention in various fields of optical nanoprobes, optoelectronic devices, catalysis, and bioimaging due to their superior optical properties, low cost, and simple functionalization.
Currently, the synthesis methods of CMs are generally classified into "top-down" and "top-down". The top-down method has the disadvantages of electrochemical oxidation and arc discharge, and the disadvantages of the two methods are expensive raw materials, complex operation and poor optical performance. Compared with the top-down method, the top-down method can be particularly used for preparing a hydrothermal method and a solvothermal method with excellent optical performance CMs. However, the synthesis methods reported in the prior art use both hydrothermal and solvothermal methods, which require long periods of high temperature and pressure, making them dangerous and inefficient. And most of the white light emitting applications are currently created by combining light of a plurality of wavelengths, it is difficult to create one single white light source application, so the development of the white light application is seriously hampered. Therefore, it is necessary to develop a safer and more efficient synthesis method.
Disclosure of Invention
In view of the problems existing in the prior art, the present invention provides a method for rapidly preparing a multi-colored carbon material based on a solvent effect, which efficiently generates high temperature by irradiating reactants with microwaves while applying little pressure to the reactants. The preparation process is safe and efficient.
The invention also provides the multicolor carbon material prepared by the method.
The invention also provides application of the multicolor carbon material in optical devices.
The technical scheme adopted by the invention for achieving the purpose is as follows:
the invention provides a method for rapidly preparing a multicolor carbon material based on a solvent effect, which comprises the following steps:
(1) And (3) synthesizing a fluorescent carbon material: adding 4-bromo-o-phenylenediamine and citric acid into a solvent, and performing ultrasonic treatment to obtain a mixed solution; heating the mixed solution for reaction; after the reaction is completed, the reactants are mixed with a solvent and are subjected to ultrasonic treatment until the reactants are completely dissolved; obtaining a white fluorescent carbon material with multicolor and high quantum yield;
(2) White light model preparation: mixing polyvinyl alcohol with deionized water and magnetically stirring to form a mixed solution; and then mixing the white fluorescent carbon material with the mixed solution, and refrigerating to obtain the white light model.
Further, in the step (1), the mass ratio of the 4-bromo-o-phenylenediamine to the citric acid is 1: 1-4:1; the concentration of the 4-bromo-o-phenylenediamine in the solvent is 33.35mg/mL; preferably, the solvent used in the present invention is water, formamide, N, N-dimethylformamide or ethanol.
Further, in the step (1), the ultrasonic time is 5min; the heating reaction is to put the mixed solution into a microwave oven and heat for 10-20min under the power of 110-120W.
Further, in the step (2), the proportion of the polyvinyl alcohol to the deionized water is 1g to 10mL; the volume ratio of the white fluorescent carbon material to the mixed solution is 1:1.
Further, the temperature of the magnetic stirring is 90 ℃ and the speed is 1000 r/min; the temperature of the refrigeration is-1-8 ℃ and the time is 2d.
The invention also provides a multicolor carbon material prepared by the method.
The invention also provides application of the multicolor carbon material in photoelectric devices.
The invention adopts a microwave method to prepare multicolor and white carbon dots by changing reaction solvents such as water, formamide, DMF and ethanol. Orange W-CMs, green D-CMs, yellow E-CMs and white F-CMs with quantum size up to 83.4% (W-water, F-formamide, D-DMF, E-ethanol) were obtained by adjusting different reaction solvents. Through fluorescence and characterization analysis, the solvent provided by the invention plays two important roles, namely, on one hand, the synthesis process is regulated by changing the polarity and the boiling point, the dehydration and carbonization degree is regulated, and on the other hand, some solvents with more reaction sites and low steric hindrance, such as formamide, easily cause a large number of surface defects of CM in the synthesis process. Finally, the white fluorescent carbon material is mixed with the PVA solution to prepare the solid model which emits bright white fluorescence under the excitation of ultraviolet light.
The beneficial effects of the invention are as follows:
(1) The preparation method provided by the invention can adjust the synthesis process by changing the polarity and the boiling point, adjust the dehydration and carbonization degree, has strong process controllability, and is safe and efficient.
(2) According to the invention, the white fluorescent carbon material is mixed with the PVA solution to prepare the solid model capable of emitting bright white fluorescence under ultraviolet excitation, and the prepared material has larger Stokes displacement and higher quantum yield, has excellent optical performance, has great application potential in a solid phase state and has wide market prospect.
Drawings
FIG. 1 is a TEM image after low-fire heating in different solvents of examples 1-4; wherein: (a) water; (b) formamide, (c) DMF; (d) ethanol.
FIG. 2 is a photoluminescence spectrum and a PL spectrum of the carbon material of examples 1-4 heated for 10 min; wherein (a) the photoluminescence spectrum of the carbon material under excitation of 560 nm after heating in water, formamide, DMF, ethanol for 10min with low fire; (b-e) corresponding PL spectra at different excitation wavelengths after heating for 10min with low fire in water, formamide, DMF, ethanol; (f) Photographs of carbon materials under irradiation of ultraviolet lamps in water, formamide, DMF, ethanol, from left to right: orange, white, green, yellow.
FIG. 3 is a fluorescence spectrum and photoluminescence spectrum of the carbon material of examples 1-4 heated for 10 min; wherein: (a) And (b) the photoluminescence spectrum of the carbon material under the irradiation of the ultraviolet lamp after the carbon material is heated in formamide for 10min under the low fire.
FIG. 4 is a photoluminescence spectrum and a photograph of the carbon material of example 2; wherein: (a) After heating for 10min with low fire, the carbon material of which formamide is a synthetic solvent has photoluminescence spectrum under the excitation of 540 and nm. (b) After heating for 10min with low fire, a photograph of the carbon material was irradiated with 532 nm laser.
FIG. 5 photoluminescence spectra and PL spectra of carbon materials of examples 1-4 heated for 20min; wherein: (a) The photoluminescence spectrum of the carbon material under excitation of 540 nm is heated for 20min with low fire in water, formamide, DMF and ethanol; (b-e) PL spectra corresponding to different excitation wavelengths after heating for 20min with low fire in water, formamide, DMF, ethanol; (f) Photographs of carbon materials under irradiation of ultraviolet lamps in water, formamide, DMF, ethanol, from left to right: orange, white, green, yellow.
FIG. 6 fluorescence spectrum and photoluminescence spectrum of carbon materials of examples 1-4 heated for 20min; (a) The carbon materials synthesized by the four different solvents are heated for 20min with low fire under the irradiation of a UV lamp to emit fluorescence. (b) Photoluminescence spectrum of the carbon material under UV lamp irradiation after 20min of low-fire heating in formamide.
FIG. 7 photoluminescence spectra and photographs of the carbon material of example 2 heated for 20min; wherein: (a) After 20min of low-fire heating, the carbon material taking formamide as a synthetic solvent has photoluminescence spectrum under the excitation of 540 and nm. (b) After 20min of low-fire heating, a photo of the carbon material was irradiated with 532 nm laser.
FIG. 8 is a UV-vis absorption spectrum of the carbon material (heated for 20 min) prepared in examples 1-4.
FIG. 9 is an FTIR spectrum of the carbon material (heated for 20 min) prepared in examples 1-4.
FIG. 10 shows the Raman spectra of the carbon materials (heated for 20 min) prepared in examples 1-4.
FIG. 11 is a fluorescence image of a white fluorescent carbon material/PVA composite material model prepared according to the present invention under ultraviolet light; wherein, the upper graph is brown yellow, and the lower graph emits white fluorescence.
Detailed Description
The technical scheme of the invention is further explained and illustrated by specific examples.
Example 1
(1) And (3) synthesizing a fluorescent carbon material: 66.7mg of 4-bromo-o-phenylenediamine and 34.2mg of citric acid were each placed in 2ml of water and sonicated for 5 minutes. The mixed solution was placed in a microwave oven and heated using a "low fire" gear (119W) for 10 or 20 minutes. After heating was completed, the reaction was mixed with water to 5ml and sonicated until completely dissolved; obtain the white fluorescent carbon material with multicolor and high quantum yield.
(2) White light model preparation: 1g of polyvinyl alcohol was mixed with 10ml of deionized water and magnetically stirred (90 ℃ C., 1000. R/min) to form a mixed solution. And (3) mixing the white fluorescent carbon material and the mixed solution in equal volume, transferring the mixture into a mold, and refrigerating the mixture for two days to obtain the white light model.
Example 2
(1) And (3) synthesizing a fluorescent carbon material: 66.7mg of 4-bromo-o-phenylenediamine and 34.2mg of citric acid were placed in 2ml of formamide, respectively, and sonicated for 5 minutes. The mixed solution was placed in a microwave oven and heated using a "low fire" gear (119W) for 10 or 20 minutes. After heating was completed, the reaction was mixed with formamide to 5ml and sonicated until complete dissolution; obtain the white fluorescent carbon material with multicolor and high quantum yield.
(2) White light model preparation: 1g of polyvinyl alcohol was mixed with 10ml of deionized water and magnetically stirred (90 ℃ C., 1000. R/min) to form a mixed solution. And (3) mixing the white fluorescent carbon material and the mixed solution in equal volume, transferring the mixture into a mold, and refrigerating the mixture for two days to obtain the white light model.
Example 3
(1) And (3) synthesizing a fluorescent carbon material: 66.7mg of 4-bromo-o-phenylenediamine and 34.2mg of citric acid were placed in 2ml of N, N-dimethylformamide, respectively, and sonicated for 5 minutes. The mixed solution was placed in a microwave oven and heated using a "low fire" gear (119W) for 10 or 20 minutes. After heating was completed, the reaction was mixed with N, N-dimethylformamide to 5ml and sonicated until complete dissolution; obtain the white fluorescent carbon material with multicolor and high quantum yield.
(2) White light model preparation: 1g of polyvinyl alcohol was mixed with 10ml of deionized water and magnetically stirred (90 ℃ C., 1000. R/min) to form a mixed solution. And (3) mixing the white fluorescent carbon material and the mixed solution in equal volume, transferring the mixture into a mold, and refrigerating the mixture for two days to obtain the white light model.
Example 4
(1) And (3) synthesizing a fluorescent carbon material: 66.7mg of 4-bromo-o-phenylenediamine and 34.2mg of citric acid were each placed in 2ml of ethanol and sonicated for 5 minutes. The mixed solution was placed in a microwave oven and heated using a "low fire" gear (119W) for 10 or 20 minutes. After heating was completed, the reaction was mixed with ethanol to 5ml and sonicated until complete dissolution. Obtain the white fluorescent carbon material with multicolor and high quantum yield.
(2) White light model preparation: 1g of polyvinyl alcohol was mixed with 10ml of deionized water and magnetically stirred (90 ℃ C., 1000. R/min) to form a mixed solution. And (3) mixing the white fluorescent carbon material and the mixed solution in equal volume, transferring the mixture into a mold, and refrigerating the mixture for two days to obtain the white light model.
Effect examples
The dimensions and morphology of the four synthetic carbon materials synthesized in examples 1-4 were characterized by Transmission Electron Microscopy (TEM). As can be seen from the TEM image of FIG. 1 (a), W-CMs 20 (example 1) aggregation occurred in water, and the average particle diameter was 17.86. 17.86 nm. As is clear from FIG. 1 (b), F-CMs20 (example 2) had an average particle diameter of 1.97. Mu.m, and a uniform dispersion and a clear snowflake shape. Due to F-CMs 20 Significantly larger than other CMs, it is hypothesized that its white light may be related to its shape and size. In FIG. 1 (c), D-CMs 20 The average size of example 3 was 2.68 nm and the distribution was uniform. FIG. 1 (d) shows E-CMs 20 The average size of (example 4) was 25.67 nm, indicating that aggregation also occurred. The larger volumes of W-CMs and E-CMs compared to D-CMs indicate that aggregation occurs in water and ethanol, and that the luminescence properties may be related to aggregation.
(II) W/F/D/E-CM10 and W/F/D/E-CM20 are short for synthetic CMs, 10 and 20 respectively represent the time of heating in microwaves to determine the ideal heating time. As shown in FIGS. 2 (b) -2 (E), at the optimal excitation wavelength, the emission centers of W-CMs10, F-CMs10, D-CMs10 and E-CMs10 are 585 nm, 656 nm, 558 nm and 560 nm, respectively. W-CMs10, F-CMs10, D-CMs10 and E-CMs10 in FIG. 2 (F) will emit orange, white, green and yellow colors when irradiated with ultraviolet light.
As can be seen from fig. 3, under excitation of 370 nm, F-CMs10 exhibit dual emission characteristics (462 nm, 581 nm), which are responsible for the generation of white light. In FIG. 4, F-CMs10 simultaneously display a long emission wavelength under 540 nm excitation and a bright red beam under 532 nm laser.
In FIGS. 5 (b) -5 (E), W-CMs20, F-CMs20, D-CMs20 and E-CMs20 exhibit similar excitation-dependent behavior at different excitation wavelengths. In fig. 2 (f), 3, 5 (f) and 6, CMs heated for 20 minutes excited fluorescence was brighter than CMs heated for 10 minutes. In FIG. 4, compared to FIG. 7, the red emission intensity of F-CMs20 is significantly greater than that of F-CMs10. All CMs exhibit excitation-dependent emission behavior, indicating that the surface states control the luminescence behavior. Meanwhile, the unique role of the solvent in the process of synthesizing CMs is an important factor that the luminescence behavior is adjustable and the emission range is wide. As a result of calculation, the Qys of the W-CMs20, F-CMs20, D-CMs20 and E-CMs20 were 49.1%, 83.4%, 62.1% and 46.7%, respectively.
FIG. 8 represents the UV-vis absorption spectra of the four CMs. There are mainly two absorption peaks in the figure caused by sp2 conjugated domains and n-pi transitions. Figure 9 represents FTIR spectra of four CMs. A large number of absorption peaks can be observed in the graph, and the comparison shows that the number and the intensity of the absorption peaks of the F-CMs are superior to those of other CMs, so that the functional groups are more, and the functional groups can be related to white fluorescence. FIG. 10 shows Raman spectra of four materials, F-CMs20 and D-CMs20 by comparison, with higher graphitization levels consistent with solvent controlled dehydration and carbonization of carbon material synthesis. The solvents affect the luminescent properties of CMs by controlling dehydration and carbonization during synthesis: the decrease in polarity results in a decrease in the lowest excited state energy; if the reaction of formamide is more, the steric hindrance is controlled to be low, and the reaction between raw materials is promoted; aggregation of CMs in different solvents induces resonance energy transfer, which in turn causes a change in fluorescence color.
Since most of the white light emitting applications are created by combining light of a plurality of wavelengths, it is difficult to create one single white light source application, so the development of the white light application is seriously hampered. The white fluorescent carbon model is obtained by combining the white fluorescent carbon material with the PVA solution, and the white fluorescent carbon model is respectively Q, F, N and U. The four models appear brown in daylight and produce bright white fluorescence under 365 nm uv light, as shown in fig. 11. Under the irradiation of an ultraviolet lamp, the material shows bright white fluorescence in both a solution state and a solid state, and has great application potential in the solid state.
Claims (6)
1. A method for rapidly preparing a multi-color carbon material based on solvent effect, comprising the steps of:
(1) And (3) synthesizing a fluorescent carbon material: adding 4-bromo-o-phenylenediamine and citric acid into a solvent, and performing ultrasonic treatment to obtain a mixed solution; heating the mixed solution for reaction; after the reaction is completed, the reactants are mixed with a solvent and are subjected to ultrasonic treatment until the reactants are completely dissolved; obtaining a white fluorescent carbon material with multicolor and high quantum yield;
(2) White light model preparation: mixing polyvinyl alcohol with deionized water and magnetically stirring to form a mixed solution; then mixing the white fluorescent carbon material with the mixed solution, and refrigerating to obtain a white light model;
in the step (1), the mass ratio of the 4-bromo-o-phenylenediamine to the citric acid is 1: 1-4:1; the concentration of the 4-bromo-o-phenylenediamine in the solvent is 33.35mg/mL;
in the step (1), the ultrasonic time is 5min; the heating reaction is to put the mixed solution into a microwave oven and heat for 10-20min under the power of 110-120W;
in the step (2), the temperature of the refrigeration is-1-8 ℃ and the time is 2d.
2. The method of claim 1, wherein the solvent is water, formamide, N-dimethylformamide or ethanol.
3. The method of claim 1, wherein in step (2), the ratio of polyvinyl alcohol to deionized water is 1g to 10ml; the volume ratio of the white fluorescent carbon material to the mixed solution is 1:1.
4. The method of claim 1, wherein the magnetic stirring is performed at a temperature of 90 ℃ and a rate of 1000 r/min.
5. A multi-colored carbon material prepared by the method of any one of claims 1-4.
6. Use of the multi-colored carbon material of claim 5 in an optoelectronic device.
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| CN110272734A (en) * | 2019-05-10 | 2019-09-24 | 武汉理工大学 | A kind of high quantum production rate carbon quantum dot preparation method and applications for NO detection |
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| CN113620274A (en) * | 2021-08-19 | 2021-11-09 | 广东工业大学 | Method for preparing lignin-based carbon quantum dots with high quantum yield quickly, simply and conveniently |
| KR20220106471A (en) * | 2021-01-22 | 2022-07-29 | 한국전력공사 | Carbon dot sensor for diagnosis of gas insulated switchgear and a production method for the same |
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| CN110272734A (en) * | 2019-05-10 | 2019-09-24 | 武汉理工大学 | A kind of high quantum production rate carbon quantum dot preparation method and applications for NO detection |
| CN112779005A (en) * | 2020-12-31 | 2021-05-11 | 苏州国纳思新材料科技有限公司 | Strong blue light carbon quantum dot and application thereof |
| KR20220106471A (en) * | 2021-01-22 | 2022-07-29 | 한국전력공사 | Carbon dot sensor for diagnosis of gas insulated switchgear and a production method for the same |
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