CN113201326A - Dye/perovskite quantum dot loaded metal-organic framework material and preparation method thereof - Google Patents
Dye/perovskite quantum dot loaded metal-organic framework material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a metal-organic framework material loaded by dye/perovskite quantum dots and a preparation method thereof. Through a step-by-step synthesis method, red dye molecules are loaded into a metal-organic framework material through an ion exchange method, green perovskite quantum dots are further grown in situ in the metal-organic framework material, the obtained dye/perovskite quantum dot loaded metal-organic framework material is compounded with red light of the dye and green light of the perovskite quantum dots, white light emission can be realized after the dye/perovskite quantum dot loaded metal-organic framework material is combined with a blue LED chip, and the metal-organic framework material has good light stability and thermal stability and is expected to be practically applied to the field of fluorescent powder for white LEDs.
Description
Technical Field
The invention relates to a metal-organic framework material loaded by dye/perovskite quantum dots and a preparation method thereof, the material can compound the luminescence of dye molecules and perovskite quantum dots, has good light stability and thermal stability, and can realize white light emission after being combined with a blue light LED chip.
Background
In the field of solid-state lighting, White Light Emitting Diodes (WLEDs) have become the mainstream choice for current lighting tools due to their advantages of high efficiency, long lifetime, green, and the like. The main realization mode of the white light LED is the combination of an LED chip and fluorescent powder, and the development of the fluorescent powder with high quality and low cost has important significance for realizing the white light LED with high performance.
The organic fluorescent dye is a luminescent material with rich luminescent characteristics, has the characteristics of various types, wide luminescent wavelength range coverage, commercial availability and the like, is widely applied to the fields of lasers, biological fluorescent markers and the like at present, and attracts wide attention and research in the field of white light emitting materials, however, most of organic fluorescent dyes only have strong luminescence in a dilute solution state, and can generate aggregation induced quenching effect when the concentration is too high, so that the use of the organic fluorescent dye in a solid state is limited.
Perovskite Quantum Dots (PQDs) are widely studied as a novel semiconductor material because of their advantages of high luminous efficiency, wide tunable range of emission spectrum, narrow luminous band, convenient and rapid preparation, etc. The general formula of the perovskite material can be ABX3It is shown that the current hot research is mainly focused on all-inorganic perovskite materials and organic-inorganic hybrid perovskite materials, mainly comprising CH3NH3PbX3And CsPbX3(X ═ I, Br, Cl). However, poor stability of perovskite structures is a common problem to all related fields that needs to be solved, including chemical, optical and optical thermal stability. Particularly PQDs to water in the airOxygen is very sensitive and, even when exposed to the environment, can lead to structural collapse and performance degradation.
Some inorganic porous materials such as mesoporous SiO2、Al2O3Zeolite, etc. are used to support and disperse dye molecules and perovskite nano-ions for solving the problems of dye aggregation and stability of perovskite quantum dots, however, the internal pore structure of these inorganic materials cannot be designed, and the affinity with organic molecules is poor, so that it is often difficult to exert their excellent optical properties. The Metal-organic Frameworks (MOFs) are novel porous materials formed by linking Metal ions and organic ligands, have the advantages of regular pore structures, large specific surface areas, excellent adjustability and the like, the special pore structure of the MOFs endows the MOFs with the receptivity to various object molecules, and the construction of various host-object Metal organic Frameworks can be realized by introducing different luminescent molecules. Particularly, due to the excellent adjustability and the strong pore confinement effect of the MOFs, the aggregation-induced fluorescence effect of the dye in the solid state can be effectively weakened, and the potential protection effect can be provided for the perovskite quantum dots, so that the construction of the host-guest type solid-state luminescent material based on the dye, the perovskite quantum dots and the MOFs in a composite mode is realized. At present, the simultaneous realization of the loading of the dye and the perovskite quantum dot in the single crystal of the MOFs is not reported, the realization of the composition of the dye and the perovskite quantum dot in the MOFs has great challenges and great significance, the single-matrix metal-organic framework material based on the loading of the dye/perovskite quantum dot can effectively avoid the problems of operation complexity, low color reproducibility and the like caused by multi-matrix fluorescent powder, and a new strategy and approach are provided for the design and development of the fluorescent powder for the white light LED.
Disclosure of Invention
The invention aims to provide a dye/perovskite quantum dot loaded metal-organic framework material and a preparation method thereof.
The metal-organic framework material loaded with the dye/perovskite quantum dots is synthesized by a step-by-step method, red light dye molecules are loaded into the metal-organic framework material by an ion exchange method, and green light perovskite quantum dots are further grown in situ in the metal-organic framework material to obtain the metal-organic framework material loaded with the dye/perovskite quantum dots.
In the invention, the metal-organic framework material is an anionic metal-organic framework material and is selected from ZJU-28, bio-MOF-1, NOTT-210 and ZJU-64.
In the invention, the dye molecule is cationic pyridine hemicyanine dye molecule and is selected from 4- (4- (dimethylamino) styryl) -1-methylpyridine, 4- (4- (dimethylamino) styryl) -1-ethylpyridine, 4- (4- (diethylamino) styryl) -1-methylpyridine and 4- (4- (diethylamino) styryl) -1-ethylpyridine.
In the invention, the perovskite quantum dot is CH3NH3PbBr3Or CsPbBr3。
The preparation method of the metal-organic framework material loaded by the dye/perovskite quantum dots comprises the following steps:
soaking the anionic metal-organic framework material in an organic solution of cationic pyridine hemicyanine dye to obtain a dye-loaded metal-organic framework material by an ion exchange method; soaking the metal-organic frame material loaded with the dye in an organic solution of lead bromide or lead nitrate, placing the metal-organic frame material in an oven at the temperature of 40-80 ℃, preserving heat for 1-5 hours, taking out the metal-organic frame material, washing the metal-organic frame material with ethanol, and adding the washed metal-organic frame material into CH3NH3And (3) standing for 20-24 hours in an ethanol solution of Br or CsBr at room temperature to obtain the metal-organic framework material loaded by the dye/perovskite quantum dots.
In the invention, the cationic pyridine hemicyanine dye has the following structural formula: (a)4- (4- (dimethylamino) styryl) -1-methylpyridine; (b)4- (4- (dimethylamino) styryl) -1-ethylpyridine; (c)4- (4- (diethylamino) styryl) -1-methylpyridine; (d)4- (4- (diethylamino) styryl) -1-ethylpyridine.
In the present invention, the organic solvent used is any one of N, N-dimethylformamide, N-dimethylacetamide, or N, N-diethylformamide.
In the invention, the metal-organic framework material loaded by the dye/perovskite quantum dots can compound red light of the dye and green light of the perovskite quantum dots, and can realize white light emission after being combined with a blue light LED chip.
The invention has the following specific beneficial effects:
1. the dye/perovskite quantum dot loaded metal-organic framework material provided by the invention provides a novel strategy and method for designing a luminescent material based on the metal-organic framework material.
2. The metal-organic framework material loaded by the dye/perovskite quantum dots solves the problems of aggregation fluorescence quenching of dye molecules in a solid state and instability of the perovskite quantum dots in air, and realizes the light emitting application of the dye and the perovskite quantum dots in the solid state.
3. The dye/perovskite quantum dot loaded metal-organic framework material is a novel fluorescent powder material for white light LEDs, avoids using expensive and scarce resources such as rare earth elements and the like, has the advantages of economy and economy, and is beneficial to large-scale application.
4. The metal-organic framework material loaded by the dye/perovskite quantum dots has good light stability and thermal stability and good practical application prospect.
5. The metal-organic framework material loaded by the dye/perovskite quantum dots is prepared and synthesized at a lower temperature, so that the defect of synthesizing the traditional inorganic fluorescent powder material at a high temperature is overcome, and the metal-organic framework material has the advantages of energy conservation, environmental friendliness and the like.
Drawings
FIG. 1 is a fluorescence spectrum and corresponding fluorescence microscopic image of the dye/perovskite quantum dot loaded metal-organic framework material step-by-step loaded dye and perovskite quantum dot of the present invention;
FIG. 2 is a powder X-ray diffraction pattern and an infrared absorption pattern of a dye/perovskite quantum dot loaded metal-organic framework material of the present invention;
FIG. 3 is a photograph and corresponding color coordinate of a device luminescence spectrum, before and after current driving, obtained after the dye/perovskite quantum dot loaded metal-organic framework material of the present invention is combined with a blue LED chip;
fig. 4 is a spectral plot of dye/perovskite quantum dot supported metal-organic framework materials of the present invention as a function of light and temperature.
Detailed Description
The present invention will be further illustrated with reference to the following examples, which are not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Example 1:
20mg of ZJU-28 crystals were weighed and soaked in 2mL of 10-5mol L-1Placing the cationic dye 4- (4- (dimethylamino) styryl) -1-methylpyridine in DMF solution in an oven at 60 ℃ for 0.5 hour, filtering and washing the obtained crystal with DMF, obtaining ZJU-28 crystal loaded with the- (4- (dimethylamino) styryl) -1-methylpyridine dye by an ion exchange method, and soaking the ZJU-28 crystal in 10mL of 1 mu mol mL-1Pb (NO) of3)2After leaving in an oven at 60 ℃ for 1 hour, the resulting solution was washed with DMF and ethanol to obtain a solution containing the dye and Pb2+Further immersing the resulting crystals in a solution of 100mg of CH3NH3The Br crystal is placed in ethanol solution for 22 hours at room temperature to obtain the loaded cationic dye 4- (4- (dimethylamino) styryl) -1-methylpyridine and CH3NH3PbBr3ZJU-28 crystalline material of perovskite quantum dots. The material can show emission peaks at 528nm and 595nm under the excitation of 460nm light source, which respectively correspond to CH3NH3PbBr3Characteristic emission peaks of perovskite quantum dots and cationic dye 4- (4- (dimethylamino) styryl) -1-methylpyridine, and 460nm LEDThe chip can realize white light emission with color coordinates in a white light region after combination, and shows good luminous stability along with the change of temperature and illumination time.
Example 2:
10mg of bio-MOF-1 crystals were weighed and soaked in 2mL of 5X 10-5mol L-1Placing the cationic dye 4- (4- (dimethylamino) styryl) -1-ethylpyridine in DMF solution in an oven at 60 ℃ for 1 hour, filtering and washing the obtained crystal with DMF, obtaining the bio-MOF-1 crystal loaded with the (4- (dimethylamino) styryl) -1-ethylpyridine dye by an ion exchange method, and soaking the obtained crystal in 5mL of 1 mu mol mL of a concentration-1PbBr of2After leaving in an oven at 70 ℃ for 3 hours, the resulting solution was washed with DMF and ethanol to obtain a solution loaded with the dye and Pb2+The obtained bio-MOF-1 crystal is continuously soaked in an ethanol solution in which 50mg CsBr crystal is dissolved, and is kept stand for 24 hours at room temperature to obtain the loaded cationic dye 4- (4- (dimethylamino) styryl) -1-ethylpyridine and CsPbBr3A bio-MOF-1 crystalline material of perovskite quantum dots. The material can display emission peaks at about 530nm and 600nm under the excitation of a 460nm light source, and the emission peaks respectively correspond to CsPbBr3The perovskite quantum dot and the characteristic emission peak of the cationic dye 4- (4- (dimethylamino) styryl) -1-ethylpyridine can realize white light emission with color coordinates in a white light region after being combined with a 460nm LED chip, and show good luminous stability along with the changes of temperature and illumination time.
The metal-organic framework material loaded with the dye/perovskite quantum dots is loaded with the dye step by step, a fluorescence spectrogram of the perovskite quantum dots and a corresponding fluorescence microscopic image are shown in figure 1, the metal-organic framework material loaded with the dye molecules presents red light emission, the metal-organic framework material loaded with the dye/perovskite quantum dots obtained by further in-situ growth of the perovskite quantum dots respectively presents different emission characteristics under the excitation of light sources with different wavelengths, including 365nm, 480nm and 532nm, and the corresponding light-emitting colors are respectively green, yellow and red, which are results displayed due to different excitation wave bands corresponding to the dye and the perovskite quantum dots. Fig. 2 is an XRD spectrum and an infrared absorption spectrum of the metal-organic framework material loaded with the dye/perovskite quantum dots of the present invention, the XRD result shows that characteristic diffraction peaks of the perovskite quantum dots appear in the material, and the infrared spectrum also shows the existence of characteristic absorption peaks of the dye molecules and the perovskite quantum dots. The results show that the metal-organic framework material loaded by the dye/perovskite quantum dots is successfully prepared by the method, and the red light of the dye and the green light of the perovskite quantum dots are compounded in a single crystal of the metal-organic framework material, so that the fluorescent powder material capable of showing yellow light emission under the excitation of the blue light is obtained. FIG. 3 shows the luminescence spectrum of the device, the photos before and after current driving and the corresponding color coordinate graph obtained by the material and the blue light LED chip, and it can be seen that the material and the blue light LED chip show bright white light emission after combination, and the color coordinate corresponding to the luminescence is located in the white light region and is very close to the color coordinate of the standard white light, thus indicating the application potential of the material as an excellent fluorescent powder material. FIG. 4 shows the luminescence properties of the dye/perovskite quantum dot loaded metal-organic framework material under illumination and temperature, and it can be seen that, even under illumination radiation for 25h, the perovskite quantum dot can still maintain 86% of the original luminescence intensity, the dye molecule can also maintain 66% of the original luminescence intensity, and simultaneously, when the temperature is increased from 30 ℃ to 160 ℃ and then is recovered to 30 ℃, the overall luminescence intensity of the material can be almost recovered to the original intensity, and these results show that the dye/perovskite quantum dot loaded metal-organic framework material of the invention has very good light stability and thermal stability, which shows that the metal-organic framework material as a main material provides good protection effect on the perovskite quantum dot and the dye molecule, and isolates them from water in the surrounding environment to a certain extent, Oxygen, etc., and thus effectively improve their luminescence stability. Particularly, in the field of white light emission, since the phosphor material is continuously illuminated in the using process, and a large amount of energy generated by the LED chip under current driving is dissipated in the form of heat energy, the temperature of the device is increased, so that the temperature and illumination have a great influence on the light emission of the phosphor material, and the service life of the white LED device is directly affected. The dye/perovskite quantum dot loaded metal-organic framework material obtained by the scheme of the invention has good illumination stability and optical thermal stability, and has great application prospect in the practical application of white light LED fluorescent powder.
Claims (9)
1. A metal-organic framework material loaded with dye/perovskite quantum dots is characterized in that the material is synthesized by a step-by-step method, red light dye molecules are loaded into the metal-organic framework material by an ion exchange method, and green light perovskite quantum dots are further grown in situ in the metal-organic framework material to obtain the metal-organic framework material loaded with the dye/perovskite quantum dots.
2. The dye/perovskite quantum dot supported metal-organic framework material according to claim 1, wherein the metal-organic framework material is an anionic metal-organic framework material selected from the group consisting of ZJU-28, bio-MOF-1, not-210, ZJU-64.
3. The dye/perovskite quantum dot supported metal-organic framework material according to claim 1, wherein the dye molecule is a cationic pyridine hemicyanine dye molecule selected from the group consisting of 4- (4- (dimethylamino) styryl) -1-methylpyridine, 4- (4- (dimethylamino) styryl) -1-ethylpyridine, 4- (4- (diethylamino) styryl) -1-methylpyridine, and 4- (4- (diethylamino) styryl) -1-ethylpyridine.
4. The dye/perovskite quantum dot supported metal-organic framework material as claimed in claim 1, wherein the perovskite quantum dot is CH3NH3PbBr3Or CsPbBr3。
5. A method of preparing the dye/perovskite quantum dot supported metal-organic framework material of claim 1, comprising the steps of:
soaking the anionic metal-organic framework material in an organic solution of cationic pyridine hemicyanine dye to obtain a dye-loaded metal-organic framework material by an ion exchange method; soaking the metal-organic frame material loaded with the dye in an organic solution of lead bromide or lead nitrate, placing the metal-organic frame material in an oven at the temperature of 40-80 ℃, preserving heat for 1-5 hours, taking out the metal-organic frame material, washing the metal-organic frame material with ethanol, and adding the washed metal-organic frame material into CH3NH3And (3) standing for 20-24 hours in an ethanol solution of Br or CsBr at room temperature to obtain the metal-organic framework material loaded by the dye/perovskite quantum dots.
6. The method for preparing a dye/perovskite quantum dot supported metal-organic framework material according to claim 5, wherein the cationic pyridine hemicyanine dye is an organic solution of the cationic pyridine hemicyanine dye: (a)4- (4- (dimethylamino) styryl) -1-methylpyridine; or (b)4- (4- (dimethylamino) styryl) -1-ethylpyridine; or (c)4- (4- (diethylamino) styryl) -1-methylpyridine; or (d)4- (4- (diethylamino) styryl) -1-ethylpyridine; the structural formula is as follows:
(a)
(b)
(c)
(d)
7. the method for preparing a dye/perovskite quantum dot supported metal-organic framework material according to claim 5, wherein the organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide.
8. Use of a dye/perovskite quantum dot supported metal-organic framework material, wherein the material is a material according to any one of claims 1 to 4 or a material prepared by the method according to any one of claims 5 to 7, and the material is used for compounding red light of a dye and green light of perovskite quantum dots and is used for realizing white light emission in combination with a blue LED chip.
9. The use of the dye/perovskite quantum dot loaded metal-organic framework material according to claim 8, wherein the blue LED chip is a commercial 450-460 nm blue LED chip.
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| CN103740361A (en) * | 2013-12-24 | 2014-04-23 | 浙江大学 | Dye/metal-organic framework composite material for white light emission and preparation method thereof |
| CN108774511A (en) * | 2018-05-31 | 2018-11-09 | 兰州大学 | The preparation of full-inorganic perovskite quantum dot/mesoporous MOF-5 composite luminescent materials and application in the led |
| CN110041915A (en) * | 2019-04-24 | 2019-07-23 | 深圳大学 | The preparation method of perovskite quantum dot and metal organic frame composite luminescent material |
| CN111171807A (en) * | 2020-01-10 | 2020-05-19 | 浙江大学 | Dye/metal-organic framework composite material with second-order and third-order nonlinear optical properties and preparation method and application thereof |
| CN111676010A (en) * | 2020-06-22 | 2020-09-18 | 江西理工大学 | Preparation method of perovskite quantum dot/Eu-MOF composite luminescent material |
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| CN103740361A (en) * | 2013-12-24 | 2014-04-23 | 浙江大学 | Dye/metal-organic framework composite material for white light emission and preparation method thereof |
| CN108774511A (en) * | 2018-05-31 | 2018-11-09 | 兰州大学 | The preparation of full-inorganic perovskite quantum dot/mesoporous MOF-5 composite luminescent materials and application in the led |
| CN110041915A (en) * | 2019-04-24 | 2019-07-23 | 深圳大学 | The preparation method of perovskite quantum dot and metal organic frame composite luminescent material |
| CN111171807A (en) * | 2020-01-10 | 2020-05-19 | 浙江大学 | Dye/metal-organic framework composite material with second-order and third-order nonlinear optical properties and preparation method and application thereof |
| CN111676010A (en) * | 2020-06-22 | 2020-09-18 | 江西理工大学 | Preparation method of perovskite quantum dot/Eu-MOF composite luminescent material |
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