CN109423278B - Fluorescent perovskite nanocrystal and preparation method and application thereof - Google Patents
Fluorescent perovskite nanocrystal and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a fluorescent perovskite nanocrystal and a preparation method and application thereof, and the structure of the fluorescent perovskite nanocrystal is MOF-ABX3Wherein, MOF and ABX3The mass ratio of (1-50) to (0.1-5), the cation halide salt solution for perovskite synthesis is added into the metal organic framework dispersion liquid, the obtained perovskite nano-crystal is uniformly dispersed in the metal organic framework crystal, and the method has good fluorescence performance and universality. The synthesis method of the perovskite nanocrystal provided by the invention can be directly used for the application of storage and protection of confidential information. Compared with the prior art, the method has the advantages of simple and repeatable operation process, very safe metal organic framework material and recorded information (no absorption and fluorescence characteristics in a visible light range and no capability of being identified by naked eyes) and good perovskite nanocrystal fluorescence characteristics, so that the method can be directly applied to the field of confidential information storage and protection.
Description
Technical Field
The invention belongs to the technical field of semiconductor nano material preparation, and particularly relates to perovskite nano crystal synthesized by repeated transformation of a metal organic framework, a preparation method of the perovskite nano crystal and application of the perovskite nano crystal in secret information storage and protection.
Background
The intelligent fluorescent material with stimulus response has wide application in the fields of information safety and the like. The material generally regulates the arrangement mode of molecules through external stimulation (such as light, electricity, heat, mechanical force and the like), so as to achieve the purpose of changing the fluorescence signal of the material. Fluorescent materials currently used in this field include various organic substances, metal complexes, inorganic quantum dots, up-conversion nanoparticles, and the like. However, these materials still have a number of disadvantages, such as: poor fluorescence performance, high price, complex synthesis and cleaning processes and the like. In addition, their strong light absorption and photoluminescence properties in the visible range determine that the recorded information can be recognized by naked eyes in sunlight or under ultraviolet lamp irradiation, which limits their application in confidential information storage and protection. Therefore, it remains a great challenge to obtain high performance, low cost, safe (invisible to the naked eye) smart fluorescent materials and systems.
The metal halide perovskite crystal material has ABX3Type of structure, A and B represent different cations, combined with an anion X to form CaTiO3Type crystal latticeAnd (5) structure. Wherein A is typically a monovalent cation; b is a metal ion; x is Cl—、Br—、I—One of (1) and (b). Due to good semiconductor performance (high mobility, long carrier diffusion length and low defect state density), the metal halide perovskite material is rapidly developed in the photovoltaic field, and the photoelectric conversion efficiency of the solar cell based on the metal halide perovskite material exceeds 20% at present. Meanwhile, the metal halide perovskite material also shows good application prospect in the field of optical display. As a direct band gap semiconductor, the metal halide perovskite nanocrystal (or quantum dot) has the outstanding characteristics of low price, solution-soluble preparation, easy processing, adjustable color, high quantum yield, narrow fluorescence peak and the like, and is a novel fluorescent material, so that the metal halide perovskite nanocrystal (or quantum dot) has wide application prospect in the field of light-emitting diodes, lasers, illumination and other photoelectric devices. Based on the above advantages, fluorescent metal halide perovskite nanocrystals also have the potential for applications in the field of information security. Recently, Wang et al (adv. Mater.2016,28,10637-10643) reported that a metal halide perovskite material was produced at low power (. apprxeq.5 mW cm)-2) The phenomenon of phase transition (from two-dimensional to three-dimensional transition) under the condition of short wavelength (325nm) light excitation and the change of fluorescence color caused by the phase transition preliminarily verifies the application possibility of the phase transition in the aspects of multicolor fluorescence patterns, display, and recording and storing of optical information. However, the method and the material still cannot meet the requirement of storage and protection of confidential information, because the two-dimensional perovskite material still has blue fluorescence characteristics as the ink for recording information, so that the information recorded by the two-dimensional perovskite material can still be recognized by naked eyes under the condition of optical excitation; secondly, this photo-induced phase inversion process cannot be repeated, which limits its practical application. At present, reports about the application of fluorescent perovskite nanocrystals in the field of confidential information storage and protection are not yet seen. Therefore, the development of novel perovskite-based safe intelligent fluorescent materials and systems has very important application value.
The Metal Organic Framework (MOF) is a crystalline porous material which is formed by mutually connecting an inorganic metal center and an organic functional group through coordination bonds and has a regular pore canal or hole structure. The metal organic framework material has the advantages of large specific surface area, easy synthesis, structural diversity, modification and the like, and has great potential in the aspects of adsorption, separation, catalysis, sensing and the like. According to the method, the perovskite nanocrystalline with high fluorescence efficiency is synthesized by a method of directly and repeatedly converting the MOF material, and in the method, the safety (no absorption and fluorescence characteristics in a visible light range and can not be identified by naked eyes) of a specific MOF material and the fluorescence characteristics of the perovskite material are simultaneously utilized, so that the application of the MOF material in the field of confidential information storage protection is realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a fluorescent perovskite nanocrystal capable of being repeatedly synthesized, a preparation method thereof and application of confidential information in storage and protection.
The purpose of the invention can be realized by the following technical scheme:
one of the purposes of the invention is to provide a fluorescent perovskite nanocrystal which is characterized in that the structure of the fluorescent perovskite nanocrystal is MOF-ABX3Wherein, MOF and ABX3The MOF is a 2D or 3D metal organic framework, and the MOF material is one of Zn-MOF, Hg-MOF, Pb-MOF, Sn-MOF, Ge-MOF, Si-MOF, Ga-MOF, Bi-MOF, In-MOF, Mn-MOF and Cu-MOF. ABX3Wherein A is MA+、FA+、Cs+、Rb+B is one of zinc, mercury, lead, tin, germanium, silicon, gallium, bismuth, indium, manganese or copper, and X is one of chlorine, bromine and iodine.
The invention also aims to provide a preparation method of the fluorescent perovskite nanocrystal, which synthesizes the metal halide perovskite nanocrystal by directly converting the MOF material containing specific metal, has extremely simple conversion process, can realize reversible conversion and has universality.
The synthesis method is simultaneously suitable for preparing the perovskite nano crystal powder and the perovskite nano crystal film. In particular, the above-described method for reproducible MOF material conversion synthesis of metal halide perovskite nanocrystals comprises the steps of:
(1) dispersing an MOF material in a solvent I to prepare a suspension with the concentration of 0.5-25 g/L; the MOF material in the step (1) is 2D or 3D MOF, and is synthesized by adopting a conventional room-temperature stirring or solvothermal method, wherein an organic ligand in the MOF material is a carboxylic acid ligand or an imidazole ligand; the MOF material is one of Zn-MOF, Hg-MOF, Pb-MOF, Sn-MOF, Ge-MOF, Si-MOF, Ga-MOF, Bi-MOF, In-MOF, Mn-MOF and Cu-MOF;
the solvent I is selected from any one of toluene, chlorobenzene, chloroform, n-hexane, cyclohexane, ethyl acetate or diethyl ether.
(2) Dissolving cationic halide salt in a solvent II, and performing ultrasonic treatment to completely dissolve the cationic halide salt to obtain cationic halide salt solution with the concentration of 0.05-25 g/L; the cation halide salt in the step (2) is MA +, FA +, Cs+、Rb+One or more mixed systems of (a); the metal is one or more of zinc, mercury, lead, tin, germanium, silicon, gallium, indium, manganese or copper, and the halogen is one or more of chlorine, bromine and iodine;
the solvent II is selected from one of methanol, ethanol, isopropanol, butanol, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile or acetone.
(3) And (3) adding the cationic halide solution obtained in the step (2) into the suspension obtained in the step (1), continuously stirring for 5-300 seconds, and filtering or centrifuging and drying the obtained dispersion liquid to obtain the perovskite nano-crystalline powder embedded in the MOF.
And (3) dispersing the perovskite nanocrystalline powder embedded in the MOF prepared in the step (3) into a solvent III, continuously stirring until the fluorescence of the perovskite nanocrystalline disappears completely, and then filtering or centrifuging and drying the powder without fluorescence to obtain the powder without fluorescence which can be directly reused in the process of converting and synthesizing the perovskite nanocrystalline, so that repeated conversion can be realized for many times. The solvent III is one of water, methanol, ethanol, acetone, DMF and DMSO.
In addition, the invention also aims to provide an application of the rapid and repeatable synthesis of perovskite nanocrystals from MOF in the aspect of confidential information storage and protection.
The specific application method comprises the following steps:
(1) preparation of precursor solution: adding metal salt and organic ligand which form the MOF material into a solvent II, then continuously adding ethanol and glycol in a volume ratio of 5-20: 1-15, and completely dissolving the ethanol and the glycol in an ultrasonic or stirring manner to obtain an MOF precursor solution; the metal salt is one of nitrate, acetate and halide of zinc, mercury, lead, tin, germanium, silicon, gallium, indium, manganese or copper. The organic ligand may be a carboxylic acid ligand or an imidazole ligand. Wherein the mass ratio of the metal salt to the organic ligand is 0.5-5: 0.1-2.
(2) Storage and encryption of confidential information: printing the precursor liquid on a matrix through a printing technology, drying, soaking and cleaning the matrix by using an alcohol solvent, and drying again to obtain a substrate with information recorded by MOF crystals, namely a process of storing confidential information; the printing technology is a traditional plate printing method including gravure printing, lithographic printing, screen printing or letterpress printing and a plateless printing method represented by ink jet; because of the security of a particular MOF material, the information recorded therewith cannot be identified by common decryption methods, which offers practical application possibilities for the storage and protection of confidential information.
(3) Decryption of confidential information: the substrate recorded with the information is processed by cation halide salt to complete the conversion from MOF to perovskite nanocrystal, and the fluorescence signal generated in the process can be easily detected, namely, the process of decrypting the information recorded by MOF is realized; the cationic halide salt is treated by one of solution immersion, solution spraying or gas phase contact reaction.
(4) Repeated encryption and decryption processes of confidential information: and (3) processing the decrypted substrate by using a solvent III to completely quench the generated fluorescent signal, namely, carrying out a re-encryption process of confidential information.
And (4) repeating the steps (3) and (4) again to obtain the substrate without fluorescence, wherein the fluorescence can be generated and quenched again, namely the process of multiple encryption and decryption of confidential information.
Compared with the prior art, the invention has the following advantages:
1) compared with other intelligent fluorescent materials, the perovskite nanocrystalline phase is cheaper and has better fluorescence performance.
2) Compared with the traditional synthesis method, the synthesis process of the fluorescent perovskite nanocrystal is simple, rapid and repeatable.
3) The invention constructs an intelligent fluorescent system using MOF-perovskite nanocrystalline as confidential information storage and protection. The use of the secure MOF material can realize the encryption of confidential information, so that the confidential information cannot be identified by naked eyes, and the security of the information is improved; in addition, the conversion synthesis of the fluorescent perovskite nanocrystalline with excellent performance realizes the decryption of confidential information, and the encryption and decryption processes of the confidential information can be repeated for many times.
Drawings
FIG. 1 is a photograph of a Pb-MOF powder prepared;
FIG. 2 shows MAPbBr embedded in MOF prepared3Photos of the nanocrystalline powder under a fluorescent lamp (left) and an ultraviolet lamp (right);
FIG. 3 shows MAPbBr embedded in MOF prepared3A nanocrystalline TEM photograph;
FIG. 4 shows MAPbBr embedded in MOF prepared3A nanocrystalline fluorescence spectrogram;
FIG. 5 is CsPbBr embedded in MOF3A fluorescence spectrogram of the nanocrystalline powder;
FIG. 6 is a mixed halogen perovskite (MAPbI)xBr3-x-yCly) Fluorescence spectrum of the nanocrystal;
FIG. 7 is a photograph of a formulated Pb-MOF precursor solution;
fig. 8 is a photograph of a repeated encryption and decryption process for the entire MOF-based conversion synthesis of perovskite nanocrystals.
Detailed Description
Example 1
Synthesis of methylaminolead bromide (MAPbBr) based on conversion of Pb-MOF3) Nanocrystal
(1) Synthesis of Pb-MOF: 90mL of 1,3,5-H3Aqueous BTC (0.01M) and 10mL Pb (NO)3)2Mixing the water solution (0.09M), stirring for 30min, washing the obtained powder with deionized water and methanol for three times respectively, and vacuum drying at 150 deg.C for 12 hr;
(2)MAPbBr3and (3) synthesis of nanocrystals: 200mg of the synthesized Pb-MOF powder was dispersed in 10mL of n-hexane to form a suspension, which was stirred to be uniformly dispersed. 10mg of amino bromide (MABr) was dissolved in 1mL of n-butanol and dissolved completely by sonication. Quickly adding 0.5mL of MABr solution into Pb-MOF suspension, continuously stirring for 30s, filtering or centrifuging the dispersion, and washing with butanol once to remove unreacted MABr to obtain MAPbBr embedded in MOF3And (3) nanocrystalline powder. The Pb-MOF prepared in this example is shown in FIG. 1, and the Pb-MOF powder is white; MAPbBr Embedded in MOF3The photograph of the nanocrystalline powder is shown in fig. 2, and it can be seen that the powder after conversion is bright yellow and emits bright green light under an ultraviolet lamp, and the TEM morphology and the fluorescence spectrum of the powder are respectively shown in fig. 3 and 4. It can be seen from the figure that the MAPbBr of about 10nm is prepared3The nanocrystals were uniformly dispersed in Pb-MOF and had a very narrow (25 nm half-peak width) fluorescence emission peak at 527 nm. This indicates that perovskite nanocrystals with high fluorescence properties can be rapidly synthesized by this simple method.
Example 2
Synthesis of Cesium lead Bromide (CsPbBr) based on conversion of Pb-MOF3) Nanocrystal
(1) Synthesis of Pb-MOF: the preparation method is the same as that in the example 1;
(2)CsPbBr3and (3) synthesis of nanocrystals: similar to the preparation method in example 1, except that the Pb-MOF dispersion solvent was selected to be toluene, 10mg of cesium bromide (CsBr) was dissolved in 1mL of methanol for the preparation of the cationic halide solution for the conversion reaction. CsPbBr Embedded in MOF prepared in this example3The fluorescence spectra of the nanocrystalline powders are respectively shown in FIG. 5, and the fluorescence emission wavelength is 529nm, which shows that the method has good universality.
Example 3
Synthesis of mixed halogen perovskites (MAPbI) based on Pb-MOF transformationxBr3-x-yCly) Nanocrystal
(1) Synthesis of Pb-MOF: the preparation method is the same as that in the example 1;
(2)MAPbIxBr3-xand (3) synthesis of nanocrystals: similar to the preparation process in example 1, the difference is the preparation of the cationic halide solution for the conversion reaction. For x ═ 0, y ═ 3, 10mg of MACl were dissolved in 1mL of n-butanol; for x ═ 0, y ═ 1, 2.32mg MACl and 7.68mg MABr were dissolved in 1mL of n-butanol; for x ═ 0, y ═ 2, 5.47mg MACl and 4.53mg MABr were dissolved in 1mL of n-butanol; for x ═ 1 and y ═ 0, 4.15mg of MAI and 5.85mg of MABr were dissolved in 1mL of n-butanol, and for x ═ 2 and y ═ 0, 7.40mg of MAI and 2.60mg of MABr were dissolved in 1mL of n-butanol. The mixed halogen perovskite (MAPbI)xBr3-x-yCly) The fluorescence spectrum of the nanocrystals is shown in fig. 6, and the fluorescence emission wavelength can be adjusted from 406nm to 746nm as the halogen changes from Cl to I, thus indicating that the fluorescent perovskite nanocrystals synthesized by the present method can cover almost the entire visible light range.
Example 4
Synthesis procedure based on example 1 and its use for confidential information storage and protection
(1) Preparation of a Pb-MOF precursor solution: 2.15g of Pb (NO)3)2And 0.58g of 1,3,5-H3BTC was added to 5mL DMSO, then 11.25mL ethanol and 7.5mL ethylene glycol were added thereto, and dissolved completely by sonication or stirring to give a precursor MOF solution. The photo is shown in FIG. 7;
(2) storage and encryption of confidential information: 5mL of the above Pb-MOF precursor solution was added to an empty cartridge of an ink jet printer. And then printing the Pb-MOF precursor liquid on parchment paper in an ink-jet printing mode, soaking and cleaning the parchment paper by using an alcohol solvent, and drying again to obtain a substrate with information recorded by MOF crystals. Because of the security of a specific MOF material, the information recorded by the MOF material cannot be identified by a common decryption method, and can be directly used for storing certain confidential information;
(3) decryption of confidential information: and treating the parchment paper substrate recorded with the information by spraying a butanol solution of MABr, so as to complete the rapid conversion from MOF to perovskite nanocrystals. The fluorescence signal generated in the process can be easily detected, namely, the process of decrypting the information recorded by the MOF can be realized;
(4) repeated encryption and decryption processes of confidential information: and soaking the decrypted parchment paper substrate with methanol, and completely quenching the fluorescent signal of the perovskite nanocrystalline after a period of time, namely realizing the re-encryption process of confidential information. Then the substrate without fluorescence is processed again by the method of steps (2) and (3), and fluorescence can be generated and quenched again, the whole process is shown as 8, thereby realizing the process of repeated encryption and decryption of confidential information. This illustrates that the present invention is well suited for use in storage and protection applications for confidential information.
Example 5
A preparation method of fluorescent perovskite nanocrystal comprises the following steps:
(1) dispersing the MOF material in toluene to prepare a suspension with the concentration of 0.5 g/L; the MOF material is 2D or 3D MOF, metal salt and organic ligand are synthesized by adopting a conventional room-temperature stirring method, the organic ligand is carboxylic acid ligand, the metal salt is Sn, and the MOF material is Sn-MOF;
(2) dissolving the cationic halide salt in a solvent II, and performing ultrasonic treatment to completely dissolve the cationic halide salt to obtain a cationic halide salt solution with the concentration of 0.05 g/L; the cationic halide salt is FA+Systems (i.e., formamidinyl halide salts); the metal used is tin and the halogen used is chlorine; the solvent II is selected from methanol.
(3) And (3) adding the cationic halide solution obtained in the step (2) into the suspension obtained in the step (1), continuously stirring for 5-300 seconds, and filtering or centrifuging and drying the obtained dispersion liquid to obtain the perovskite nano-crystalline powder embedded in the MOF. The dosage of the cationic halide salt solution obtained in the step (2) and the suspension obtained in the step (1) is that the fluorescent perovskite nanocrystalline MOF and ABX are finally obtained3The mass ratio of (1): 0.1.
(4) and (3) dispersing the perovskite nanocrystalline powder embedded in the MOF prepared in the step (3) into methanol, continuously stirring until the fluorescence of the perovskite nanocrystalline disappears completely, filtering or centrifuging and drying the powder without fluorescence, and directly reusing the obtained powder without fluorescence in the process of converting and synthesizing the perovskite nanocrystalline, so that repeated conversion can be realized for many times.
The perovskite nanocrystalline rapidly and repeatedly synthesized by MOF is applied to the aspect of confidential information storage and protection. The specific application method comprises the following steps:
(1) preparation of precursor solution: adding metal salt and organic ligand which form the MOF material into a solvent II methanol, then continuously adding ethanol and glycol with the volume ratio of 5:1, and completely dissolving the mixture in an ultrasonic or stirring manner to obtain MOF precursor liquid; the metal salt is zinc. The organic ligand may be a carboxylic acid ligand. Wherein the mass ratio of the metal salt to the organic ligand is 0.5: 0.1.
(2) Storage and encryption of confidential information: printing the precursor liquid on a matrix through a printing technology, drying, soaking and cleaning the matrix by using an alcohol solvent, and drying again to obtain a substrate with information recorded by MOF crystals, namely a process of storing confidential information; the printing technology is a traditional gravure method; because of the security of a particular MOF material, the information recorded therewith cannot be identified by common decryption methods, which offers practical application possibilities for the storage and protection of confidential information.
(3) Decryption of confidential information: the substrate recorded with the information is processed by cation halide salt to complete the conversion from MOF to perovskite nanocrystal, and the fluorescence signal generated in the process can be easily detected, namely, the process of decrypting the information recorded by MOF is realized; the cationic halide salt is treated by solution soaking.
(4) Repeated encryption and decryption processes of confidential information: and (3) processing the decrypted substrate by using a solvent III to completely quench the generated fluorescent signal, namely, carrying out a re-encryption process of confidential information.
(5) And (4) repeating the steps (3) and (4) again to obtain the substrate without fluorescence, wherein the fluorescence can be generated and quenched again, namely the process of multiple encryption and decryption of confidential information.
Example 6
A preparation method of fluorescent perovskite nanocrystal comprises the following steps:
(1) dispersing an MOF material in chlorobenzene as a solvent I to prepare a suspension with the concentration of 25 g/L; the MOF material in the step (1) is 2D or 3D MOF, and is synthesized by adopting a conventional solvothermal method, wherein an organic ligand in the MOF material is an imidazole ligand; the MOF material is Bi-MOF;
(2) dissolving cation halide salt in a solvent IIN, N-dimethylformamide, and performing ultrasonic treatment to completely dissolve the cation halide salt to obtain a cation halide salt solution with the concentration of 2.5 g/L; the cationic halide salt is Rb+A system; the metal is bismuth, and the halogen is iodine;
(3) and (3) adding the cationic halide solution obtained in the step (2) into the suspension obtained in the step (1), continuously stirring for 5-300 seconds, and filtering or centrifuging and drying the obtained dispersion liquid to obtain the perovskite nano-crystalline powder embedded in the MOF. The dosage of the cationic halide salt solution obtained in the step (2) and the suspension obtained in the step (1) is that the fluorescent perovskite nanocrystalline MOF and ABX are finally obtained3In a mass ratio of 50: 0.1.
(4) and (3) dispersing the perovskite nanocrystalline powder embedded in the MOF prepared in the step (3) into a solvent III DMF, continuously stirring until the fluorescence of the perovskite nanocrystalline completely disappears, then filtering or centrifuging and drying the powder without fluorescence, and directly reusing the obtained powder without fluorescence in the process of converting and synthesizing the perovskite nanocrystalline, so that repeated conversion can be realized for many times.
The perovskite nanocrystalline rapidly and repeatedly synthesized by MOF is applied to the aspect of confidential information storage and protection. The specific application method comprises the following steps:
(1) preparation of precursor solution: adding metal salt and organic ligand which form the MOF material into a solvent II, then continuously adding ethanol and glycol in a volume ratio of 20:15, and completely dissolving the ethanol and the glycol in an ultrasonic or stirring manner to obtain MOF precursor liquid; the metal salt is bismuth and the organic ligand may be an imidazole ligand. Wherein the mass ratio of the metal salt to the organic ligand is 5: 2.
(2) Storage and encryption of confidential information: printing the precursor liquid on a matrix through a printing technology, drying, soaking and cleaning the matrix by using an alcohol solvent, and drying again to obtain a substrate with information recorded by MOF crystals, namely a process of storing confidential information; the printing technology is an ink jet printing method; because of the security of a particular MOF material, the information recorded therewith cannot be identified by common decryption methods, which offers practical application possibilities for the storage and protection of confidential information.
(3) Decryption of confidential information: the substrate recorded with the information is processed by cation halide salt to complete the conversion from MOF to perovskite nanocrystal, and the fluorescence signal generated in the process can be easily detected, namely, the process of decrypting the information recorded by MOF is realized; the cationic halide salt is treated in one of the gas phase contact reactions.
(4) Repeated encryption and decryption processes of confidential information: the decrypted substrate is treated with solvent III DMF to completely quench the generated fluorescence signal, namely, the process of encrypting the confidential information again.
(5) And (4) repeating the steps (3) and (4) again to obtain the substrate without fluorescence, wherein the fluorescence can be generated and quenched again, namely the process of multiple encryption and decryption of confidential information.
It should be emphasized that the above-described embodiments of the present disclosure are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the disclosure, and that many changes and modifications may be made to the above-described embodiments of the disclosure without departing substantially from the spirit and principles of the disclosure, all of which are intended to be included within the scope of the disclosure.
Claims (10)
1. A fluorescent perovskite nanocrystal which is characterized in thatThe structure of which is MOF-ABX3Wherein, MOF and ABX3The mass ratio of (1-50) to (0.1-5), MOF is 2D or 3D metal organic framework, A is MA+、FA+、Cs+、Rb+B is one of zinc, mercury, lead, tin, germanium, silicon, gallium, bismuth, indium, manganese or copper, and X is one of chlorine, bromine and iodine;
the fluorescent perovskite nanocrystal is prepared by the following method:
(1) dispersing an MOF material in a solvent I to prepare a suspension with the concentration of 0.5-25 g/L; the MOF material is one of Zn-MOF, Hg-MOF, Pb-MOF, Sn-MOF, Ge-MOF, Si-MOF, Ga-MOF, In-MOF, Bi-MOF, Mn-MOF and Cu-MOF;
(2) dissolving cationic halide salt in a solvent II, and performing ultrasonic treatment to completely dissolve the cationic halide salt to obtain cationic halide salt solution with the concentration of 0.05-25 g/L;
(3) and (3) adding the cationic halide solution obtained in the step (2) into the suspension obtained in the step (1), continuously stirring for 5-300 seconds, and filtering or centrifuging and drying the obtained dispersion liquid to obtain the perovskite nano-crystalline powder embedded in the MOF.
2. A method of preparing a fluorescent perovskite nanocrystal as claimed in claim 1, comprising the steps of:
(1) dispersing an MOF material in a solvent I to prepare a suspension with the concentration of 0.5-25 g/L; the MOF material is one of Zn-MOF, Hg-MOF, Pb-MOF, Sn-MOF, Ge-MOF, Si-MOF, Ga-MOF, In-MOF, Bi-MOF, Mn-MOF and Cu-MOF;
(2) dissolving cationic halide salt in a solvent II, and performing ultrasonic treatment to completely dissolve the cationic halide salt to obtain cationic halide salt solution with the concentration of 0.05-25 g/L; the cation of the cationic halide salt is MA+、FA+、Cs+、Rb+One of (1);
(3) and (3) adding the cationic halide solution obtained in the step (2) into the suspension obtained in the step (1), continuously stirring for 5-300 seconds, and filtering or centrifuging and drying the obtained dispersion liquid to obtain the perovskite nano-crystalline powder embedded in the MOF.
3. The method for preparing fluorescent perovskite nanocrystals according to claim 2, wherein the MOF material of step (1) is synthesized by conventional room temperature stirring or solvothermal method, and the organic ligands in the MOF material are carboxylic acid ligands or imidazole ligands; the solvent I is selected from any one of toluene, chlorobenzene, chloroform, n-hexane, cyclohexane, ethyl acetate or diethyl ether.
4. The method for preparing fluorescent perovskite nanocrystal according to claim 2, wherein the cation of the cation halide salt in the step (2) is MA +, FA +, Cs+、Rb+One of (1); the halogen used by the cation halide salt is one of chlorine, bromine and iodine; the solvent II is selected from one of methanol, ethanol, isopropanol, butanol, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile or acetone.
5. The preparation method of fluorescent perovskite nanocrystal according to claim 2, characterized in that the perovskite nanocrystal powder embedded in the MOF prepared in step (3) is dispersed in a solvent iii, continuously stirred until the fluorescence of the perovskite nanocrystal disappears completely, and then the powder without fluorescence is filtered or centrifuged and dried, and the obtained powder without fluorescence can be directly reused in the process of converting and synthesizing the perovskite nanocrystal, thereby realizing repeated conversion for many times.
6. The method according to claim 5, wherein the solvent III is one of water, methanol, ethanol, acetone, DMF, and DMSO.
7. Use of a fluorescent perovskite nanocrystal as defined in claim 1, wherein the fluorescent perovskite nanocrystal is used in confidential information storage and protection.
8. The use of a fluorescent perovskite nanocrystal as claimed in claim 7, wherein the specific application method comprises the following steps:
(1) preparation of precursor solution: adding metal salt and organic ligand which form the MOF material into a solvent II, then continuously adding ethanol and glycol, and completely dissolving the mixture in an ultrasonic or stirring manner to obtain MOF precursor liquid;
(2) storage and encryption of confidential information: printing the precursor liquid on a matrix through a printing technology, drying, soaking and cleaning the matrix by using an alcohol solvent, and drying again to obtain a substrate with information recorded by MOF crystals, namely a process of storing confidential information;
(3) decryption of confidential information: treating the substrate recorded with the information with a cation halide salt to complete the conversion from the MOF to the perovskite nanocrystals, namely decrypting the information recorded by the MOF;
(4) repeated encryption and decryption processes of confidential information: and (3) processing the decrypted substrate by using a solvent III to completely quench the generated fluorescent signal, namely, carrying out a re-encryption process of confidential information.
9. Use of a fluorescent perovskite nanocrystal as claimed in claim 8, wherein the non-fluorescent substrate obtained in step (4) is subjected to steps (3) and (4) again, and fluorescence can be generated and quenched again, i.e. the process of multiple encryption and decryption of confidential information.
10. The use of a fluorescent perovskite nanocrystal as claimed in claim 8, wherein the printing technology in step (2) is a traditional plateless printing method including gravure, offset, screen or embossing; the cationic halide salt in the step (3) is treated by one of solution soaking, solution spraying or gas phase contact reaction.
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| CN112877059B (en) * | 2021-01-20 | 2023-08-22 | 深圳技术大学 | MAPbBr with long fluorescence lifetime 3 Preparation method of perovskite nanocrystalline and method for degrading organic pollutants by photocatalysis |
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| CN114958333B (en) * | 2021-02-20 | 2024-03-22 | 中国科学院化学研究所 | High-fluorescence-intensity hydrophobic perovskite nanocrystalline and preparation method and application thereof |
| CN113189162B (en) * | 2021-05-19 | 2024-02-09 | 南昌大学 | Electrochemical luminescence method based on perovskite@covalent organic framework composite material |
| CN113278327A (en) * | 2021-06-10 | 2021-08-20 | 华东理工大学 | Double-encryption anti-counterfeiting perovskite ink and preparation method thereof |
| CN113429581B (en) * | 2021-07-13 | 2022-03-25 | 中国科学技术大学 | Conductive MOF material and preparation method and application thereof |
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| CN115093442A (en) * | 2022-07-14 | 2022-09-23 | 陕西师范大学 | Perovskite nanocrystalline with high fluorescence quantum yield and preparation method thereof |
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