CN113861965A - Composite fluorescent material with multiple fluorescent characteristics and preparation method and application thereof - Google Patents
Composite fluorescent material with multiple fluorescent characteristics and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a micro flower-like rare earth metal framework structure organic composite fluorescent material loaded with perovskite nanocrystals or a composite material thereof. The rare earth metal skeleton structure organic particles with micron-sized dimensions have high fluorescence intensity due to excellent aggregation-induced emission effect. Meanwhile, the flower-shaped structure has the characteristics of large specific surface area and multiple active sites, which is beneficial to the adhesion and dispersion of the perovskite nanocrystalline or the composite material thereof, so that the fluorescence quenching phenomenon of the perovskite nanocrystalline or the composite material thereof can be reduced, and the fluorescence luminous intensity of the perovskite nanocrystalline or the composite material thereof can be improved. In addition, the perovskite-rare earth metal framework structure organic composite fluorescent material has multi-fluorescence characteristic and can be used for identifying various ions and small molecules.
Description
Technical Field
The invention belongs to the field of development and application of photoelectric materials, and particularly relates to a composite fluorescent material with multiple fluorescent characteristics, and a preparation method and application thereof.
Background
Due to the structural advantages of diversity of spatial structure, high regularity of structural height, high thermal stability, adjustable pore diameter, large specific surface area, high porosity and the like, the metal framework structure organic compound (MOF) shows good optical, magnetic, adsorption/separation and catalytic properties, so that the MOF has wide research and application in the fields of gas adsorption and separation, sensors, drug sustained release, catalytic reaction and the like. In recent years, organic compounds having a metal skeleton structure in which a rare earth element is a metal site also exhibit an excellent fluorescence emission effect. Among them, the rare earth metal skeleton structure organic compound with aggregation-induced emission characteristic is undoubtedly a fluorescent material with great potential, and is expected to play an important application value in the fields of biomedical detection, treatment, high-sensitivity detection and the like.
However, there are two significant problems with such materials that need to be solved: (1) the fluorescence intensity of the organic compound with the rare earth metal framework structure and the aggregation-induced emission characteristic is closely related to the particle size and the aggregation state of the organic compound. The smaller the particle size, the lower the fluorescence brightness. The more dispersed the particles, the lower the fluorescence intensity; how to enhance the fluorescence intensity is an important research direction and application requirement. (2) The increase in particle size can increase the luminous intensity, but the dissolution effect in the solvent is significantly reduced. How to improve the dispersibility of the material in the solvent has a significant influence on the processing complexity and the application feasibility of the material.
Therefore, the invention firstly prepares the rare earth metal framework organic particles with the micro-flower rice structure, and the micron-sized size of the rare earth metal framework organic particles obviously improves the fluorescence luminous intensity of the organic particles. Meanwhile, the flower-like structure of the organic framework structure particles enables the particles to have large specific surface area and multiple active site characteristics. On the basis, the perovskite nanocrystalline or the composite material thereof with dispersed high fluorescence luminous intensity is used as a gain material, so that the fluorescence luminous intensity is further improved. In addition, the perovskite-rare earth metal framework structure organic composite fluorescent material also has the characteristic of multiple fluorescence, and can be used for identifying various ions and small molecules.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention aims to provide a micrometer flower-shaped rare earth metal framework structure organic composite fluorescent material loaded with perovskite nanocrystals or a composite material thereof. The rare earth metal skeleton structure organic particles with micron-sized dimensions have high fluorescence intensity due to excellent aggregation-induced emission effect. Meanwhile, the flower-like structure of the organic framework structure particles enables the particles to have large specific surface area and multiple active site characteristics, so that the perovskite nanocrystals or the composite materials thereof are favorably attached and dispersed on the surfaces of the organic framework structure particles. The well dispersed perovskite nano-crystal or the composite material thereof can reduce the self fluorescence quenching phenomenon, thereby improving the fluorescence luminous intensity. In addition, the perovskite-rare earth metal framework structure organic composite fluorescent material has simple preparation process, has multiple fluorescent characteristics and can be used for Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-Plasma and identification of small molecules such as glucose and citric acid. The specific technical scheme is as follows:
the invention provides a composite fluorescent material with multiple fluorescent characteristics, and a preparation method of the composite fluorescent material comprises the following steps:
(1) adding rare earth metal salt, benzoic acid derivative and carboxyl phenyl boric acid derivative into N, N-dimethylformamide aqueous solution for ultrasonic dissolution to obtain rare earth metal precursor solution A, wherein the mass ratio of the rare earth metal salt to the benzoic acid derivative to the carboxyl phenyl boric acid derivative is 1: (0.1-0.5): (0.1-0.3), the volume fraction of the N, N-dimethylformamide aqueous solution is 50-90 vol.%, and the solid-to-liquid ratio of the rare earth metal salt to the N, N-dimethylformamide aqueous solution is 1: (0.03-0.3), the power of ultrasonic dispersion is 100-500W, the ultrasonic frequency is 50-150Hz, and the ultrasonic time is 1-3 h;
(2) reacting the rare earth metal precursor liquid A for 8-24h under the conditions of heating, pressurizing and magnetic stirring to obtain a rare earth metal framework structure organic fluorescent material mixed solution B, wherein the heating temperature is 150-; the synthesis of the organic fluorescent material with the micrometer flower-like structure rare earth metal framework structure can be induced by a magnetic stirring mode;
(3) centrifuging the rare earth metal framework structure organic fluorescent material mixed solution B, and then drying in vacuum to obtain micrometer flower-like structure rare earth metal framework structure organic fluorescent material powder C, wherein the centrifugal rotation speed is 8,000-10,000rpm, the centrifugal time is 30-60min, the vacuum drying temperature is 80-120 ℃, and the vacuum drying time is 12-18 h;
(4) dissolving the rare earth metal framework structure organic fluorescent material powder C in a mixed solvent D to obtain rare earth metal framework structure organic fluorescent material dispersion liquid E, and adding inorganic perovskite nano-crystals or composite materials thereof into the rare earth metal framework structure organic fluorescent material dispersion liquid E to obtain multi-fluorescence characteristic perovskite-organic metal framework structure composite fluorescent material solution F loaded with the inorganic perovskite nano-crystals or the composite materials thereof;
the mixed solvent D contains at least two of absolute ethyl alcohol, glycerol and n-hexanol;
(5) coating the perovskite-rare earth metal framework structure composite fluorescent material solution F on the surface of a transparent substrate, and then drying by using an infrared sintering mode to obtain the perovskite-organic metal framework structure composite fluorescent material G, wherein the infrared drying power is 100-500W, and the drying time is 30-60 min.
The rare earth metal salt comprises at least one of halide salt, nitrate, carbonate, phosphate and sulfate, and the rare earth is one of europium, gadolinium, terbium, dysprosium, samarium and thulium.
The benzoic acid derivative comprises one or more of benzoic acid, isophthalic acid, phthalic acid, terephthalic acid, trimesic acid, hemimellitic acid, phenylacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, p-phenylenediacetic acid, pyromellitic acid and hemimellitic acid.
The carboxyl phenyl boric acid derivative comprises one or more of 2-carboxyl phenyl boric acid, 4-carboxyl phenyl boric acid, 3- (carboxymethyl) phenyl boric acid, 2, 5-dicarboxyl phenyl boric acid and 3, 5-dicarboxyl phenyl boric acid.
The rare earth metal precursor liquid has the mass ratio of the benzoic acid derivative to the carboxyl phenyl boric acid derivative of (0.4-4): 1. the synthesis of the rare earth metal framework structure organic fluorescent material with a rod-shaped structure can be induced by regulating the proportion of the benzoic acid derivative and the carboxyphenylboronic acid derivative.
The rare earth metal framework structure organic fluorescent material powder C with the micrometer flower-shaped structure is a water-soluble material and an alcohol-soluble material.
The particle size of the organic fluorescent material powder C with the rare earth metal framework structure of the micrometer flower-like structure is 1-10 mu m, and the deposition specific surface area is 10-100m2·g-1. The rare earth metal framework structure organic fluorescent material with the micrometer flower-like structure has aggregation-induced emission characteristics, and the larger the particle size is, the higher the fluorescence emission intensity is. The micron-sized flower-like structure is beneficial to improving the luminous intensity of the organic fluorescent material with the rare earth metal framework structure, the formed flower-like structure gaps and the large specific surface area characteristic are beneficial to the dispersion and the attachment of the perovskite nano-crystal or the composite material thereof, and the reduction of the fluorescent intensity caused by the fluorescent quenching characteristic of the perovskite nano-crystal or the composite material thereof can be avoided. In addition, the rare earth metal skeleton structure organic particles with the micro-flower rice structure are composed of a large number of rod-shaped particles, and the dissolution effect of the rod-shaped particles in different dissolution is obviously better than that of large-size spherical particles.
The inorganic perovskite nano crystal with multiple fluorescence characteristics or the composite material thereof comprises ABX3(A is an alkali metal element; B isContains +2 valence state elements; x is halogen element) nanocrystal, ABX synthesized by exchanging halogen anions3-nX’nCore-shell structure nanocrystalline and nano two-dimensional material surface in-situ growth ABX3One or more of the nanocrystals.
The transparent substrate is one of glass, FTO, ITO, transparent PVC, transparent PET and transparent PI.
The composite fluorescent material with multiple fluorescent characteristics can be used for Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-Plasma and identification of small molecules such as glucose and citric acid.
The invention has the beneficial effects that: the rare earth metal skeleton structure organic particles with micron-sized dimensions have high fluorescence intensity due to excellent aggregation-induced emission effect. Meanwhile, the flower-like structure of the organic framework structure particles enables the particles to have large specific surface area and multiple active site characteristics, so that the perovskite nanocrystals or the composite materials thereof are favorably attached and dispersed on the surfaces of the organic framework structure particles. The well dispersed perovskite nano-crystal or the composite material thereof can reduce the self fluorescence quenching phenomenon, thereby improving the fluorescence luminous intensity. In addition, the composite fluorescent material has multiple fluorescence characteristics and can be used for identifying various ions and small molecules.
Drawings
Fig. 1 is an SEM image of a perovskite-rare earth metal skeleton structure organic composite fluorescent material in example 1 of the present invention;
FIG. 2 is a PL diagram of a perovskite-rare earth metal skeleton structure organic composite fluorescent material in example 1 of the present invention and a rare earth metal skeleton structure organic fluorescent material in a comparative example;
FIG. 3 is a PL diagram of the perovskite-rare earth metal skeleton structure organic composite fluorescent material with different ion additions in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following examples and drawings, and it should be understood that the described examples are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without any creative efforts shall fall within the protection scope of the present invention.
The organic fluorescent material with the rare earth metal framework structure in the prior art has the problems of low fluorescence luminous intensity, poor solubility in different solvents and the like. In order to solve the problems, the invention aims to design and prepare a micrometer flower-shaped rare earth metal framework structure organic composite fluorescent material loaded with perovskite nanocrystals or a composite material thereof. The rare earth metal skeleton structure organic particles with micron-sized dimensions have high fluorescence intensity due to excellent aggregation-induced emission effect. Meanwhile, the flower-like structure of the organic framework structure particles enables the particles to have large specific surface area and multiple active site characteristics, so that the perovskite nanocrystals or composite materials thereof can be favorably attached and dispersed on the surfaces of the organic framework structure particles. The well dispersed perovskite nano-crystal or the composite material thereof can reduce the self fluorescence quenching phenomenon, thereby improving the fluorescence luminous intensity. In addition, the organic preparation process of the perovskite-rare earth metal framework structure is simple, and the composite fluorescent material has the multi-fluorescence characteristic and can be used for Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-Plasma and identification of small molecules such as glucose and citric acid. The embodiment of the invention provides a preparation method and application of a composite fluorescent material with multiple fluorescent characteristics.
Example 1
A composite fluorescent material with multiple fluorescent characteristics is prepared by the following steps:
(1) europium nitrate, cerotriacetic acid and 2-carboxyphenylboronic acid are added into an N, N-dimethylformamide aqueous solution for ultrasonic dissolution, so as to obtain a rare earth metal europium precursor solution A, wherein the mass ratio of the europium nitrate to the cerotriacetic acid to the 2-carboxyphenylboronic acid is 1: 0.3: 0.2, the volume fraction of the aqueous solution of N, N-dimethylformamide is 70 vol.%, and the solid-to-liquid ratio of the aqueous solution of europium nitrate to the aqueous solution of N, N-dimethylformamide is 1: 0.16; in the rare earth metal europium precursor liquid, the mass ratio of the cerotriacetic acid to the 2-carboxyl phenyl boric acid is 2: 1. the power of ultrasonic dispersion is 500W, the ultrasonic frequency is 150Hz, and the ultrasonic time is 1 h.
(2) Reacting the rare earth metal europium precursor solution A for 16 hours under the conditions of heating, pressurizing and magnetic stirring to obtain a rare earth metal framework structure organic fluorescent material mixed solution B, wherein the heating temperature is 180 ℃, the pressure is 0.2MPa, and the magnetic stirring speed is 3,000 rpm;
(3) centrifuging the rare earth metal framework structure organic fluorescent material mixed solution B, and then drying in vacuum to obtain micrometer flower-like structure rare earth metal framework structure organic fluorescent material powder C, wherein the centrifugal speed is 8,000rpm, the centrifugal time is 45min, the vacuum drying temperature is 100 ℃, and the vacuum drying time is 18 h;
(4) dissolving the rare earth metal framework structure organic fluorescent material powder C in a mixed solvent D to obtain a rare earth metal framework structure organic fluorescent material dispersion liquid E, and dissolving the high-fluorescence-characteristic inorganic perovskite nanocrystalline CsPbBr3Adding the mixture into organic fluorescent material dispersion liquid E with a rare earth metal framework structure to obtain loaded inorganic perovskite nanocrystalline CsPbBr3The perovskite-organic metal framework structure composite fluorescent material solution F with multiple fluorescence characteristics;
the mixed solvent D is prepared from absolute ethyl alcohol and glycerol according to a mass ratio of 1: 1, mixing and preparing;
(5) coating the perovskite-rare earth metal framework structure composite fluorescent material solution F on the surface of transparent PET, and drying by using an infrared sintering mode to obtain a perovskite-organic metal framework structure composite fluorescent material G, wherein G is CsPbBr3Eu-MOF, infrared drying power is 300W, and drying time is 50 min.
The rare earth metal framework structure organic fluorescent material powder C with the micrometer flower-shaped structure is a water-soluble material and an alcohol-soluble material.
The particle size of the rare earth metal framework structure organic fluorescent material powder C with the micrometer flower-like structure is 8 mu m, and the deposition specific surface area is 35m2·g-1. FIG. 1 shows the perovskite-rare earth metal skeleton structure of organic composite fluorescent material CsPbBr in example 13SEM picture of/Eu-MOF. Perovskite-rare earth metal framework structure organic composite fluorescent material CsPbBr3The PL profile of the/Eu-MOF is shown in FIG. 2.
The solution containing different ions or small molecules is dripped on the perovskite-organic metal framework structure composite fluorescent material G, and the different ions or small molecules can generate different influences on the fluorescence luminous intensity of the composite fluorescent material G, so that the solution can be used for identifying the ions and the small molecules. FIG. 3 is a PL diagram of the perovskite-rare earth metal skeleton structure organic composite fluorescent material with different ion additions in example 1 of the present invention. As can be seen from FIG. 3, CsPbBr3The Eu-MOF can accurately identify Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-Ions, and small glucose and citric acid molecules.
Example 2
A composite fluorescent material with multiple fluorescent characteristics is prepared by the following steps:
(1) adding rare earth metal salt, benzoic acid derivative and carboxyl phenyl boric acid derivative into N, N-dimethylformamide aqueous solution for ultrasonic dissolution to obtain rare earth metal precursor solution A, wherein the mass ratio of the rare earth metal salt to the benzoic acid derivative to the carboxyl phenyl boric acid derivative is 1: 0.4: 0.1, the volume fraction of the aqueous solution of N, N-dimethylformamide is 90 vol.%, and the solid-to-liquid ratio of the rare earth metal salt to the aqueous solution of N, N-dimethylformamide is 1: 0.3; the power of ultrasonic dispersion is 100W, the ultrasonic frequency is 100Hz, and the ultrasonic time is 1 h.
The rare earth metal salt is prepared from europium chloride and gadolinium nitrate according to a molar mass ratio of 3: 1, the mixture of formulations.
The benzoic acid derivative is benzoic acid and m-phenylenediacetic acid according to the mass ratio of 1: 1, the mixture of formulations.
The carboxyl phenyl boric acid derivative is 4-carboxyl phenyl boric acid and 2, 5-dicarboxyl phenyl boric acid according to the mass ratio of 1: 5, and (3) preparing the mixture.
(2) Reacting the rare earth metal precursor liquid A for 8 hours under the conditions of heating, pressurizing and magnetic stirring to obtain a rare earth metal skeleton structure organic fluorescent material mixed solution B, wherein the heating temperature is 150 ℃, the pressure is 2MPa, and the magnetic stirring speed is 1,000 rpm;
(3) centrifuging the rare earth metal framework structure organic fluorescent material mixed solution B, and then drying in vacuum to obtain micrometer flower-like structure rare earth metal framework structure organic fluorescent material powder C, wherein the centrifugal speed is 10,000rpm, the centrifugal time is 60min, the vacuum drying temperature is 80 ℃, and the vacuum drying time is 15 h;
(4) dissolving the rare earth metal framework structure organic fluorescent material powder C in a mixed solvent D to obtain a rare earth metal framework structure organic fluorescent material dispersion liquid E, and dissolving the high-fluorescence-property inorganic perovskite nanocrystalline CsSnBr2I is added into organic fluorescent material dispersion liquid E with a rare earth metal framework structure to obtain loaded inorganic perovskite nanocrystalline CsSnBr2I, a multi-fluorescence perovskite-organic metal framework structure composite fluorescent material solution F;
the mixed solvent D is absolute ethyl alcohol, glycerol and n-hexanol according to a mass ratio of 1: 1: 1, preparing a mixture;
(5) coating the perovskite-rare earth metal framework structure composite fluorescent material solution F on the surface of transparent glass, and then drying by using an infrared sintering mode to obtain a perovskite-organic metal framework structure composite fluorescent material G, wherein G is CsSnBr2I/Eu0.75Gd0.25-MOF, infrared drying power 500W, drying time 30 min.
The rare earth metal framework structure organic fluorescent material powder C with the micrometer flower-shaped structure is a water-soluble material and an alcohol-soluble material.
The particle size of the rare earth metal framework structure organic fluorescent material powder C with the micrometer flower-like structure is 5 mu m, and the deposition specific surface area is 25m2·g-1。
Dripping solution containing different ions or small molecules onto the perovskite-organic metal framework structure composite fluorescent material G, wherein the different ions or small molecules can be compoundedThe fluorescent material G has different effects on the fluorescence intensity, and thus can be used for ion and small molecule recognition. CsSnBr2I/Eu0.75Gd0.25MOF can accurately identify Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-Ions, and small glucose and citric acid molecules.
Example 3
A composite fluorescent material with multiple fluorescent characteristics is prepared by the following steps:
(1) adding rare earth metal salt, benzoic acid derivative and carboxyl phenyl boric acid derivative into N, N-dimethylformamide aqueous solution for ultrasonic dissolution to obtain rare earth metal precursor solution A, wherein the mass ratio of the rare earth metal salt to the benzoic acid derivative to the carboxyl phenyl boric acid derivative is 1: 0.2: 0.3, the volume fraction of the aqueous solution of N, N-dimethylformamide is 50 vol.%, and the solid-to-liquid ratio of the rare earth metal salt to the aqueous solution of N, N-dimethylformamide is 1: 0.03; the power of ultrasonic dispersion is 300W, the ultrasonic frequency is 50Hz, and the ultrasonic time is 2 h.
The rare earth metal salt is prepared by mixing dysprosium carbonate and samarium sulfate according to a molar mass ratio of 1: 1, the mixture of formulations.
The benzene acid derivative is phthalic acid, p-phenylene diacetic acid and pyromellitic acid according to the mass ratio of 1: 1: 1, the mixture of formulations.
The carboxyl phenyl boric acid derivative is 3- (carboxymethyl) phenyl boric acid and 3, 5-dicarboxyphenyl boric acid according to the mass ratio of 2: 1, the mixture of formulations.
(2) Reacting the rare earth metal precursor liquid A for 24 hours under the conditions of heating, pressurizing and magnetic stirring to obtain a rare earth metal skeleton structure organic fluorescent material mixed solution B, wherein the heating temperature is 165 ℃, the pressure is 1.2MPa, and the magnetic stirring speed is 5,000 rpm;
(3) centrifuging the rare earth metal framework structure organic fluorescent material mixed solution B, and then drying in vacuum to obtain micrometer flower-like structure rare earth metal framework structure organic fluorescent material powder C, wherein the centrifugal speed is 9,000rpm, the centrifugal time is 30min, the vacuum drying temperature is 120 ℃, and the vacuum drying time is 12 h;
(4) dissolving the rare earth metal framework structure organic fluorescent material powder C in a mixed solvent D to obtain rare earth metal framework structure organic fluorescent material dispersion liquid E, and dissolving the high-fluorescence-characteristic inorganic perovskite nanocrystalline CsPbI3Adding rGO into the organic fluorescent material dispersion liquid E with the rare earth metal framework structure to obtain a multi-fluorescence characteristic perovskite-organic metal framework structure composite fluorescent material solution F loaded with inorganic perovskite nanocrystals;
the mixed solvent D is absolute ethyl alcohol and n-hexanol according to a mass ratio of 1: 1, mixing and preparing.
(5) Coating the perovskite-rare earth metal framework structure composite fluorescent material solution F on the surface of ITO, and then drying by using an infrared sintering mode to obtain a perovskite-organic metal framework structure composite fluorescent material G, wherein G is CsPbI3/rGO/Dy0.5Sm0.5-MOF, infrared drying power of 100W and drying time of 60 min.
The rare earth metal framework structure organic fluorescent material powder C with the micrometer flower-shaped structure is a water-soluble material and an alcohol-soluble material.
The particle size of the rare earth metal framework structure organic fluorescent material powder C with the micrometer flower-like structure is 2 mu m, and the deposition specific surface area is 10m2·g-1。
The solution containing different ions or small molecules is dripped on the perovskite-organic metal framework structure composite fluorescent material G, and the different ions or small molecules can generate different influences on the fluorescence luminous intensity of the composite fluorescent material G, so that the solution can be used for identifying the ions and the small molecules. CsPbI3/rGO/Dy0.5Sm0.5MOF can accurately identify Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-Ions, glucose small molecules, citric acid and other small molecules.
Comparative example
The technical proposal of the embodiment 1 is changedTo add no perovskite nanocrystalline CsPbBr3And obtaining the rare earth metal framework structure organic fluorescent material Eu-MOF, wherein the PL diagram of the rare earth metal framework structure organic fluorescent material Eu-MOF is shown in figure 2.
FIG. 2 shows perovskite-rare earth metal skeleton structure organic composite fluorescent material CsPbBr in example 1 of the present invention3PL diagram of/Eu-MOF and PL diagram of comparative example rare earth metal framework structure organic fluorescent material Eu-MOF. As can be seen from the comparison of FIG. 2, CsPbBr was not added3Eu-MOF ratio CsPbBr of3At least two of the Eu-MOF are CsPbBr in the range of 450-600nm3And Eu-MOF, and a characteristic emission peak.
From the above, the perovskite nanocrystalline or the composite material thereof loaded organic composite fluorescent material with the micrometer flower-like rare earth metal framework structure prepared by the embodiment of the invention is provided. The rare earth metal skeleton structure organic particles with micron-sized dimensions have high fluorescence intensity due to excellent aggregation-induced emission effect. Meanwhile, the flower-like structure of the organic framework structure particles enables the particles to have large specific surface area and multiple active site characteristics, so that the perovskite nanocrystals or the composite materials thereof are favorably attached and dispersed on the surfaces of the organic framework structure particles. The well dispersed perovskite nano-crystal or the composite material thereof can reduce the self fluorescence quenching phenomenon, thereby improving the fluorescence luminous intensity. In addition, the perovskite-rare earth metal framework structure organic composite fluorescent material has simple preparation process, has multiple fluorescent characteristics and can be used for Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-Plasma and identification of small molecules such as glucose and citric acid.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The composite fluorescent material with multiple fluorescent characteristics is characterized in that the preparation method of the composite fluorescent material comprises the following steps:
(1) adding rare earth metal salt, benzoic acid derivative and carboxyl phenyl boric acid derivative into N, N-dimethylformamide aqueous solution for ultrasonic dissolution to obtain rare earth metal precursor solution A, wherein the mass ratio of the rare earth metal salt to the benzoic acid derivative to the carboxyl phenyl boric acid derivative is 1: (0.1-0.5): (0.1-0.3), the volume fraction of the N, N-dimethylformamide aqueous solution is 50-90 vol.%, and the solid-to-liquid ratio of the rare earth metal salt to the N, N-dimethylformamide aqueous solution is 1: (0.03-0.3);
(2) reacting the rare earth metal precursor liquid A for 8-24h under the conditions of heating, pressurizing and magnetic stirring to obtain a rare earth metal framework structure organic fluorescent material mixed solution B, wherein the heating temperature is 150-;
(3) centrifuging the rare earth metal framework structure organic fluorescent material mixed solution B, and then drying in vacuum to obtain micrometer flower-like structure rare earth metal framework structure organic fluorescent material powder C, wherein the centrifugal rotation speed is 8,000-10,000rpm, the centrifugal time is 30-60min, the vacuum drying temperature is 80-120 ℃, and the vacuum drying time is 12-18 h;
(4) dissolving the rare earth metal framework structure organic fluorescent material powder C in a mixed solvent D to obtain rare earth metal framework structure organic fluorescent material dispersion liquid E, and adding inorganic perovskite nano-crystals or composite materials thereof into the rare earth metal framework structure organic fluorescent material dispersion liquid E to obtain multi-fluorescence characteristic perovskite-organic metal framework structure composite fluorescent material solution F loaded with the inorganic perovskite nano-crystals or the composite materials thereof;
the mixed solvent D contains at least two of absolute ethyl alcohol, glycerol and n-hexanol;
(5) coating the perovskite-rare earth metal framework structure composite fluorescent material solution F on the surface of a transparent substrate, and then drying by using an infrared sintering mode to obtain the perovskite-organic metal framework structure composite fluorescent material G, wherein the infrared drying power is 100-500W, and the drying time is 30-60 min.
2. The multiple fluorescent composite of claim 1, wherein the rare earth metal salt in step (1) comprises at least one of halide, nitrate, carbonate, phosphate and sulfate, and the rare earth is one of europium, gadolinium, terbium, dysprosium, samarium and thulium.
3. The multi-fluorescent composite phosphor according to claim 1, wherein the benzene acid derivative in step (1) comprises one or more of benzoic acid, isophthalic acid, phthalic acid, terephthalic acid, trimesic acid, hemimellitic acid, phenylacetic acid, isophthalic acid, orthophthalic acid, terephthallic acid, pyromellitic acid and hemimellitic acid.
4. The multiple fluorescent composite fluorescent material of claim 1, wherein the carboxyphenylboronic acid derivative in step (1) includes one or more of 2-carboxyphenylboronic acid, 4-carboxyphenylboronic acid, 3- (carboxymethyl) phenylboronic acid, 2, 5-dicarboxyphenylboronic acid, and 3, 5-dicarboxyphenylboronic acid.
5. The multiple fluorescence characteristic composite fluorescent material according to claim 1, wherein in the rare earth metal precursor liquid in the step (1), the mass ratio of the benzoic acid derivative to the carboxyphenylboronic acid derivative is (0.4-4): 1.
6. the composite fluorescent material with multiple fluorescent characteristics according to claim 1, wherein the organic fluorescent material powder C with a rare earth metal skeleton structure in a micro flower-like structure in the step (3) is a water-soluble material or an alcohol-soluble material.
7. The multiple fluorescent characteristics composite fluorescent material of claim 1, wherein the particle size of the organic fluorescent material powder C with a rare earth metal skeleton structure having a micro flower-like structure in step (3) is 1-10 μm, and the deposition specific surface area is 10-100m2·g-1。
8. The multiple fluorescent composite fluorescent material of claim 1, wherein the inorganic perovskite nanocrystals or the composite thereof in step (4) comprise ABX3Nanocrystalline, halogen anion exchange synthesized ABX3-nX’nCore-shell structure nanocrystalline and nano two-dimensional material surface in-situ growth ABX3One or more of nanocrystals; wherein A is an alkali metal element; b is an element containing a valence of + 2; x is a halogen element.
9. The multiple fluorescence characteristic composite fluorescent material of claim 1, wherein the transparent substrate in step (5) is one of glass, FTO, ITO, transparent PVC, transparent PET and transparent PI.
10. The multiple fluorescent composite phosphor of claim 1, wherein said multiple fluorescent composite phosphor is used for Ca2+、Ba2+、Fe3+、NH4 +、F-、I-、CO3 2-、SO4 2-And PO4 3-And (4) recognition of ions, glucose molecules and citric acid molecules.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409957A (en) * | 2022-01-24 | 2022-04-29 | 吉林大学 | Me-MOF @ activated carbon composite material, preparation method and application thereof in fluorescent recognition of Fe3+In (1) |
| CN115849436A (en) * | 2022-11-14 | 2023-03-28 | 北京科技大学 | graphene/Zr-BDC MOF/perovskite quantum dot high-thermal-conductivity composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410266A (en) * | 2018-03-09 | 2018-08-17 | 南开大学 | A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials |
| CN110950375A (en) * | 2019-12-02 | 2020-04-03 | 山东省分析测试中心 | CsPb2Br5Middle doped CsPbBr3Composite perovskite material and preparation method and application thereof |
| CN113134392A (en) * | 2021-04-26 | 2021-07-20 | 北京师范大学 | perovskite-MOFs composite photocatalyst and preparation method and application thereof |
-
2021
- 2021-11-09 CN CN202111319554.4A patent/CN113861965A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410266A (en) * | 2018-03-09 | 2018-08-17 | 南开大学 | A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials |
| CN110950375A (en) * | 2019-12-02 | 2020-04-03 | 山东省分析测试中心 | CsPb2Br5Middle doped CsPbBr3Composite perovskite material and preparation method and application thereof |
| CN113134392A (en) * | 2021-04-26 | 2021-07-20 | 北京师范大学 | perovskite-MOFs composite photocatalyst and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| MEI SHILIANG等: "Facile synthesis and optical properties of CsPbX3/ZIF-8 composites for wide-color-gamut display", 《NANOMATERIALS》 * |
| SHIPENG WAN等: "Perovskite-type CsPbBr3 quantum dots/UiO-66(NH2) nanojunction as efficient visible-light-driven photocatalyst for CO2 reduction", 《CHEMICAL ENGINEERING JOURNAL》 * |
| ZHANG DIWEI等: "Encapsulation of CH3NH3PbBr3 Perovskite Quantum Dots in MOF-5 Microcrystals as a Stable Platform for Temperature and Aqueous Heavy Metal Ion Detection", 《INORGANIC CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409957A (en) * | 2022-01-24 | 2022-04-29 | 吉林大学 | Me-MOF @ activated carbon composite material, preparation method and application thereof in fluorescent recognition of Fe3+In (1) |
| CN115849436A (en) * | 2022-11-14 | 2023-03-28 | 北京科技大学 | graphene/Zr-BDC MOF/perovskite quantum dot high-thermal-conductivity composite material and preparation method thereof |
| CN115849436B (en) * | 2022-11-14 | 2024-02-06 | 北京科技大学 | graphene/Zr-BDC MOF/perovskite quantum dot high-heat-conductivity composite material and preparation method thereof |
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